PROCESS FOR CONVERTING HEAVY HYDROCARBON LOADS WITH RECYCLED OF DESASPHALTEE OIL

专利摘要:
The invention relates to a process for converting a heavy hydrocarbon feedstock containing a fraction of at least 50% having a boiling point of at least 300 ° C and containing sulfur, Conradson carbon, metals or , and nitrogen, comprising at least two successive hydroconversion stages, which can be separated by an intermediate separation step, and at least one step of deasphalting a heavy fraction of the effluent resulting from hydroconversion, with recycling at least a portion of the deasphalted oil (DAO) during hydroconversion, downstream of the first hydroconversion stage. DAO is either recycled at the end of the deasphalter or after having undergone a fractionation step producing a heavy fraction of the DAO which then constitutes the part of the recycled DAO. This process makes it possible to simultaneously improve the level of conversion and the stability of the liquid effluents.
公开号:FR3075809A1
申请号:FR1762868
申请日:2017-12-21
公开日:2019-06-28
发明作者:Joao Marques；Jan Verstraete
申请人:IFP Energies Nouvelles IFPEN；
IPC主号:

专利说明:

Field of the invention
The present invention relates to the refining and conversion of heavy hydrocarbon feedstocks originating either from crude oil or from the distillation of crude oil, said feeds comprising a fraction of at least 50% having a boiling temperature at least 300 ° C, and containing among others asphalt, sulfur, nitrogen impurities and metals. It is sought to convert these charges into lighter products, which can be used as fuel, for example to produce gasoline or diesel, or raw materials for petrochemicals.
In particular, the invention relates to a process for converting such a heavy load comprising hydroconversion stages in a three-phase reactor operating in a bubbling bed and deasphalting of a fraction of the product resulting from hydroconversion, in which the oil deasphalted, called DAO for DeAsphalted Oil in English, resulting from deasphalting is recycled during hydroconversion.
General context
The feedstocks which it is desired to treat in the context of the present invention are either crude oils or heavy fractions of hydrocarbons resulting from the distillation of crude oil, also called petroleum residues, and contain a fraction of at least at least 50% having a boiling point of at least 300 ° Q, preferably at least 350 ° C and preferably at least 375 ° C. These are preferably vacuum residues containing a fraction of at least 50% and have a boiling point of at least 450 ° C, and preferably at least 500 ° C.
These fillers generally have a sulfur content of at least 0.1%, sometimes at least 1% and even at least 2% by weight, a Conradson carbon content of at least 0.5% by weight and preferably at least 5% by weight, a content of C7 asphaltenes at least 1% by weight and preferably at least 3% by weight and a metal content of at least 20 ppm by weight and preferably at least minus 100 ppm weight.
The valuation of these heavy loads is relatively difficult, both from the technical point of view and from the economic point of view.
Indeed, the market is mainly demanding of fuels which can be distilled at atmospheric pressure at a temperature below 380 ° C, even at 320 ° C. As regards crude oils, their atmospheric distillation leads to variable atmospheric residue contents which depend on the origin of the crude oils treated. This content generally varies between 20% and 50% for conventional crude oils, but can reach 50% to 80% for heavy and extra-heavy crude oils such as those produced in Venezuela or in the Athabasca region in the northern Canada. It is therefore necessary to convert these residues, by transforming the heavy molecules from residues to produce refined products made up of lighter molecules. These refined products generally have a much higher hydrogen to carbon ratio than the heavy cuts of departure. A series of processes used to produce refined light cuts, such as hydrocracking, hydrotreatment and hydroconversion processes, is therefore based on the addition of hydrogen to the molecules, preferably at the same time as the cracking of these heavy molecules.
The conversion of heavy loads depends on a large number of parameters such as the composition of the load, the technology of the reactor used, the severity of the operating conditions (temperature, pressure, partial hydrogen pressure, residence time, etc.) , the type of catalyst used and its activity. By increasing the severity of the operation, the conversion of heavy loads into light products is increased, but by-products, such as coke precursors and sediments, begin to be formed significantly via side reactions. The heavy conversion of heavy loads therefore very often results in the formation of solid, very viscous and / or sticky particles composed of asphaltenes, coke and / or fine particles of catalyst. The excessive presence of these products leads to coking and deactivation of the catalyst, to fouling of the process equipment, and in particular of the separation and distillation equipment. As a result, the refiner is forced to reduce the conversion of heavy loads in order to avoid stopping the hydroconversion unit.
The formation of these sediments in hydrotreatment and hydroconversion processes therefore very strongly depends on the quality of the charge and the severity of the operation. More specifically, the asphaltenes present in the feed are mainly converted by dealkylation under severe hydroconversion conditions and thereby form molecules comprising highly condensed aromatic nuclei which precipitate in the form of sediments.
Hydroconversion processes for heavy hydrocarbon charges are well known to those skilled in the art. In particular, the conventional heavy load conversion schemes include a solvent deasphalting step (SDA for Solvent DeAsphalting in English) and a hydroconversion step carried out in a fixed bed, in a moving bed, in a bubbling bed and / or in a hybrid bed. . The hydroconversion steps being carried out in a fixed bed, in a mobile bed, in a bubbling bed and / or in a hybrid bed depending on the charge to be treated, these steps therefore always contain at least one catalyst which is maintained in the reactor during the surgery. In the present application, the term hybrid bed refers to a mixed bed of catalysts of very different particle size, simultaneously comprising at least one catalyst which is maintained in the reactor and at least one entrained catalyst (known as "slurry" according to English terminology). Saxon) which enters the reactor with the feed and which is entrained outside the reactor with the effluents. Deasphalting and hydroconversion are conventionally carried out successively. A distinction is made in particular between two types of heavy load conversion processes combining deasphalting and hydroconversion: - a first type of process, known as the "indirect route", implements the deasphalting unit placed upstream of the unit hydroconversion. According to this route, the feedstock is treated at least in part in a deasphalting unit before being sent at least in part to a hydroconversion unit comprising one or more hydroconversion reactors in the presence of hydrogen. US Patent 7,214,308 thus describes a process for converting atmospheric or vacuum residue from the distillation of heavy crude oils, in which the residue is first sent to a solvent deasphalting unit producing a flow of DAO and a asphalt stream, the two streams are then treated separately in reactors operating in a bubbling bed. The process then allows a higher level of conversion of the residue because the separate hydroconversion of the DAO flow uses a catalyst specific to the treatment of DAO and can be operated so as to achieve a more advanced conversion. A main drawback of the indirect route lies in the large size required for the deasphalt paver, leading to significant investment and operating costs. - a second type of process, known as the "direct route", implements a deasphalting unit placed downstream of the hydroconversion unit. In general, in this type of process, an atmospheric distillation step, and optionally a vacuum distillation step successive to the atmospheric distillation step, is carried out between the two unit steps constituted by hydroconversion and deasphalting. This is the case, for example, of the process described in patent FR 2 753 984, in which a heavy charge is first sent to a hydroconversion section comprising at least one three-phase reactor containing a hydroconversion catalyst in a bubbling bed and of hydrogen and operating in an updraft of liquid and gas. The conditions applied in the hydroconversion reaction section make it possible to obtain a liquid effluent with a reduced content of Conradson carbon, of metals, of nitrogen and of sulfur. This effluent is then separated into several fractions, including one or more residual fractions: the hydroconverted liquid effluent is sent to an atmospheric distillation zone producing a distillate and an atmospheric residue, and at least part of the atmospheric residue is sent to a zone vacuum distillation after which a vacuum distillate and a vacuum residue are recovered The vacuum residue is then sent at least in part to a deasphalting section in which a liquid-liquid extractor is used. using a solvent under deasphalting conditions known to a person skilled in the art, making it possible to obtain a DAO and a residual asphalt. The DAO thus obtained is then hydrotreated, either in a fixed bed, in a mobile bed, in a bubbling bed and / or in a hybrid bed, under conditions which make it possible in particular to reduce its content of metals, sulfur, nitrogen and Conradson carbon and to obtain, after further separation by distillation, a gaseous fraction, an atmospheric distillate which can be split into a petrol and diesel fraction then sent to the fuel pool and a heavier hydrotreated fraction. This heavier fraction can then be sent to a catalytic cracking or catalytic hydrocracking section for example.
The documents US 2010 / 320122A, US 6,017,441, US 3,905,892, US 4,176,048, US 2012 / 061293A and US 8,287,720 describe different possible configurations for the direct route, in which a first hydroconversion step is carried out followed by the deasphalting step. the heavy cut resulting from an intermediate separation of the hydroconverted effluent, then a second stage of hydroconversion, hydrotreatment or hydrocracking of the DAO is carried out. In these configurations, the formation of coke and sediments can always occur during the second hydroconversion stage in the case where the DAO is co-treated with a feed containing asphaltenes. In addition, a large amount of asphalt is produced during the deasphalting stage after the first hydroconversion stage with low asphaltene conversion, as in the case of the scheme proposed in US Pat. No. 4,176,048. This asphalt is a low value product which is more difficult to convert into fuels.
Another configuration according to the direct route consists in carrying out the step of deasphalting heavy cuts after a hydroconversion step thus making it possible to minimize the amount of asphalt produced, then to recycle the DAO at the entrance to the first zone of hydroconversion or in fractionation zones upstream of the first hydroconversion zone, as described in patent applications FR 2 964 388 and FR 2 999 599. This configuration requires a significant increase in the volume of the reaction zones as well as of the zones of separation increasing the investment required and the operating cost compared to a conversion process without recycling of CAD. In addition, in this configuration, coke and sediment formation problems can always be encountered during the hydroconversion stage where the DAO is recycled and co-treated with the heavy load containing asphaltenes.
Objectives and summary of the invention
The present invention aims to solve, at least partially, the problems mentioned above in relation to the heavy load conversion methods of the prior art incorporating hydroconversion and deasphalting steps.
In particular, one of the objectives of the invention is to provide a process for converting heavy loads of hydrocarbons integrating hydroconversion and deasphalting steps in which the stability of the effluents is improved for a given level of conversion of heavy loads, thus allowing to further push the conversion in the process, that is to say to operate the hydroconversion so as to obtain a higher conversion rate.
Another object of the invention is to provide such a process in which the formation of coke and sediments is limited during hydroconversion, thus reducing the problems of deactivation of the catalysts used in the reaction zones and of fouling of the equipment put implemented in the process.
Another objective of the invention is also to provide a good quality DAO, that is to say having a reduced content of nitrogen, sulfur, metals and Conradson carbon.
Thus, to achieve at least one of the abovementioned objectives, among others, the present invention provides a process for converting a heavy load of hydrocarbons containing a fraction of at least 50% having a boiling temperature at least 300 ° C, and containing sulfur, Conradson carbon, metals, and nitrogen, comprising the following successive stages: - an initial hydroconversion stage (ai) of at least part of said heavy load of hydrocarbons in the presence of hydrogen in an initial hydroconversion section, carried out under conditions making it possible to obtain a liquid effluent with reduced sulfur, Conradson carbon, metal and nitrogen content; - (n-1) additional hydroconversion stage (s) (a, ·) in (n-1) additional hydroconversion section (s), in the presence of hydrogen, of at least part or all of the liquid effluent from the previous hydroconversion step (aM) or optionally from a heavy fraction from an optional intermediate separation step (by) in an intermediate separation section between two steps of consecutive hydroconversion separating part or all of the liquid effluent from the previous hydroconversion step (a ^) to produce at least one heavy fraction boiling mainly at a temperature greater than or equal to 350 ° C, the ( n-1) additional hydroconversion stage (s) (al) being carried out so as to obtain a hydroconverted liquid effluent with reduced sulfur, Conradson carbon, metals, and nitrogen content, n being the total number hydroconversion stages, with n greater than or equal to 2, / 'being an integer ranging from 2 to n and y being an integer ranging from 1 to (n-1), and the initial and additional hydroconversion sections each comprising at least one three-phase reactor containing at least one hydroconversion catalyst; a first fractionation stage (c) in a first fractionation section of part or all of the hydroconverted liquid effluent from the last additional hydroconversion stage (an) producing at least one heavy fraction boiling mainly at a temperature greater than or equal to 350 ° C, said heavy cut containing a residual fraction boiling at a temperature greater than or equal to 540 ° C; - a deasphalting step (d) in a deasphalting machine of part or all of said heavy cut resulting from the fractionation step (c), with at least one hydrocarbon solvent, to obtain a DAO deasphalted oil and an asphalt residual; - optionally a second fractionation step (e) in a second fractionation section of part or all of the DAO resulting from the deasphalting step (d) into at least one heavy fraction of DAO and a light fraction of CAD; a recycling step (f) of at least part of the DAO from step (d) and / or at least part of the heavy fraction of the DAO from step (e) to an additional hydroconversion step (a1) and / or an intermediate separation step (by).
The heavy hydrocarbon feedstock preferably has a sulfur content of at least 0.1% by weight, a Conradson carbon content of at least 0.5% by weight, a C7 asphaltenes content of at least 1% by weight , and a metal content of at least 20 ppm by weight.
The heavy hydrocarbon feedstock can be crude oil or consist of atmospheric residues and / or vacuum residues from atmospheric distillation and / or vacuum of crude oil, and preferably consists of vacuum residues from vacuum distillation of crude oil.
According to an implementation of the invention, said three-phase reactor containing at least one hydroconversion catalyst is a three-phase reactor operating in a bubbling bed, with an updraft of liquid and gas.
According to an implementation of the invention, the three-phase reactor containing at least one hydroconversion catalyst is a three-phase reactor operating in a hybrid bed, said hybrid bed comprising at least one catalyst kept in said three-phase reactor and at least one catalyst driven out of said three-phase reactor.
According to an implementation of the invention, the initial hydroconversion step (ai) is carried out under an absolute pressure of between 2 and 38 MPa, at a temperature between 300 ° C and 550 ° C, at a space speed WH time in relation to the volume of each three-phase reactor between 0.05 h "1 and 10 h" 1 and under a quantity of hydrogen mixed with the heavy hydrocarbon charge between 50 and 5000 normal cubic meters (Nm3) per cubic meter (m3) heavy load of hydrocarbons.
According to an implementation of the invention, the additional hydroconversion step or steps (an) are carried out at a temperature between 300 ° C and 550 ° C, and higher than the temperature operated in the initial hydroconversion step (a ^, under an amount of hydrogen mixed with the heavy hydrocarbon charge between 50 and 5000 normal cubic meters (Nm3) per cubic meter (m3) of heavy hydrocarbon charge and less than the amount of hydrogen operated at l 'initial hydroconversion stage (a ^, at an absolute pressure between 2 and 38 MPa, and at an hourly space velocity WH relative to the volume of each three-phase reactor between 0.05 h'1 and 10 h'1.
According to an implementation of the invention, the intermediate separation section comprises one or more flash balloons arranged in series, and / or one or more stripping columns with steam and / or hydrogen, and / or a atmospheric distillation column, and / or a vacuum distillation column, and is preferably constituted by a single flash balloon.
According to an implementation of the invention, the first fractionation section comprises one or more flash balloons arranged in series, and / or one or more stripping columns with steam and / or hydrogen, and / or a atmospheric distillation column, and / or a vacuum distillation column, and is preferably constituted by a set of several flash flasks in series and atmospheric and vacuum distillation columns.
According to an implementation of the invention, the deasphalting step (d) is carried out in an extraction column at a temperature between 60 ° C and 250 ° C with at least one hydrocarbon solvent having from 3 to 7 atoms carbon, and a solvent / charge ratio (volume / volume) of between 3/1 and 16/1, and preferably between 4/1 and 8/1.
According to an implementation of the invention, part of the heavy hydrocarbon charge is sent to at least one additional hydroconversion section and / or to at least one intermediate separation section and / or to the first fractionation section. and / or in the deasphalt.
According to an implementation of the invention, an external hydrocarbon feedstock is sent to the process in the initial hydroconversion section and / or in at least one additional hydroconversion section and / or in at least one intermediate separation section and / or in the first fractionation section and / or in the deasphalt.
According to an implementation of the invention, the method further comprises at least one following recycling step: - recycling (n) part or all of the light fraction of the DAO resulting from step ( e) in the initial hydroconversion section and / or in at least one additional hydroconversion section and / or in at least one intermediate separation section and / or in the first fractionation section; - recycling (r2) of part of the heavy fraction of the DAO from step (f) in the first fractionation section; - recycling (r3) of part of the CAD from step (d) in the first fractionation section; - recycling (r4) of part or all of the residual asphalt from step (d) in the initial hydroconversion section and / or in at least one additional hydroconversion section; - recycling (r5) of part of the hydroconverted liquid effluent from a given additional hydroconversion section: - in the initial hydroconversion section, and / or - in another additional hydroconversion section positioned upstream of said given section, and / or - in an intermediate separation section positioned upstream of said given section; - recycling (r6) of part of the heavy fraction and / or part or all of one or more intermediate fractions from a given intermediate section: - in the initial hydroconversion section, and / or - in an additional hydroconversion section positioned upstream from said given intermediate section, and / or - in another intermediate separation section positioned upstream from said given section; - recycling (r7) of part of the heavy fraction and / or part or all of one or more intermediate fractions from the first fractionation section: - in the initial hydroconversion section, and / or - in an additional hydroconversion section, and / or - in an intermediate separation section.
According to an implementation of the invention, n is equal to 2.
According to an implementation of the invention, the method comprises the recycling (f) of all of the DAO from step (d) or of all of the heavy fraction from the second fractionation step (e) in the last additional hydroconversion step (a, ·), and preferably in the additional hydroconversion step (a2) when n is equal to 2 and that in addition all of the liquid effluent from the step (at) is sent to step (b ^, all of the heavy fraction from step (b ^ is sent to step (a2), all of the hydroconverted liquid effluent from step (a2) is sent in step (c), and the entire heavy cut from step (c) is sent to step (d).
According to an implementation of the invention, the method comprises the recycling (f) of all of the DAO from step (d) or of all of the heavy fraction from the second fractionation step (e) at an intermediate separation step (by), and preferably at the intermediate separation step (bi) between the initial hydroconversion step (a ^ and the additional hydroconversion step (a2) when n is equal to 2 and that in addition all of the liquid effluent from step (ai) is sent to step (bi), all of the heavy fraction from step (bi) is sent to the step (a2), all of the hydroconverted liquid effluent from step (a2) is sent to step (c), and all of the heavy cut from step (c) is sent to the 'step (d).
According to an implementation of the invention, the method does not include an intermediate separation step (b,) and includes the recycling (f) of all of the DAO from step (d) to the last step. additional hydroconversion (a, ·), and preferably in the additional hydroconversion step (a2) when n is equal to 2 and that in addition all of the liquid effluent from step (a ^ is sent to step (a2), all of the hydroconverted liquid effluent from step (a2) is sent to step (c), and all of the heavy cut from step (c ) is sent to step (d).
According to an implementation of the invention, the hydroconversion catalyst of said at least one three-phase reactor of the initial hydroconversion section and of the additional hydroconversion section (s) contains at least one non-group VIII metal -noble chosen from nickel and cobalt and at least one metal from group VIB chosen from molybdenum and tungsten, and preferably comprising an amorphous support. Other objects and advantages of the invention will appear on reading the detailed description which follows of the process, as well as examples of particular implementation of the invention, given by way of nonlimiting examples, the description being partly made with reference to the appended figures described below.
Brief description of the figures
Figure 1 is a block diagram of the implementation of the conversion method according to the invention.
FIG. 2 is a diagram of the method according to a first embodiment in which at least part of a heavy fraction of the DAO is recycled in a second hydroconversion section.
FIG. 3 is a diagram of the method according to a third embodiment in which at least part of the CAD is recycled in the separation section intermediate to the two hydroconversion sections.
FIG. 4 is a diagram of the method according to a second embodiment in which at least part of the CAD is recycled in a second hydroconversion section.
FIG. 5 is a diagram of the method according to a fourth embodiment in which at least part of the CAD is recycled in a second hydroconversion section succeeding a first hydroconversion section without intermediate separation.
In the figures, the same references designate identical or analogous elements.
Description of the invention
The process for converting heavy hydrocarbon feedstocks according to the invention incorporates hydroconversion of said feedstocks and deasphalting of at least part of the hydroconverted effluent in the form of a succession of specific steps.
In the following description, reference is made to FIG. 1 which illustrates the general implementation of the conversion method according to the invention.
In the present invention, it is proposed to simultaneously improve the conversion level and the stability of the liquid effluents by a sequence comprising at least two successive hydroconversion stages, which can be separated by an intermediate separation stage, and at least one stage. deasphalting of a heavy fraction of the effluent from the hydroconversion, with recycling of at least part of the DAO downstream of the first hydroconversion step. The CAD is either recycled at the outlet of the deasphalt paver, or after having undergone a fractionation stage producing a heavy fraction of the CAD which then constitutes the part of the recycled CAD. This configuration makes it possible to achieve a conversion of the heavy hydrocarbon charge greater than 70%, and preferably greater than 80%, this level of conversion not always being able to be achieved using the conventional methods which are limited by the stability of the liquid effluents.
The net conversion is defined as being the ratio of (residue flow rate in the feed - the flow rate of the residue in the product) / (residue flow rate in the feed), for the same load-product cut point; typically this cutting point is between 450 ° C and 550 ° C, and often around 540 ° C; in this definition, the residue being the fraction boiling from this cutting point, for example, the fraction 540 ° C +.
Thus, a process is proposed for converting a heavy load of hydrocarbons, for example a crude oil or the heavy fraction of hydrocarbons resulting from the atmospheric or vacuum distillation of a crude oil, said load containing a fraction of '' at least 50% having a boiling point of at least 300 ° C, comprising the following successive stages: - an initial hydroconversion stage (a ^ of at least part of said heavy hydrocarbon charge in the presence of hydrogen in an initial hydroconversion section A !, carried out under conditions making it possible to obtain a liquid effluent with reduced sulfur, Conradson carbon, metals, and nitrogen content; - (n-1) step (s ) additional hydroconversion (s) (a, ·) in (n-1) additional hydroconversion section (s) A ,, in the presence of hydrogen, at least part or all of l liquid effluent from the previous hydroconversion stage (aM) o u optionally a heavy fraction resulting from an optional intermediate separation step (by) between two consecutive hydroconversion steps separating part or all of the liquid effluent resulting from the previous hydroconversion step (aM) for produce at least one heavy fraction boiling mainly at a temperature greater than or equal to 350 ° C., the (n-1) additional hydroconverson step (s) (a, ·) being carried out so as to obtain a liquid effluent hydroconverted with reduced sulfur, Conradson carbon, metals, and nitrogen content; n being the total number of hydroconversion steps, with n greater than or equal to 2, / 'being an integer ranging from 2 to n and y being an integer ranging from 1 to (n-1), and the sections of initial hydroconversion At and additional A, each comprising at least one three-phase reactor containing at least one hydroconversion catalyst; - a first fractionation step (c) in a first fractionation section C of part or all of the hydroconverted liquid effluent from the last additional hydroconversion step (an) to produce at least one cut heavy, mainly boiling at a temperature greater than or equal to 350 ° C, said heavy cut containing a residual fraction boiling at a temperature greater than or equal to 540 ° C; - a deasphalting step (d) in a deasphalting machine D of part or all of said heavy cut resulting from the fractionation step (c), with at least one hydrocarbon solvent, to obtain a deasphalted DAO oil and a residual asphalt; - optionally a second fractionation step (e) in a second fractionation section E of part or all of the DAO resulting from the deasphalting step (d) into at least one heavy fraction of DAO and a light fraction DAO; a recycling step (f) of at least part of the DAO from step (d) and / or at least part of the heavy fraction of the DAO from step (e) to an additional hydroconversion step (a, ·) and / or an intermediate separation step (by).
According to a preferred implementation, the method according to the invention contains two hydroconversion steps, and an optional step of intermediate separation between these two hydroconversion steps. According to this implementation, n is equal to 2, and the method then comprises: - an initial hydroconversion step (ai) of at least part of said heavy hydrocarbon charge in the presence of hydrogen in a section d 'initial hydroconversion A1; carried out under conditions which make it possible to obtain a liquid effluent with a reduced sulfur, Conradson carbon, metal and nitrogen content; - an additional hydroconversion step (a2) in an additional hydroconversion section A2, in the presence of hydrogen, of at least some or all of the liquid effluent from the initial hydroconversion step (a ,) or optionally a heavy fraction from an optional intermediate separation step (bi) between the initial hydroconversion (aj) and additional (a2) steps separating part or all of the liquid effluent from l 'initial hydroconversion step (aj) to produce at least one heavy fraction boiling mainly at a temperature greater than or equal to 350 ° C, the additional hydroconversion step (a2) being carried out so as to obtain a hydroconverted liquid effluent with reduced sulfur, Conradson carbon, metal, and nitrogen content, the initial hydroconversion sections A, and additional A2, each comprising at least one three-phase reactor eu containing at least one hydroconversion catalyst; - a first fractionation step (c) in a first fractionation section C of part or all of the hydroconverted liquid effluent from the additional hydroconversion step (a2) to produce at least one heavy boiling cut mainly at a temperature greater than or equal to 350 ° C, said heavy cut containing a residual fraction boiling at one at a temperature greater than or equal to 540 ° C; - a deasphalting step (d) in a deasphalting machine D of part or all of said heavy cut resulting from the fractionation step (c), with at least one hydrocarbon solvent, to obtain a deasphalted DAO oil and a residual asphalt; - optionally a second fractionation step (e) in a second fractionation section E of part or all of the DAO resulting from the deasphalting step (d) into at least one heavy fraction of DAO and a light fraction DAO; a recycling step (f) of at least part of the DAO from step (d) and / or at least part of the heavy fraction of the DAO from step (e) to an additional hydroconversion step (a2) and / or an intermediate separation step (by).
The DAO obtained by the process according to the invention contains little or no C7 asphaltenes, compounds known to inhibit the conversion of residual cuts, both by their ability to form heavy hydrocarbon residues, commonly called coke, and by their tendency to produce sediments which strongly limit the operability of the hydrotreatment and hydroconversion units. The DAO obtained by the process according to the invention is also more aromatic than a DAO produced from a heavy petroleum charge resulting from the primary fractionation of crude oil (called "straight run" according to English terminology) because it is derived an effluent that has previously undergone a high level of hydroconversion.
The mixture of at least part of the DAO and of the effluent from the first hydroconversion section (s) in the process according to the invention makes it possible to supply the posterior hydroconversion step (s) with a charge having a reduced C7 asphaltene content and a higher content of aromatic compounds both compared to a process comprising a hydroconversion unit without recycling of the DAO, and compared to a process comprising a hydroconversion unit with recycling of the DAO upstream of a first hydroconversion or hydrotreatment step. Therefore, it is possible to impose more severe operating conditions in the process according to the invention, in particular in the additional hydroconversion stages, and thus to reach higher levels in terms of conversion of the feedstock, all by limiting the production of sediments. The effluent from the last additional hydroconversion stage is separated into several sections. The deasphalting is then carried out on the heavy cut or cuts produced in this separation step. The use of these cuts obtained at the highest level of conversion thus makes it possible to minimize the size required for the deasphalt paver and to minimize the amount of asphalt produced. According to the invention, the DAO extracted by deasphalting is always recycled after the initial hydroconversion stage, either at the entry of one of the intermediate separation sections, or at the entry of one of the additional hydroconversion sections , preferably at the entrance to the section of the last additional hydroconversion step. According to these two implementations, the size of the reactors of the first hydroconversion sections is not impacted, and according to the second implementation, neither the size of the intermediate separation equipment nor the size of the reactors of the preliminary hydroconversion stages are not impacted. Injecting the DAO downstream of the initial hydroconversion section avoids the prior hydrogenation of the DAO, thus preserving its aromatic character (characterized by the aromatic carbon content measured by the ASTM D 5292 method) which provides a gain on the stability of liquid effluents from areas where the highest conversion levels are reached. An operation to achieve higher conversion rates can therefore be envisaged in the method according to the invention.
Charge
The feedstock treated in the process according to the invention is a heavy feedstock of hydrocarbons containing a fraction of at least 50% having a boiling point of at least 300 ° C, preferably at least 350 ° C, even more preferably at least 375 ° C.
This heavy hydrocarbon feedstock may be crude oil, or it may come from the refining of crude oil or from the processing of another hydrocarbon source in a refinery.
Preferably, the feedstock is crude oil or consists of atmospheric residues and / or vacuum residues from atmospheric distillation and / or vacuum of crude oil.
The heavy hydrocarbon feedstock can also consist of atmospheric and / or vacuum residues from atmospheric distillation and / or vacuum of effluents from thermal conversion, hydrotreatment, hydrocracking and / or d hydroconversion.
Preferably, the charge consists of residues under vacuum. These vacuum residues generally contain a fraction of at least 50% having a boiling temperature of at least at least 450 ° C, and the folds often at least 500 ° C, or even at least 540 ° C. Vacuum tailings can come directly from crude oil, or other refining units, such as, among other things, hydrotreating of tailings, hydrocracking of tailings, and visbreaking of tailings. Preferably, the vacuum residues are vacuum residues from the vacuum distillation column of the primary crude fractionation (known as "straight run" according to English terminology).
The feed can also consist of vacuum distillates, either coming directly from crude oil, or from cuts from other refining units, such as, inter alia, cracking units, such as catalytic cracking in a FCC fluid bed (for "Fluid Catalytic Cracking" and hydrocracking, and thermal conversion units, such as coking units or visbreaking units.
It can also consist of aromatic cuts extracted from a lubricant production unit, deasphalted oils from a deasphalting unit (raffinates from the deasphalting unit), asphalts from a deasphalting unit ( residues from the deasphalting unit).
The heavy hydrocarbon feed can also be a residual fraction resulting from the direct liquefaction of coal (an atmospheric residue and / or a vacuum residue resulting for example from the H-Coal ™ process), a vacuum distillate resulting from direct liquefaction of coal, such as for example the H-Coal ™ process, or else a residual fraction resulting from the direct liquefaction of lignocellulosic biomass alone or in mixture with coal and / or an oil fraction.
All these charges can be used to constitute the heavy charge of hydrocarbons treated according to the invention, alone or as a mixture.
The heavy charge of hydrocarbons treated according to the invention contains impurities, such as metals, sulfur, nitrogen, Conradson carbon. It may also contain heptane insolubles, also called C7 asphaltenes. The metal contents can be greater than or equal to 20 ppm by weight, preferably greater than or equal to 100 ppm by weight. The sulfur content may be greater than or equal to 0.1%, or even greater than or equal to 1%, and may be greater than or equal to 2% by weight. The level of C7 asphaltenes (compounds insoluble in heptane according to standard NFT60-115 or standard ASTM D 6560) amounts to at least 1% and is often greater than or equal to 3% by weight. Asphaltenes C7 are compounds known to inhibit the conversion of residual cuts, both by their ability to form heavy hydrocarbon residues, commonly called coke, and by their tendency to produce sediments which greatly limit the operability of the units of hydrotreating and hydroconversion. The Conradson carbon content can be greater than or equal to 0.5%, or even at least 5% by weight. The Conradson carbon content is defined by standard ASTM D 482 and represents for a person skilled in the art a well-known evaluation of the quantity of carbon residues produced after pyrolysis under standard conditions of temperature and pressure. Initial hydroconversion stage (a-,)
In accordance with the invention, the heavy hydrocarbon feedstock is treated in the presence of hydrogen in a first hydroconversion step (ai), within an initial hydroconversion section. The initial hydroconversion section comprises one or more three-phase reactors containing at least one hydroconversion catalyst, the reactors possibly being arranged in series and / or in parallel. These reactors can, among other things, be reactors of the fixed bed, moving bed, bubbling bed, and / or hybrid bed type, depending on the load to be treated. The invention is particularly suitable for three-phase reactors operating in a bubbling bed, with an updraft of liquid and gas. Thus, this initial hydroconversion step (a ^ is advantageously implemented in an initial hydroconversion section A, comprising one or more three-phase hydroconversion reactors, which can be in series and / or in parallel, operating in a bubbling bed , typically using technology and under the conditions of the H-Oil ™ process as described for example in US patents 4,521,295 or US 4,495,060 or US 4,457,831 or US 4,354,852, or in the article AlChE, March 19-23 , 1995, Houston, Texas, paper number 46d, "Second generation ebullated bed technology", or in chapter 3.5 "Hydroprocessing and Hydroconversion of Residue Fractions" of the book "Catalysis by Transition Métal Sulphides", published by Éditions Technip en 2013. According to this implementation, each three-phase reactor is operated in a fluidized bed called a bubbling bed, each reactor advantageously includes a recirculation pump allowing the maintenance of the catalytic converter. bubbling bed lyser by continuous recycling of at least part of a liquid fraction advantageously drawn off at the head of the reactor and reinjected at the bottom of the reactor.
The first hydroconversion stage (a ^ is carried out under conditions making it possible to obtain a liquid effluent with reduced sulfur, Conradson carbon, metals, and nitrogen content.
In this step (a ^, the charge is preferably transformed under specific hydroconversion conditions. The step (a ^ is preferably operated under an absolute pressure of between 2 MPa and 38 MPa, more preferably between 5 MPa and 25 MPa and even more preferably between 6 MPa and 20 MPa, at a temperature between 300 ° C and 550 ° C, more preferably between 350 ° C and 500 ° C and more preferably between 370 ° C and 450 ° C. The hourly space speed (WH) relative to the volume of each three-phase reactor is preferably between 0.05 h'1 and 10 h'1. According to a preferred implementation, the WH is between 0, 1 h'1 and 10 h'1, more preferably between 0.1 h "1 and 5 h" 1 and even more preferably between 0.15 h "1 and 2 h" 1. According to another implementation , the WH is between 0.05 h'1 and 0.09 h'1. The quantity of hydrogen mixed with the feed is preferably pregnant between 50 and 5000 normal cubic meters (Nm3) per cubic meter (m3) of liquid charge, preferably between 100 and 2000 Nm3 / m3 and very preferably between 200 and 1000 Nm3 / m3. The initial hydroconversion stage (ai) being carried out in a fixed bed, in a mobile bed, in a bubbling bed and / or in a hybrid bed depending on the charge to be treated, this stage therefore contains at least one hydroconversion catalyst which is kept in the reactor.
The hydroconversion catalyst used in the initial hydroconversion step (a ^ of the process according to the invention may contain one or more elements from groups 4 to 12 of the periodic table of the elements, which may or may not be deposited on a support. It is advantageously possible to use a catalyst comprising a support, preferably amorphous, such as silica, alumina, silica-alumina, titanium dioxide or combinations of these structures, and very preferably of the alumina.
The catalyst may contain at least one non-noble group VIII metal chosen from nickel and cobalt, and preferably nickel, said group VIII element being preferably used in combination with at least one metal from group VIB chosen from molybdenum and tungsten, and preferably the metal of group VIB is molybdenum.
In the present description, the groups of chemical elements are given according to the CAS classification (CRC Handbook of Chemistry and Physics, CRC press editor, editor-in-chief D.R. Lide, 81st edition, 2000-2001). For example, group VIII according to the CAS classification corresponds to the metals in columns 8, 9 and 10 according to the new IUPAC classification.
Advantageously, the hydroconversion catalyst used in the initial hydroconversion stage (a ^ comprises an alumina support and at least one metal from group VIII chosen from nickel and cobalt, preferably nickel, and at least one metal from group VIB selected from molybdenum and tungsten, preferably molybdenum, preferably the hydroconversion catalyst comprises nickel as part of group VIII and molybdenum as part of group VIB.
The content of non-noble group VIII metal, in particular nickel, is advantageously between 0.5% to 10% expressed by weight of metal oxide (in particular NiO), and preferably between 1% to 6 % by weight, and the content of group VIB metal, in particular molybdenum, is advantageously between 1% and 30% expressed by weight of metal oxide (in particular of molybdenum trioxide Mo03), and preferably between 4% and 20% by weight. The metal contents are expressed as a percentage by weight of metal oxide relative to the weight of the catalyst.
This catalyst is advantageously used in the form of extrudates or beads. The extrudates have, for example, a diameter between 0.5 and 4.0 mm and a length between 1 and 5 mm. These catalysts are well known to those skilled in the art.
In one of the embodiments according to the invention, the initial hydroconversion step (ai) is carried out in a hybrid bed, comprising simultaneously at least one catalyst which is maintained in the reactor and at least one entrained catalyst which enters the reactor. with the load and which is entrained outside the reactor with the effluents. In this case, a type of entrained catalyst, also called "slurry" according to English terminology, is therefore used in addition to the hydroconversion catalyst which is kept in the reactor in a bubbling bed. The entrained catalyst has a difference in particle size and density adapted to its entrainment. The term “entrainment of the dispersed catalyst” means its circulation in the three-phase reactor (s) by liquid flows, said catalyst circulating with the charge in said three-phase reactor (s), and being withdrawn from said three-phase reactor (s) with the liquid effluent produced. These catalysts are well known to those skilled in the art.
The entrained catalyst can advantageously be obtained by injecting at least one active phase precursor directly into the hydroconversion reactor (s) and / or into the feed before the introduction of said feed into the hydroconversion step (s). The addition of precursor can be introduced continuously or discontinuously (depending on the operation, the type of charges processed, the product specifications sought and the operability). According to one or more embodiments, the entrained catalyst precursor (s) is (are) pre-mixed (s) with a hydrocarbon oil composed for example of hydrocarbons of which at least 50% by weight relative to the weight total of the hydrocarbon oil have a boiling temperature between 180 ° C and 540 ° C, to form a premixed precursor diLié. According to one or more embodiments, the precursor or the pre-mixture of diluted precursor is dispersed in the heavy hydrocarbon feed, for example by dynamic mixing (for example using a rotor, an agitator, etc. ), by static mixing (for example using an injector, by gavage, via a static mixer, etc.), or only added to the load to obtain a mixture. All of the mixing and stirring techniques known to those skilled in the art can be used to disperse the precursor or the mixture of precursors diluted in the feed of one or more hydroconversion stages.
The said precursor (s) of active phase of the unsupported catalyst may or may be in liquid form such as, for example, metal precursors soluble in organic media, such as, for example, molybdenum octoates and / or molybdenum naphthenates, or water-soluble compounds, such as for example phosphomolybdic acids and / or ammonium heptamolybdates.
Said entrained catalyst can be formed and activated ex situ, outside the reactor under conditions suitable for activation, and then be injected with the feed. Said entrained catalyst can also be formed and activated in situ under the reaction conditions of one of the hydroconversion stages.
According to one embodiment, said entrained catalyst can be supported. In this case, the supported catalyst can advantageously be obtained: - by grinding the supported hydroconversion catalyst, fresh or spent or by grinding a mixture of fresh and spent catalysts, or - by impregnation of at least one phase precursor active on a support having a particle size suitable for its training and preferably a size between 0.001 and 100 μm. The active phase can be that described above for the hydroconversion catalyst used in the initial hydroconversion step (ai), as well as the support. Their description is not repeated here.
In one of the implementations of the method according to the invention, a different hydroconversion catalyst is used in each reactor of this initial hydroconversion stage (a ^, the catalyst proposed to each reactor being adapted to the charge sent to this reactor.
In one of the implementations of the method according to the invention, several types of catalyst are used in each reactor.
In one of the implementations of the method according to the invention, each reactor contains one or more catalysts suitable for operation in a bubbling bed, and optionally one or more additional entrained catalysts.
As is known, and for example described in patent FR 3,033,797, the hydroconversion catalyst, when it is used, can be partly replaced by fresh catalyst, and / or used catalyst but of catalytic activity higher than the used catalyst to be replaced, and / or the regenerated catalyst, and / or the rejuvenated catalyst (catalyst coming from a rejuvenation zone in which most of the deposited metals are removed, before sending the spent and rejuvenated catalyst to a regeneration zone in which the carbon and the sulfur which it contains is eliminated, thereby increasing the activity of the catalyst), by drawing off the used catalyst preferably at the bottom of the reactor, and by introducing the replacement catalyst either at the top or at the bottom of the reactor. This replacement of used catalyst is preferably carried out at regular time intervals, and preferably by puffing or almost continuously. The replacement of used catalyst can be done in whole or in part with used catalyst and / or regenerated and / or rejuvenated from the same reactor and / or from another reactor of any hydroconversion stage. The catalyst can be added with the metals in the form of metal oxides, with the metals in the form of metal sulfides, or after preconditioning. For each reactor, the rate of replacement of the spent hydroconversion catalyst with fresh catalyst is advantageously between 0.01 kg and 10 kg per cubic meter of feedstock treated, and preferably between 0.1 kg and 3 kg per cubic meter load processed. This withdrawal and this replacement are carried out using devices advantageously allowing the continuous operation of this hydroconversion step.
As regards the replacement at least in part with regenerated catalyst, it is possible to send the spent catalyst withdrawn from the reactor to a regeneration zone in which the carbon and the sulfur which it contains is removed and then to return this catalyst regenerated in the hydroconversion stage. As regards the replacement, at least in part, of rejuvenated catalyst, it is possible to send the spent catalyst withdrawn from the reactor to a rejuvenation zone in which most of the deposited metals are removed, before sending the spent catalyst and rejuvenated in a regeneration zone in which the carbon and the sulfur which it contains is eliminated and then this regenerated catalyst is returned in the hydroconversion stage.
The initial hydroconversion section A, can also receive, in addition to the heavy hydrocarbon charge, at least one of the following effluents: - one or more external hydrocarbon charges (in the sense external to the process according to invention and different from the initial charge), preferably cuts of hydrocarbons external to the process, such as atmospheric distillates, vacuum distillates, atmospheric residues, or vacuum residues; - part of the heavy fraction from one or more intermediate separation steps (by) carried out between two consecutive additional hydroconversion steps (a,), these steps (a,) and (by) being described below; - part or all of one or more intermediate fractions from one or more intermediate separation stages (by) carried out between two consecutive additional hydroconversion stages (ai); - part of the effluent from one or more additional hydroconversion stages (ai); - part of the heavy cut and / or one or more of the intermediate cuts and / or one or more of the light cuts from the first fractionation step (c) of the process according to the invention; - part or all of the residual asphalt produced in the deasphalter D in the deasphalting step (d); - part or all of the light fraction of the DAO produced in the second fractionation step (e) of the process according to the invention. Intermediate separation step (bt) - optional The liquid effluent from the initial hydroconversion step (ai) can then undergo an intermediate separation step (bj) in an intermediate separation section Br, carried out between the initial step hydroconversion (ai) and an additional hydroconversion step following the initial hydroconversion step. This additional hydroconversion step is described below. According to the invention, this intermediate separation step (bj) is preferred, but it remains optional. Indeed, the liquid effluent from the initial hydroconversion stage (ai) can alternatively be sent directly to the additional hydroconversion stage.
Preferably, at least part of the liquid effluent from the initial hydroconversion step (a ^ is sent to the intermediate separation step (b,). The intermediate separation step (br) separates a part or all of the liquid effluent from the initial hydroconversion stage (a ^ to produce at least one so-called heavy liquid fraction boiling mainly at a temperature greater than or equal to 350 ° C.
This first intermediate separation step therefore produces at least two fractions, the heavy liquid fraction of which as described above, the other cut or cuts being light and intermediate cuts.
The light fraction thus separated contains the dissolved light gases (H2 and CrC ^, naphtha (fraction boiling at a temperature below 150 ° C), kerosene (fraction boiling between 150 ° C and 250 ° C), and at least one diesel fuel (fraction boiling between 250 ° C and 375 ° C).
The light fraction can then be sent at least in part to a fractionation unit (not shown in the figures) where the light gases (H2 and CrC4) are extracted from said light fraction, for example by passing through a flash balloon. The hydrogen gas thus recovered can advantageously be recycled at the entrance to the initial hydroconversion stage (ai). The fractionation unit to which the light fraction can be sent may also include a distillation column. In this case, the naphtha, kerosene and diesel fractions of the light fraction sent to said column are separated.
The heavy liquid fraction resulting from the intermediate separation stage (b /), boiling mainly at a temperature greater than or equal to 350 ° C., contains at least one fraction boiling at a temperature greater than or equal to 540 ° C., called residue under empty (which is the unconverted fraction). The heavy liquid fraction from the intermediate separation step (bi), boiling mainly at a temperature greater than or equal to 350 ° C, can also contain a fraction boiling between 375 and 540 ° C, called vacuum distillate. It can optionally also contain part of the diesel fraction boiling between 250 and 375 ° C.
This heavy liquid fraction is then sent in whole or in part to a second hydroconversion step (82), as described below. The intermediate separation step (b,) can therefore separate the liquid effluent from the initial hydroconversion step (a ^ in addition to two liquid fractions, depending on the separation means used.
The intermediate separation section B includes any separation means known to those skilled in the art.
The intermediate separation section B, can thus include one or more of the following separation equipment: one or more flash flasks arranged in series, one or more stripping columns with steam and / or hydrogen, an atmospheric distillation column , a vacuum distillation column.
Preferably, this intermediate separation step (bj) is carried out by one or more flash balloons arranged in series.
According to a preferred implementation, the intermediate separation step (bj) is carried out by a single flash balloon. Preferably, the flash balloon is at a pressure and a temperature close to the operating conditions of the last reactor of the initial hydroconversion stage (ai). This implementation is particularly preferred because it reduces the number of equipment and therefore the investment cost.
According to another implementation, the intermediate separation step (bj) is carried out by a sequence of several flash balloons, operating under operating conditions different from those of the last reactor of the initial hydroconversion step (a ^, and leading to the production of at least the light liquid fraction, which can then be sent at least partly to a fractionation unit, and at least the heavy liquid fraction, which is then sent at least partly to a second hydroconversion stage (a2).
In another implementation, the intermediate separation step (b,) is carried out by one or more stripping columns with steam and / or hydrogen. By this means, the effluent from the initial hydroconversion stage (ai) is separated into at least the light liquid fraction and at least the heavy liquid fraction. The heavy liquid fraction is then sent at least in part to a second hydroconversion stage (a2).
In another implementation; the intermediate separation step (bj) is carried out in an atmospheric distillation column separating the liquid effluent from the initial hydroconversion step (ai). The heavy liquid fraction recovered from the atmospheric distillation column is then sent at least in part to a second hydroconversion stage (a2).
In another implementation; the intermediate separation step (bj) is carried out by an atmospheric distillation column separating the liquid effluent from the initial hydroconversion step (a ^, and by a vacuum distillation column receiving the residue from the column of atmospheric distillation and producing the heavy liquid fraction which is then sent at least in part to a second hydroconversion stage (a2). The intermediate separation stage (b,) can also consist of a combination of the various work described above, in a different order from that described above.
Optionally, before being sent to a second hydroconversion step (a2) according to the invention, the heavy liquid fraction can be subjected to a stripping step with steam and / or hydrogen using one or more stripping columns, in order to remove from the heavy fraction the compounds having a boiling point below 540 ° C.
The intermediate separation section B can also receive, in addition to part or all of the liquid effluent from the initial hydroconversion step (ai), at least one of the following effluents: - a part of the heavy hydrocarbon feedstock sent to the hydroconversion stage (bypass); - one or more fillers of external hydrocarbons, preferably cuts of hydrocarbons external to the process, such as atmospheric distillates, vacuum distillates, atmospheric residues, vacuum residues; - a part of the heavy fraction resulting from one or more intermediate separation stages By carried out between two consecutive additional hydroconversion stages (a ^, subsequent to step (a ^, as detailed below; - a part or all of one or more intermediate fractions from one or more intermediate separation steps (b,) carried out between two consecutive additional hydroconversion steps (ai); - part of the liquid effluent from one or more steps additional hydroconversion (ai) described below; - part of the heavy cut and / or one or more of the intermediate cuts and / or one or more of the light cuts resulting from the first fractionation step ( c) detailed below; - part or all of the DAO produced in the deasphalter D in the deasphalting stage (d); - part or all of the heavy fraction of the DAO pr oduit in the second fractionation stage (e); - part or all of the light fraction of the DAO produced in the second fractionation stage (e).
In this case, the additional effluent can be sent to the inlet of the intermediate separation section, or between two different equipment from the intermediate separation section, for example between the flash tanks, stripping columns and / or distillation columns. Additional hydroconversion stage (s) (ai) and optional intermediate separation stage (s) (bj)
According to the invention, part or all of the effluent from the initial hydroconversion step (ai), or preferably a part or all of the heavy fraction from the intermediate separation step ( bj), is treated in the presence of hydrogen in an additional hydroconversion step (a2) carried out in an additional hydroconversion section A2, which follows the initial hydroconversion step (ai) or optionally the intermediate separation step (bj).
The process according to the invention can comprise more than one additional hydroconversion step (a, ·), as well as more than one intermediate separation step (by) between two consecutive additional hydroconversion steps (a, ·).
Thus, the method according to the invention comprises (n-1) additional hydroconversion step (s) (a;) in (n-1) additional hydroconversion section (s) A, ·, in the presence of hydrogen, at least part or all of the liquid effluent from the previous hydroconversion step (aH) or possibly a heavy fraction from the optional intermediate separation step (by ) between two consecutive hydroconversion steps separating part or all of the liquid effluent from the previous hydroconversion step (a ^) to produce at least one heavy fraction boiling mainly at a temperature greater than or equal to 350 ° C, the (n-1) additional hydroconversion step (s) (a,) being carried out so as to obtain a hydroconverted liquid effluent with reduced sulfur, Conradson carbon, metals, and nitrogen content. n is the total number of hydroconversion steps, with n greater than or equal to 2. / and j are indices. / is an integer ranging from 2 to n and y being an integer ranging from 1 to (n-1).
The additional hydroconversion section (s) A, - each comprise at least one three-phase reactor containing at least one hydroconversion catalyst, as described for the initial hydroconversion section Ai. The initial hydroconversion step and the additional hydroconversion step (s) are separate steps, carried out in different hydroconversion sections.
The (n-1) additional hydroconversion stage (s) (a,) are implemented in a similar manner to what has been described for the initial hydroconversion stage, and their description is therefore not not repeated here. This applies in particular to the operating conditions, the equipment used, the hydroconversion catalysts used, with the exception of the details given below.
As for the initial hydroconversion stage (aj), the (n-1) additional hydroconversion stage (s) (a, ·) are advantageously implemented in initial hydroconversion sections A, comprising one or more three-phase hydroconversion reactors, which can be in series and / or in parallel, preferably operating in a bubbling bed, as described above for the initial hydroconversion step (ar). According to this preferred implementation, each three-phase reactor is operated in a fluidized bed called a bubbling bed. Each reactor advantageously comprises a recirculation pump allowing the catalyst to be maintained in a bubbling bed by continuous recycling of at least part of a liquid fraction advantageously drawn off at the head of the reactor and reinjected at the bottom of the reactor.
In these additional hydroconversion stages, the operating conditions can be more severe than in the initial hydroconversion stage, in particular by using a higher reaction temperature, remaining in the range between 300 ° C. and 550 ° C., preferably between 350 ° C and 500 ° C, and dines more preferably between 370 ° C and 450 ° C, or by reducing the amount of hydrogen introduced into the reactor, remaining in the range between 50 and 5000 Nm3 / m3 of liquid charge, preferably between 100 and 2000 Nm3 / m3, and even more preferably between 200 and 1000 Nm3 / m3. The other pressure and WH parameters are in the same ranges as those described for the initial hydroconversion stage.
The catalyst used in the reactor (s) of an additional hydroconversion stage may be the same as that used in the reactor (s) of the initial hydroconversion stage, or may also be a catalyst more suitable for the hydroconversion of residual sections containing a DAO. In this case, the catalyst may have a porosity of the support or contain metal contents, suitable for the hydroconversion of charges containing DAO cuts. With regard to the possible replacement of the used catalyst, the catalyst replacement rate applied in the reactor (s) of an additional hydroconversion stage can be the same as that used for the reactor (s) of the initial hydroconversion stage , or be more suitable for the hydroconversion of residual sections containing a DAO. In this case, the catalyst replacement rate can be lower, suitable for hydroconversion of charges containing DAO cuts.
The other intermediate separation stages (by) which can each be carried out between two consecutive additional hydroconversion stages (A) are also implemented in a similar manner to what has been described for the intermediate separation stage (bj) , and the description of these steps (by) is therefore not repeated here.
In a preferred implementation, the method according to the invention always comprises an intermediate separation step (by) between two consecutive additional hydroconversion steps (s) (al). According to an alternative implementation, the effluent from an additional hydroconversion step (al) is sent directly to another additional hydroconversion step (a / + J) following step (a, · ).
According to a preferred implementation, the method comprises a single additional hydroconversion step (a2), and an intermediate separation step (bj). With reference to the figures in particular, this is the case where n is equal to 2, with / 'taking the unique value of 2 and y the unique value of 1.
According to the invention, at least part of the DAO resulting from the deasphalting stage (d) detailed below, and / or at least part of the heavy fraction of the DAO resulting from a second fractionation stage ( e) also detailed below, is recycled by being sent to an additional hydroconversion step (a1) and / or to an intermediate separation step (b /). The process according to the invention thus excludes recycling of the DAO or of a heavy fraction of the DAO in the initial hydroconversion stage.
The DAO or the heavy fraction of the DAO thus recycled can then be co-treated in an additional hydroconversion section A, with at least part of the effluent coming from the initial hydroconversion step (aj) or from an additional hydroconversion step (a, ·), or more preferably co-treated with at least part of the heavy fraction resulting from an intermediate separation step (by).
Each additional hydroconversion section A, · can also receive, in addition to the effluent from the initial hydroconversion step or from a previous additional hydroconversion step (aH) or, more preferably, in addition of the heavy fraction from an intermediate separation step (by), at least one of the following effluents: - part of the heavy hydrocarbon feedstock sent to the initial hydroconversion step (bypass); one or more fillers of external hydrocarbons, preferably cuts of hydrocarbons external to the process, such as atmospheric distillates, vacuum distillates, atmospheric residues, or vacuum residues; - part of the heavy fraction from one or more subsequent intermediate separation steps By carried out between two consecutive additional hydroconversion steps (ai); - part or all of one or more intermediate fractions from one or more subsequent intermediate (by) separation steps performed between two consecutive additional hydroconversion steps (ai); - part of the effluent from one or more subsequent additional hydroconversion hydroconversion stages (a ^); - part of the heavy cut and / or one or more of the intermediate cuts and / or one or more of the light cuts from the first fractionation step (c) of the process according to the invention; - part or all of the CAD produced in the deasphalter D in the deasphalting stage (d); - part or all of the heavy fraction of the DAO produced in the second fractionation stage (e) of the process according to the invention; - part or all of the light fraction of the DAO produced in the second fractionation stage (e); - part or all of the residual asphalt produced in the deasphalter D in the deasphalting step (d).
Each intermediate separation section By can also receive, in addition to part or all of the hydroconverted liquid effluent resulting from the initial hydroconversion step (a ^ or from a previous additional hydroconversion step (a ^), at least one of the following effluents: - part of the heavy hydrocarbon feedstock sent to the hydroconversion stage (bypass); - one or more external hydrocarbon feeds, preferably cuts of external hydrocarbons to the process, such as atmospheric distillates, vacuum distillates, atmospheric residues, vacuum residues; - part of the heavy fraction resulting from one or more intermediate By · subsequent separation steps carried out between two hydroconversion steps consecutive additional (ai); - part or all of one or more intermediate fractions from one or more intermediate separation stages subsequent ediaries (bj) performed between two consecutive additional hydroconversion stages (ai); - part of the liquid effluent from one or more additional additional hydroconversion steps (ai); - part of the heavy cut and / or one or more of the intermediate cuts and / or one or more of the light cuts from the first fractionation step (c); - part or all of the CAD produced in the deasphalter D in the deasphalting stage (d); - part or all of the heavy fraction of the DAO produced in the second fractionation stage (e); - part or all of the light fraction of the DAO produced in the second fractionation stage (e).
In this case, the additional effluent can be sent to the inlet of the intermediate separation section Bh or between two different pieces of equipment from the intermediate separation section B y, for example between the flash tanks, the stripping columns and / or the distillation columns.
First fractionation stage (c) The hydroconverted liquid effluent from the last additional hydroconversion stage (an) then undergoes at least partially a fractionation stage (c) in a first fractionation section C.
This first fractionation step (c) separates part or all of the effluent from step (an) into several fractions including at least one heavy liquid fraction boiling mainly at a temperature above 350 ° C, preferably higher at 500 ° C and preferably greater than 540 ° C. The heavy liquid cup contains a fraction boiling at a temperature above 540 ° C, called vacuum residue (which is the fraction not converted). It can contain part of the diesel fraction boiling between 250 and 375 ° C and a fraction boiling between 375 and 540 ° C called vacuum distillate.
This first fractionation stage therefore produces at least two fractions including the heavy liquid fraction as described above, the other cut or cuts being light and intermediate cuts.
The first fractionation section C comprises any separation means known to those skilled in the art.
The first fractionation section C can thus include one or more of the following separation devices: one or more flash balloons arranged in series, and preferably a series of at least two successive flash balloons, one or more stripping columns at the steam and / or hydrogen, an atmospheric distillation column, a vacuum distillation column.
According to one implementation, this first fractionation step (c) is carried out by a sequence of at least two successive flash balloons.
According to another implementation, this first fractionation step (c) is carried out by one or more stripping columns with steam and / or hydrogen.
According to another preferred embodiment, this first fractionation step (c) is carried out by an atmospheric distillation column, and more preferably by an atmospheric distillation column and a vacuum column receiving the atmospheric residue.
According to the most preferred implementation, this first fractionation step (c) is carried out by one or more flash flasks, an atmospheric distillation column and a vacuum column receiving the atmospheric residue. This configuration reduces the size of the downstream deasphalters, thereby minimizing investment and operating costs.
The first fractionation section C can also receive, in addition to part or all of the hydroconverted liquid effluent from the last additional hydroconversion step (an), at least one of the following effluents: - a part of the heavy hydrocarbon feedstock sent to the hydroconversion stage (bypass); one or more fillers of external hydrocarbons, preferably cuts of hydrocarbons external to the process, such as atmospheric distillates, vacuum distillates, atmospheric residues, vacuum residues; - part of the heavy fraction from one or more intermediate separation stages By carried out between two consecutive additional hydroconversion stages (a ^; - part of the liquid effluent from one or more additional hydroconversion stages ( ai); - part of one or more of the intermediate cuts from the first fractionation stage (c); - part of the CAD produced in the deasphalt paver D in the deasphalting stage (d); - part of the heavy fraction of the DAO produced in the second fractionation stage (e); - part or all of the light fraction of the DAO produced in the second fractionation stage (e).
In this case, the additional effluent can be sent to the inlet of the intermediate separation section, or between two different equipment from the intermediate separation section, for example between the flash tanks, stripping columns and / or distillation columns. Deasphalting stage (d)
The heavy cut resulting from the first fractionation step (c) then undergoes, in accordance with the method according to the invention, in part or in whole a deasphalting step (d) in a deasphalter D, with at least one hydrocarbon solvent, to extract a DAO and a residual asphalt.
The deasphalt paver D can also receive at least one of the following effluents: - part of the heavy hydrocarbon feedstock sent to the hydroconversion stage (bypass); one or more fillers of external hydrocarbons, preferably sections of hydrocarbons external to the process, such as atmospheric distillates, vacuum distillates, atmospheric residues, vacuum residues; - part of the heavy fraction from one or more intermediate separation steps (by) carried out between two consecutive additional hydroconversion steps (ai) (not shown in Figure 1); - part of the liquid effluent from the initial hydroconversion step (a ^ or from one or more additional hydroconversion steps (a,) (not shown in Figure 1); The deasphalting step (d ) using a solvent (or SDA for Solvent DeAsphalting in English) is carried out under conditions well known to those skilled in the art. Reference may therefore be made to the article by Billon and others published in 1994 in the volume 49, N ° 5 of the Revue of the Institut Français du Pétrde, page 495 to 507, to the book "Refining and conversion of heavy petroleum products" by JF Le Page, SG Chatila and M Davidson, Technip Edition, page 17 - 32 or to US patents 4,239,616; US 4,354,922; US 4,354,928; US 4,440,633; US 4,536,283; and US 4,715,946.
The deasphalting can be carried out in one or more mixer-settlers or in one or more extraction columns. The deasphalter D thus comprises at least one mixer-settler or at least one extraction column.
Deasphalting is a liquid-liquid extraction generally carried out at an average temperature between 60 ° C and 250 ° C with at least one hydrocarbon solvent. The solvents used for deasphalting are solvents with a low boiling point, preferably paraffinic solvents, and preferably heavier than propane, and preferably having from 3 to 7 carbon atoms. Preferred solvents include propane, butane, isobutane, pentane, isopentane, neopentane, hexane, isohexanes, C6 hydrocarbons, heptane, C7 hydrocarbons, light or more less apolar, as well as the mixtures obtained from the abovementioned solvents. Preferably, the solvent is butane, pentane or hexane, as well as their mixtures. The solvent (s) are optionally added with at least one additive. The solvents that can be used and the additives are widely described in the literature. The solvent / charge ratios (volume / volume) entering the deasphalt paver D are generally between 3/1 and 16/1, and preferably between 4/1 and 8/1. It is also possible and advantageous to carry out the recovery of the solvent according to the opticritical process, that is to say by using a solvent under supercritical conditions in the separation section. This process makes it possible in particular to significantly improve the overall economy of the process.
In the context of the present invention, it is preferred to implement a technique using at least one extraction column and preferably only one (eg the Solvahl ™ process). Advantageously, such as in the Solvahl ™ process with a single extraction column, the solvent / charge ratios (volume / volume) entering the deasphalt paver D are low, typically between 4/1 and 8/1, or even between 4 / 1 and 6/1.
According to a preferred implementation, the deasphalting is carried out in an extraction column at a temperature between 60 ° C. and 250 ° C. with at least one hydrocarbon solvent having from 3 to 7 carbon atoms, and a solvent / charge ratio ( volume / volume) between 4/1 and 6/1.
The deasphalter D produces a DAO practically free of C7 asphaltenes and a residual asphalt concentrating most of the impurities from the residue, said residual asphalt being drawn off.
The DAO yield is generally between 40% by weight and 95% by weight depending on the operating conditions and the solvent used, and according to the charge sent to the deasphalt paver D and in particular the quality of the heavy liquid cut resulting from the first fractionation step (c ).
Table 1 below gives the ranges of typical operating conditions for deasphalting as a function of the solvent:
table 1
The deasphalting conditions are adapted to the quality of the CAD to be extracted and to the load entering the deasphalter D.
These conditions allow a significant reduction in the sulfur content, in Conradson carbon and in the content of C7 asphaltenes.
The DAO obtained advantageously has a C7 asphaltene content of less than 2% by weight in general, preferably less than 0.5% by weight, preferably less than 0.05% by weight, measured as insoluble C7.
According to the invention, the DAO thus produced is either sent to a second fractionation step (e) of the method according to the invention, or recycled at least in part to one or more of the intermediate separation steps (bj) and / or directly at the entry of one or more additional hydroconversion steps (ai), and more preferably at the entry of the last additional hydroconversion step (a „).
Second fractionation stage (e) - optional
The DAO from the deasphalting step (d) can undergo, at least in part, a second fractionation in a second fractionation section E, in order to produce at least two fractions.
Preferably, part or all of the DAO from the deasphalting step (d) is sent to this second fractionation step (e).
The second fractionation section E comprises any separation means known to those skilled in the art.
The second fractionation section E can thus include one or more of the following separation devices: one or more flash balloons arranged in series, and preferably a sequence of at least two successive flash balloons, one or more stripping columns at the steam and / or hydrogen, an atmospheric distillation column, a vacuum distillation column.
According to one implementation, this second fractionation step (e) is carried out by a sequence of at least two successive flash balloons.
According to another implementation, this second fractionation step (e) is carried out by one or more stripping columns with steam and / or hydrogen.
According to another preferred embodiment, this second fractionation step (e) is carried out by an atmospheric distillation column, and more preferably by an atmospheric distillation column and a vacuum column receiving the atmospheric residue.
According to another preferred implementation, this second fractionation step (e) is carried out by one or more flash flasks, an atmospheric distillation column and a vacuum column receiving the atmospheric residue.
According to another preferred implementation, this second fractionation step (e) is carried out by a vacuum column.
The choice of equipment in the fractionation section E preferably depends on the choice of equipment in the first fractionation section C and the loads introduced into the deasphalter D.
According to the method of the invention, the heavy fraction of the DAO thus produced in the second fractionation section E is then recycled at least in part to one or more intermediate separation stages and / or directly at the inlet of one or more several additional hydroconversion steps (ai), and more preferably at the entry of the last additional hydroconversion step (an).
According to a preferred implementation, the heavy cut resulting from the first fractionation section C of the process according to the invention is an atmospheric residue which leaves a column of atmospheric distillation. The absence of a vacuum distillation column avoids the concentration of sediment and rapid fouling of the vacuum distillation column. The atmospheric residue thus produced is then sent to the deasphalting machine D to operate the deasphalting step (d), producing a residual asphalt and a DAO practically free of C7 asphaltenes and sediments, but containing both a fraction of distillate under vacuum and a fraction of vacuum residue. This DAO thus obtained can then be sent to the second fractionation section E of the process according to the invention, composed of a vacuum distillation column and having the objective of separating the DAO into at least a slight fraction of the DAO whose boiling point is mainly below 500 ° C and at least a heavy fraction of the DAO whose boiling point is mainly above 500 ° C. As the DAO produced in the deasphalter D is free of sediment and contains almost no more C7 asphaltenes, the vacuum distillation column will only clog very slowly, thus avoiding frequent stops and decommissioning for cleaning of the vacuum distillation column. The heavy fraction of the DAO thus produced is then advantageously recycled at least in part at the entry of the last additional hydroconversion stage (an).
The process according to the invention therefore improves the stability of the liquid effluents treated during the hydroconversion, and more particularly during the additional hydroconversion stages receiving at least part of the DAO and / or of the heavy fraction of the DAO, all by considerably increasing the conversion of the heavy hydrocarbon feedstock. DAO or heavy fraction of DAO recycling step (f)
The method according to the invention comprises recycling at least part of the DAO from step (d) and / or at least part of the heavy fraction of DAO from step (e) an additional hydroconversion step (a;) and / or an intermediate separation step (by).
This recycling has been described previously in relation to the deasphalting (d) and second fractionation (e) stages. Recycling stage (r-, to r7) of other effluents from stages (e)
The process according to the invention can include other recycling, the recycled effluents being able to come from the second fractionation stage (e), from the deasphalting stage (d), from an additional hydroconversion stage (ai) , or an intermediate separation step (bj).
According to one implementation, the method comprises recycling (n) part or all of the light fraction of the DAO resulting from step (e) in the initial hydroconversion section At and / or in at least one additional hydroconversion section A, and / or in at least one intermediate separation section By and / or in the first fractionation section C.
According to one implementation, the method comprises the recycling (r2) of part of the heavy fraction of the DAO from step (e) in the first fractionation section C.
According to one implementation, the method comprises recycling (r3) part of the CAD from step (d) in the first fractionation section C.
According to one implementation, the method comprises recycling (r4) part or all of the residual asphalt from step (d) in the initial hydroconversion section Αί and / or in at least one additional hydroconversion section A, ·. Preferably, the residual asphalt is recycled in a hydroconversion section different from that which receives the DAO or the heavy fraction of the DAO.
According to one implementation, the method comprises recycling (r5) of part of the hydroconverted liquid effluent from an additional hydroconversion section A, · given: - in the initial hydroconversion section A1; and / or - in another additional hydroconversion section A, positioned upstream of said section A, · given, and / or - in an intermediate separation section By positioned upstream of said section A, · given.
According to one implementation, the method comprises the recycling (r6) of part of the heavy fraction and / or part or all of one or more intermediate fractions from a given intermediate section By: - in the initial hydroconversion section A1; and / or - in an additional hydroconversion section A, positioned upstream of said given intermediate section By, and / or - in another intermediate separation section By positioned upstream of said given By section.
According to one implementation, the method comprises the recycling (r7) of part of the heavy fraction and / or part or all of one or more intermediate fractions from the first fractionation section C: - in the initial hydroconversion section A1; and / or - in an additional hydroconversion section A, ·, and / or - in an intermediate separation section By.
The following embodiments are described with reference to the corresponding figures
FIG. 1 schematically represents the general case of the method according to the invention, including different options corresponding to different embodiments.
According to the process illustrated in Figure 1, the heavy load of hydrocarbons 1 is sent via a pipe in an initial hydroconversion section ΑΛ composed of one or more three-phase reactors, which can be in series and / or in parallel. These hydroconversion reactors can, in addition, be reactors of the fixed bed, moving bed, bubbling bed, and / or hybrid bed type, depending on the charge to be treated, and are preferably reactors operating in bubbling beds. The initial hydroconversion stage carried out in section Ai represents the first hydroconversion stage of the heavy hydrocarbon charge 1, and may include the co-treatment of one or more external charges 2 and / or one or more recycling effluents from other stages of the process.
The different recycling effluents that can be injected into section A · are as follows: - part of the total effluent (6, 10) from one or more additional hydroconversion sections Aj; - part or all of one or more intermediate fractions from one or more intermediate separation sections Bj (not shown in Figure 1); - part of the heavy fraction from one or more intermediate separation sections Bj; - part or all of one or more intermediate sections 12 from the first fractionation section C; - A part of the heavy cut 13 from the first fractionation section C; - part or all of the residual asphalt 14 from the deasphalter D; - part or all of the light fraction 16 of the DAO from the second fractionation section E. The liquid effluent 3 from the initial hydroconversion section ΑΛ can be sent either directly to the additional hydroconversion section A2, either to the intermediate separation section via a pipe. This pipe offers the possibility of purging a fraction of this effluent 3 and therefore sending either all or only a part of the liquid effluent from A to the intermediate separation section.
Section B · represents the first intermediate separation section where the intermediate separation step (bί) is carried out. It receives part or all of the liquid effluent from the previous hydroconversion stage, optionally with an injection of a heavy load of hydrocarbons 1 and / or an injection of one or more external charges 2 and / or an injection of '' one or more recycling effluents. The different recycling effluents that can be injected into section Βί are: - part of the total effluent (6, 10) from one or more additional hydroconversion sections A; - part or all of one or more intermediate fractions from one or more intermediate separation sections Bj (not shown in Figure 1); - a part of the heavy fraction 9 from one or more intermediate separation sections Bj downstream; - part or all of one or more intermediate sections 12 from the first fractionation section C; - A part of the heavy cut 13 from the first fractionation section C; - part or all of the DAO 15 from the deasphalt paver D; - part or all of the light fraction of DAO 16 from the second fractionation section E; - part or all of the heavy fraction of DAO 17 from the second fractionation section E.
The heavy fraction 5 from the first intermediate separation section Βί is then sent at least in part to the additional hydroconversion section A2 via a pipe, while the light fraction 4 from the section B! is purged via another line. A heavy fraction 5 can be purged; it is either part or all of the heavy fraction 5 which is sent to the additional hydroconversion section A2. Part of the effluent 5 can also be recycled to the initial hydroconversion section A !.
Section A2 represents the second hydroconversion section where an additional hydroconversion step (a2) is carried out. Section A2 is made up of one or more three-phase reactors, which can be in series and / or in parallel. These hydroconversion reactors can, in addition, be reactors of the fixed bed, moving bed, bubbling bed, and / or hybrid bed type, depending on the charge to be treated, and are preferably reactors operating in bubbling beds.
This section A2 can receive part or all of the liquid effluent from the initial hydroconversion section A, and / or at least part of the heavy fraction from the first intermediate separation section ΒΛ. This section A2 can also receive for co-treatment part of the heavy load of hydrocarbons 1 and / or one or more additional loads 2 and / or one or more recycling effluents. The different recycling effluents that can be injected into section A2 are: - part of the total effluent 10 from one or more additional hydroconversion sections A downstream; - part or all of one or more intermediate fractions from one or more intermediate separation sections Bj downstream (not shown in Figure 1); - a part of the heavy fraction 9 from one or more intermediate separation sections Bj downstream; - part or all of one or more intermediate sections 12 from the first fractionation section C; - A part of the heavy cut 13 from the first fractionation section C; - part or all of the DAO 15 from the deasphalt paver D; - part or all of the residual asphalt 14 from the deasphalter D; - part or all of the light fraction of DAO 16 from the second fractionation section E; - part or all of the heavy fraction 17 of the DAO from the second fractionation section E. The liquid effluent 6 from the second hydroconversion section A2 can be sent to a third hydroconversion section, either to a second intermediate separation section via a pipe which offers the possibility of purging a fraction of said effluent and therefore sending either all or only part of said effluent from section A2 to the second intermediate separation section B2 (not shown) ), as well as recycling part of said effluent to one or more hydroconversion sections upstream of section A2 or to the intermediate separation section Bt located between sections At and A2.
The process according to the invention can thus include n hydroconversion steps and (n-1) intermediate separation steps.
The section Β] = ιν1 represents the last section of intermediate separation. It receives part or all of the liquid effluent 7 from the previous hydroconversion step Ai = ni, and optionally an injection of heavy hydrocarbon feedstock 1 and / or an injection of one or more external feedstocks 2 and / or an injection of one or more recycling effluents. The different recycling effluents that can be injected into the section Bi = n.i are: - part of the effluent 10 from the last hydroconversion section An; - part or all of one or more intermediate sections (12) from the first fractionation section C; - part of the heavy cut from the first fractionation section C; - part or all of the DAO 15 from the deasphalt paver D; - part or all of the light fraction of DAO 16 from the second fractionation section E; - part or all of the heavy fraction of DAO 17 from the second fractionation section E.
The An section represents the last hydroconversion step where the additional hydroconversion step (an) is performed. The An section is made up of one or more three-phase reactors, which can be in series and / or in parallel. These hydroconversion reactors can, in addition, be reactors of the fixed bed, moving bed, bubbling bed, and / or hybrid bed type, depending on the charge to be treated, and are preferably reactors operating in bubbling beds.
This section An can receive part or all of the effluent from the previous hydroconversion stage An.! and / or the heavy fraction of the previous intermediate separation section Bj = n.!. This section An can also receive for co-processing part of the heavy load of hydrocarbons 1 and / or one or more external loads 2 and / or one or more recycling effluents. The various recycling effluents that can be injected into the section An are: - part or all of one or more intermediate cuts 12 coming from the first fractionation section C; - Part of the heavy cut from 13 from the first fractionation section C; - part or all of the residual asphalt 14 from the deasphalter D; - part or all of the DAO 15 from the deasphalt paver D; - part or all of the light fraction of DAO 16 from the second fractionation section E; - part or all of the heavy fraction of DAO 17 from the second fractionation section E.
Section C represents the first fractionation section in which all or at least part of the hydroconverted liquid effluent 10 from the last hydroconversion section An is sent via a pipe to be fractionated into several sections. By way of example, FIG. 1 represents three sections, a light section 11, which leaves the process according to the invention and which is optionally sent to an after-treatment, an intermediate section 12 and a heavy section 13. The latter two sections can be partially or totally sent to other processes and / or recycled to one or more hydroconversion stages of the process according to the invention and / or recycled to one or more intermediate separation sections of the process according to the invention.
The first fractionation section C can also receive, either at the input or between two different pieces of equipment making up this section C, part of the heavy load of hydrocarbons 1 and / or external loads 2 and / or one of the following recycling effluents: - part of the heavy fraction from one or more intermediate separation stages By (not shown in Figure 1); - part of the liquid effluent from one or more hydroconversion stages (ai and a {) (not shown in Figure 1); - part of the DAO 15 produced in the deasphalting machine D; - part of the heavy fraction of DAO 17 produced in the second fractionation section E; - part or all of the light fraction 16 of the DAO produced in the second fractionation step E.
Section D represents the deasphalting machine operating the deasphalting step (d) (SDA) in which the DAO 15 and the residual asphalt 14 are extracted from at least part of the heavy cut 13 from the first fractionation section C The deasphalt paver D can also receive part of the heavy load of hydrocarbons 1 and / or additional loads 2 and / or one of the following recycling effluents: - part of the heavy fraction from one or more sections intermediate separation B) (not shown in Figure 1); - part of the liquid effluent from the initial hydroconversion section Ai or from one or more additional hydroconversion sections A, (not shown in Figure 1);
The DAO produced in the deasphalter D can either be sent, in part or in whole, in the second fractionation section E, or recycled, in part or in whole, to one or more of the additional hydroconversion sections Ai and / or to one or more several of the intermediate separation sections By.
Section E represents a second fractionation section of the method according to the invention in which the fractionation step (e) of all or at least part of the CAD is carried out in at least two sections. By way of example, the process illustrated in FIG. 1 shows two sections, a light section 16, which can leave the process according to the invention and / or be recycled in different sections of the process as previously described, and a heavy section 17 The latter can then be partially or completely recycled in one or more additional hydroconversion sections A and / or recycled on one or more intermediate separation sections By.
The circuit 18 in dotted lines in FIG. 1 represents the multiple possible exchanges of catalyst between the various hydroconversion stages, as well as the purging and the addition of fresh and spent catalysts.
Four preferred implementations of the general diagram of FIG. 1 are illustrated in FIGS. 2 to 5 while limiting more and more the number of equipments and thus the investment costs.
FIG. 2 illustrates the invention in a preferred implementation comprising the recycling of the heavy fraction of the DAO at the entry of the last hydroconversion stage.
According to this implementation, the method comprises the following successive stages: the initial hydroconversion stage (a ^, the intermediate separation stage (bi), a second hydroconversion stage (a2) which is the only stage d additional hydroconversion, the first fractionation step (c), the deasphalting step (d) and the second fractionation step (e).
The heavy hydrocarbon feedstock 1 is sent via a pipe to the initial hydroconversion section A-, at high hydrogen pressure 19. The section is identical to that described in relation to FIG. 1. The liquid effluent 3 from of the section A ^ is separated in the intermediate separation section B ^ In the separation section the conditions are generally chosen so as to obtain two liquid fractions, a light fraction 4 and a heavy fraction 5. The section can include any means of separation known to a person skilled in the art, and preferably does not include an atmospheric distillation column or a vacuum distillation column, but a steam or hydrogen stripping column, and is more preferably formed by a sequence of flash balloons, and even more preferably by a single flash balloon.
The heavy liquid fraction 5 at the outlet of the intermediate separation section B ^ is then sent via a pipe in the second hydroconversion step A2 at high hydrogen pressure 20. This section A2 conforms to the description of the section of initial hydroconversion A, in FIG. 1. The hydroconverted liquid effluent 6 obtained at the end of this second hydroconversion step is separated in the first fractionation section C. In this section C, the conditions are chosen so as to obtain at least two liquid fractions, a light section 11 and a heavy section 13. The section preferably comprises a set of flash flasks and an atmospheric distillation column.
The heavy cut 13 is then sent via a line into the deasphalter D to obtain a DAO 15 which is sent to the second fractionation section E via a line and a residual asphalt 14 which is purged via another line.
The DAO fraction is then separated in the second fractionation section E, where the conditions are chosen so as to obtain at least two liquid fractions, a light fraction of DAO 16 and a heavy fraction of DAO 17. Section E comprises preferably a set of flash flasks and a vacuum distillation column.
The heavy fraction of the DAO 17 is then mixed, in part or in whole as shown, with the heavy liquid fraction 5 coming from the intermediate separation section B1 and the mixture is then sent to the second hydroconversion section A2.
FIG. 3 illustrates the invention in another implementation comprising the recycling of the DAO in the intermediate separation section.
According to this implementation, the method comprises the following successive stages: the initial hydroconversion stage (a ^, the intermediate separation stage (b ^, a second hydroconversion stage (a2) which is the only stage d additional hydroconversion, the first fractionation step (c), and the deasphalting step (d). There is no second fractionation step (e).
The heavy hydrocarbon feedstock 1 is sent via a pipe to an initial hydroconversion section A, at high hydrogen pressure 19. The section At is identical to that described in relation to FIG. 1. The liquid effluent 3 from from section Αί is separated in the intermediate separation section B, at the same time as the recycled DAO 15 from the deasphalter D. In the intermediate separation section Bi, the conditions are chosen so as to obtain two liquid fractions, a light fraction 4 and a heavy fraction 5. The section Bi can comprise any separation means known to those skilled in the art, and preferably does not include an atmospheric distillation column or a vacuum distillation column, but a steam stripping column or with hydrogen, and is more preferably constituted by a series of flash balloons, and even more preferably by a single flash balloon.
The heavy liquid fraction 5 at the outlet of the intermediate separation section B! is then sent to the second hydroconversion section A2 at high hydrogen pressure 20. This section A2 conforms to the description of the initial hydroconversion section A, of FIG. 1. The hydroconverted liquid effluent 6 obtained in l after this second hydroconversion step is separated in the first fractionation section C. In this section C, the conditions are chosen so as to obtain at least two liquid fractions, a light cut 11 and a heavy cut 13. The section preferably comprises using a set of flash balloons and an atmospheric distillation column.
The heavy cut 13 is then sent via a line into the deasphalter D to obtain a DAO which is recycled to the intermediate separation section B ^ and a residual asphalt 14 which is purged via another line.
The DAO is then mixed, in part or in whole as shown, with the liquid effluent 3 from the initial hydroconversion section A, and the mixture is then sent to the intermediate separation section B ^
FIG. 4 illustrates the invention in another preferred implementation comprising the recycling of the DAO at the entry of the last hydroconversion step.
According to this implementation, the method comprises the following successive stages: the initial hydroconversion stage (a ^, the intermediate separation stage (b ^, a second hydroconversion stage (a2) which is the only stage d additional hydroconversion, the first fractionation step (c), and the deasphalting step (d). There is no second fractionation step (e).
The heavy hydrocarbon charge 1 is sent via a pipe to an initial hydroconversion section Αί at high hydrogen pressure 19. The section At is identical to that described in relation to FIG. 1. The liquid effluent 3 from the section At is separated in the intermediate separation section Bi. In the separation section ΒΛ, the conditions are chosen so as to obtain two liquid fractions, a light fraction 4 and a heavy fraction 5. The section can include any separation means known to those skilled in the art, and preferably does not include neither an atmospheric distillation column nor a vacuum distillation column, but a steam or hydrogen stripping column, and is more preferably constituted by a series of flash balloons, and even more preferably by a single flash balloon.
The heavy liquid fraction 5 at the outlet of the intermediate separation section ΒΛ is then sent via a pipe in the second hydroconversion step A2 at high hydrogen pressure 20. This section A2 conforms to the description of the hydroconversion section initial At of FIG. 1. The hydroconverted liquid effluent 6 obtained at the end of this second hydroconversion step is separated in the first fractionation section C. In this section C, the conditions are chosen so as to obtain at least two liquid fractions, a light section 11 and a heavy section 13. The section preferably comprises a set of flash flasks and columns of atmospheric and vacuum distillation.
The heavy cut 13 is then sent via a pipe into the deasphalting machine D to obtain a DAO 15 which is recycled via a pipe to the second hydroconversion section A2 and a residual asphalt 14 which is purged via another pipe.
The DAO is then mixed, in part or in whole as shown, with the heavy liquid fraction 5 coming from the intermediate separation section ΒΛ and the mixture is then sent to the second hydroconversion section A2.
FIG. 5 illustrates the invention in another implementation not comprising an intermediate separation step.
According to this implementation, the method comprises the following successive stages: the initial hydroconversion stage (a ^, a second hydroconversion stage (a2) which is the only additional hydroconversion stage, the first fractionation stage ( c), and the deasphalting step (d). There is no second fractionation step (e).
The heavy hydrocarbon charge 1 is sent via a pipe to an initial hydroconversion section At at high hydrogen pressure 19. The section At is identical to that described in relation to FIG. 1. The liquid effluent 3 from the section At is then sent via a pipe to the second hydroconversion section A2 at high hydrogen pressure 20. This section A2 conforms to the description of the initial hydroconversion section At in FIG. 1. The liquid effluent hydroconverted 6 obtained at the end of this second hydroconversion step is separated in the first fractionation section C. In this section C, the conditions are chosen so as to obtain at least two liquid fractions, a light cut 11 and a cut heavy 13. The section preferably comprises using a set of flash flasks and atmospheric and vacuum distillation columns.
The heavy cut 13 is then sent via a pipe into the deasphalting machine D to obtain the DAO 15 which is recycled via a pipe to the second hydroconversion section A2 and a residual asphalt 14 which is purged via another pipe.
DAO 15 is mixed, in part or in whole as shown, with the liquid effluent 3 from the initial hydroconversion section A1; and the mixture is sent to the second hydroconversion section A2.
Examples
The following examples illustrate an example of implementation of the method according to the invention, without limiting its scope, and some of its performances, in comparison with methods according to the prior art.
Examples 1 and 2 are not in accordance with the invention. Examples 3 and 4 are in accordance with the invention.
Charge
The heavy hydrocarbon feedstock is a vacuum residue (RSV) originating from a Ural crude oil, the main characteristics of which are presented in Table 2 below.
table 2
This heavy load RSV is the same fresh load for the different examples.
Example 1: Process. of. reference without, recycling. of. / a DA O. [not in accordance with IJnventiqn)
This example illustrates a process for hydroconversion of a heavy hydrocarbon feedstock according to the state of the art comprising two successive hydroconversion stages each comprising a reactor operating in a bubbling bed, followed by a deasphalting stage without recycling of CAD.
First step, hydro-version
The fresh charge from Table 2 is sent entirely to a first hydroconversion section A '·, in the presence of hydrogen to undergo a first hydroconversion step (a'i), said section comprising a three-phase reactor containing a catalyst d 'NiMo / alumina hydroconversion having an NiO content of 4% by weight and a MoO3 content of 10% by weight, the percentages being expressed relative to the total mass of the catalyst. The reactor operates in a bubbling bed operating with an upward flow of liquid and gas.
The operating conditions applied in the first hydroconversion step are presented in Table 3 below.
table 3
These operating conditions make it possible to obtain a hydroconverted liquid effluent with a reduced content of Conradson carbon, of metals and of sulfur. The conversion of the 540 ° C + fraction at the outlet of the first hydroconvision stage is 43% by weight. Étape.de. Intermediate separation The hydroconverted liquid effluent from the first hydroconversion stage (a’i) is then sent to an intermediate separation section B5! composed by a single gas / liquid separator operating at the pressure and at the temperature of the reactor of the first hydroconversion stage. A light fraction and a so-called heavy fraction are thus separated. The light fraction is mainly composed of molecules with a boiling point below 350 ° C and the louide fraction is mainly composed of hydrocarbon molecules boiling at a temperature greater than or equal to 350 ° C.
The composition of this heavy fraction is presented in Table 4.
table 4
Second.step, d [hydr_oçonyersw. (A’g) ...
The heavy fraction, the composition of which is given in Table 4, is sent to a second hydroconversion section A’2 in the presence of hydrogen to undergo a second hydroconversion stage (a’2).
The second hydroconversion section A’2 comprises a three-phase reactor A’2 containing a NiMo / alumina hydroconversion catalyst having an NiO content of 4% by weight and a MoO3 content of 10% by weight, the percentages being expressed relative to
to the total mass of the catalyst. The section operates in a bubbling bed operating with an upward flow of liquid and gas.
The operating conditions applied in the second hydroconversion step (a’2) are presented in Table 5 below.
table 5
These operating conditions make it possible to obtain a hydroconverted liquid effluent with a reduced content of Conradson carbon, of metals and of sulfur. The conversion of the 540 ° C + fraction carried out during this second hydro-conversion stage is 38% by weight.
First stage. fractionation The hydroconverted liquid effluent from the hydroconversion stage (a'2) is sent to a fractionation stage (c ') carried out in a fractionation section C' composed of an atmospheric distillation column and a column vacuum distillation after which a boiling vacuum distillate fraction is recovered at a temperature essentially between 350 ° C and 500 ° C (DSV) and an ifaction vacuum residue not converted boiling at a temperature greater than or equal to 500 ° C (RSV) whose yields relative to the fresh load and product qualities are given in table 6 below.
table 6 Stage, of. deasphalting
The RSV from the distillation zone of the fractionation section C ’is then advantageously sent to a deasphalting step (d’) in a deasphalter D ’in
which it is treated in an extractor using the butane solvent under deasphalting conditions making it possible to obtain a DAO and a residual asphalt.
The operating conditions applied in the deasphalter are as follows: - Total pressure = 3 MPa; - Average temperature = 95 ° C; - Solvent / charge ratio = 8 v / v.
At the outlet of the deasphalt paver, a DAO and a residual asphalt are obtained, having the characteristics given in table 7 below.
table 7
PejÎOÆMÇesMÎQbales
With this conventional process, not in accordance with the invention, the overall conversion of the 540 ° C + fraction of the fresh feed is 64% by weight. The fraction of the vacuum residue not converted contains 0.20% by weight of sediments. β / fe.mpje.Procédé. with.recycling fa..DAO. at. .rentrée. of. the first step. d [hydroçonversion. (not.in accordance with the invention}
In this example 2, the state of the art is illustrated in a process for hydroconversion of a heavy hydrocarbon feedstock comprising two successive hydroconversion steps each comprising a reactor operating in a bubbling bed, followed by a step of deasphalting with a recycling of the DAO at the entry of the first hydroconversion stage.
First step, çf’hyçfroçon version
The fresh charge in Table 2 is first mixed with the DAO from the deasphalting step (d ”) in a volume ratio of fresh charge / DAO equal to 75/25. This mixture is then sent entirely to a first hydroconversion section A ”! in
presence of hydrogen to undergo a first hydroconversion step (aThis section A ”! is identical to that described in Example 1.
The conditions applied in this first hydroconversion section A ”! are shown in Table 8 below.
Table 8 The increase in the WH reactor, compared to the WH during the first hydroconversion stage according to Example 1, is due to the recycling of the DAO, the fresh charge flow rate being kept constant. These operating conditions make it possible to obtain a hydroconverted liquid effluent with a reduced content of Conradson carbon, of metals and of sulfur. The conversion by pass of the 540 ° C + fraction at the outlet of the first hydroconversion stage is 34% by weight. Intermediate separation step. The hydroconverted liquid effluent from the first hydroconversion step (a ”·,) is then sent to an intermediate separation section B”! composed by a single gas / liquid separator operating at the pressure and temperature of the reactor of the first hydroconversion stage. A light fraction and a heavy fraction are thus separated. The light fraction is mainly composed of molecules with a boiling point below 350 ° C and the so-called heavy fraction is mainly composed of hydrocarbon molecules boiling at a temperature greater than or equal to 350 ° C.
The composition of this heavy fraction is presented in Table 9.
table 9
Qeuxjème.étaped ^
The heavy fraction, the composition of which is given in Table 9, is sent entirely to a second hydroconversion section A ”2 in the presence of hydrogen to undergo a second hydroconversion step (a” 2). This section A ”2 is identical to that described in example 1.
The operating conditions applied during this second hydroconversion step (a ”2) are presented in table 10 below.
table 10
These operating conditions make it possible to obtain a hydroconverted liquid effluent with a reduced content of Conradson carbon, of metals and of sulfur. The conversion by pass of the 540 ° C + fraction carried out during this second hydroconversion step is 34% by weight.
First stage, fractionation The hydroconverted liquid effluent from the hydroconversion stage (a ”2) is sent a fractionation stage (c”) carried out in a fractionation section C ”composed of an atmospheric distillation column and d '' a vacuum distillation column after which a fraction is distilled under vacuum boiling at a temperature essentially between 350 ° C and 500 ° C (DSV) and a fraction residue under vacuum not converted boiling mainly at a higher temperature or equal to 500 ° C (RSV) whose yields relative to the fresh load and product qualities are given in table 11 below.
table 11 Stage, of. deasphalting
The RSV from the first fractionation section C ”is then advantageously sent to a deasphalting step (d”) in a deasphalter D ”, in which it is treated as described in example 1 (same equipment and same conditions).
At the outlet of the deasphalt paver, a DAO and a residual asphalt are obtained having the characteristics given in table 12 below.
table 12
After the deasphalt paver D, 16% of the DAO produced is purged, while the rest of the DAO, ie 84%, is sent upstream of the first hydroconversion stage (a ”·,).
Global performance
With this conventional process comprising a recycling of the DAO at the entry of the first hydroconversion stage, not in accordance with the invention, the overall conversion of the 540 ° C + fraction of the fresh feed is 71% by weight. The unconverted vacuum residue fraction contains 0.34% by weight of sediment.
Example 3.; Process according to. ([invention,. aimed at reducing. the. sediment content. of the residue under, unconverted vacuum
In this example, the process according to the invention is illustrated in an implementation comprising two successive hydroconversion stages each comprising a reactor operating in a bubbling bed followed by a deasphalting stage with recycling of the DAO at the inlet of the last hydroconversion reactor.
First stage. of hydrgggn. version
The fresh charge in Table 2 is sent in full to a first hydroconversion section At in the presence of hydrogen to undergo a first hydroconversion step (ai). This section At is identical to that described in example 1.
The operating conditions applied to this first hydroconversion step (ai) are presented in Table 13 below.
table 13
These operating conditions make it possible to obtain a hydroconverted liquid effluent with a reduced content of Conradson carbon, of metals and of sulfur. The conversion of the 540 ° C + fraction carried out during this first hydro-conversion stage is 43% by weight. Step. of. separation, intermediate The hydroconverted liquid effluent is then sent to an intermediate separation section ΒΛ composed by a single gas / liquid separator operating at the pressure and the temperature of the reactor of the first hydroconversion stage. A light fraction and a heavy fraction are thus separated. The light fraction is mainly composed of molecules with a boiling point below 350 ° C and the so-called heavy fraction is mainly composed of hydrocarbon molecules boiling at a temperature greater than or equal to 350 ° C.
The composition of this heavy fraction is presented in Table 14.
table 14
In this example of the method according to the invention, the heavy effluent from the intermediate separation section BΛ is mixed in full with the DAO from the deasphalting step (d) in a heavy effluent / DAO volume ratio of 75 / 25. The composition of this charge is presented in Table 15.
table 15
In this example according to the invention, this mixture is sent entirely to a second hydroconversion section A2 in the presence of hydrogen to undergo a second hydroconversion step (a2). Said section A2 is identical to that described in example 1.
The operating conditions applied in the hydroconversion step (a2) are presented in table 16 below.
table 16
These operating conditions make it possible to obtain a hydroconverted liquid effluent with a reduced content of Conradson carbon, of metals and of sulfur. The pass conversion of the 540 ° C + fraction carried out during this second hydroconversion step is 33% by weight.
First section; de.fractionation The hydroconverted liquid effluent from the hydroconversion stage (a2) is sent to a fractionation stage (c) carried out in a fractionation section C composed of an atmospheric distillation column and a vacuum distillation column following which a fraction is distilled under vacuum boiling at a temperature essentially between 350 ° C and 500 ° C (DSV) and a fraction residue under unconverted vacuum boiling at a temperature greater than or equal to 500 ° C (RSV) . The yields relative to the fresh load and product qualities are given from this first fractionation section are shown in Table 17 below.
table 17
Comparing with example 1, we notice a higher level of hydrotreatment with a lower density, lower contents of sulfur, nitrogen, metals, asphaltenes and Conradson carbon. In addition, RSV contains less sediment and is therefore more stable, in particular thanks to the presence of heavy aromatics from the DAO recycled before the second hydroconversion stage.
Comparing with Example 2, we notice that the hydrotreatment level is slightly lower, but that the RSV contains much less sediment. This cut is therefore more stable, in particular thanks to the presence of heavy aromatics from the recycled CAD cut upstream of the second hydroconversion stage. In Example 2, the DAO is recycled upstream of the first hydroconversion stage and the heavy aromatics are more hydrogenated compared to the process according to the invention. Step, from. deasphalting
The RSV from the first fractionation section is then advantageously sent to a deasphalting step (d) in a deasphalter, in which it is treated as described in example 1 (same equipment and same conditions).
At the outlet of the deasphalt paver, a DAO and a residual asphalt are obtained having the characteristics given in table 18 below.
table 18 PMQiWanœs .globales
According to the process of the invention illustrated in this example, comprising a recycling of the DAO at the last hydroconversion stage with a recycle ratio of 0.56, an overall conversion of the 540 ° C. fraction + of the fresh charge is achieved. 71% by weight for identical operating conditions (i.e. 7 more conversion points). The unconverted fraction, the vacuum residue, contains 0.07% by weight of sediment.
It is therefore noted that, compared to Example 1, the conversion is higher and that the RSV which leaves the vacuum distillation column in the first fractionation stage is more stable, since it contains less sediment. Compared to Example 2, the overall conversion is identical, but the residual RSV contains much less sediment. Ê * e / r P / e, 4,:. Process..as lin lin yentjon, aiming at .aujrement..the .. globafe conversion from there. fraction 540 ° C +
In this example, the process according to the invention is illustrated in an implementation comprising two successive hydroconversion stages each comprising a reactor operating in a bubbling bed followed by a deasphalting stage with recycling of the DAO at the inlet of the last hydroconversion reactor. As the sediment content is reduced in the process according to the invention, this latter reactor will be operated under more severe conditions in order to increase the overall conversion of the process.
First step_ of hydroçon version
The fresh charge in Table 2 is sent in full to a first hydroconversion section ΑΛ in the presence of hydrogen to undergo a first hydroconversion step (ai). This section Ai is identical to that described in Example 1.
The operating conditions applied to this first hydroconversion step (ai) are presented in Table 19 below.
table 19
These operating conditions make it possible to obtain a hydroconverted liquid effluent with a reduced content of Conradson carbon, of metals and of sulfur. The conversion of the 540 ° C + fraction carried out during this first hydro-conversion stage is 43% by weight. Step. of. separation, intermediate The hydroconverted liquid effluent is then sent to an intermediate separation section ΒΛ composed by a single gas / liquid separator operating at the pressure and the temperature of the reactor of the first hydroconversion stage. A light fraction and a heavy fraction are thus separated. The light fraction is mainly composed of molecules with a boiling point below 350 ° C and the so-called heavy fraction is mainly composed of hydrocarbon molecules boiling at a temperature greater than or equal to 350 ° C.
The composition of this heavy fraction is presented in Table 20.
table 20
Peuxjème.étapepWyd.roçgnve.r.sipn.
In this example of the method according to the invention, the heavy effluent from the intermediate separation section BΛ is mixed in full with the DAO from the deasphalting step (d) in a heavy effluent / DAO volume ratio of 75 / 25. The composition of this charge is presented in Table 21.
table 21
In this example according to the invention, this mixture is sent entirely to a second hydroconversion section A2 in the presence of hydrogen to undergo a second hydroconversion step (a2). Said section A2 is identical to that described in example 1.
The operating conditions applied in the hydroconversion stage (a2) are presented in table 22 below. Compared to the other examples, the reaction temperature was increased by 5 ° C.
table 22
These operating conditions make it possible to obtain a hydroconverted liquid effluent with a reduced content of Conradson carbon, of metals and of sulfur. The pass conversion of the 540 ° C + fraction carried out during this second hydroconversion step is 38% by weight.
First section; de.fractionation The hydroconverted liquid effluent from the hydroconversion stage (a2) is sent to a fractionation stage (c) carried out in a fractionation section C composed of an atmospheric distillation column and a vacuum distillation column following which a fraction is distilled under vacuum boiling at a temperature essentially between 350 ° C and 500 ° C (DSV) and a fraction residue under unconverted vacuum boiling at a temperature greater than or equal to 500 ° C (RSV) . The yields relative to the fresh load and product qualities are given from this first fractionation section are shown in Table 23 below.
table 23
Comparing with example 1, we notice a higher level of hydrotreatment with a lower density, lower contents of sulfur, nitrogen, metals, asphaltenes and Conradson carbon. Despite the highest severity, RSV contains the same sediment content and therefore remains stable, in particular thanks to the presence of heavy aromatics from the DAO recycled upstream of the second hydroconversion stage.
Comparing with Example 2, we notice that the level of hydrotreatment is very similar, but that the RSV contains less sediment. This cut is therefore more stable, in particular thanks to the presence of heavy aromatics from the recycled CAD cut upstream of the second hydroconversion stage. In Example 2, the DAO is recycled upstream of the first hydroconversion stage and the heavy aromatics are more hydrogenated compared to the process according to the invention. Step, see deasphalting
The RSV from the first fractionation section is then advantageously sent to a deasphalting step (d) in a deasphalter, in which it is treated as described in example 1 (same equipment and same conditions).
At the outlet of the deasphalt paver, a DAO and a residual asphalt having the characteristics given in table 24 below are obtained.
table 24
Overall performance
According to the process of the invention illustrated in this example, comprising a recycling of the DAO at the last hydroconversion stage operated under more severe conditions, an overall conversion of the 540 ° C + fraction of the fresh charge of 73% is achieved. weight for identical operating conditions. The unconverted fraction, the vacuum residue, contains 0.19% by weight of sediment.
It is therefore noted that, compared to example 1, the conversion is much higher (+10 conversion points), but that the RSV which leaves the vacuum distillation column at the first fractionation stage remains stable, because it contains approximately the same sediment content. Compared to Example 2, the conversion is higher (+3 conversion points), but the residual RSV contains much less sediment and remains stable under these more severe conditions.

权利要求:
Claims (19)
[1" id="c-fr-0001]
1. Process for the conversion of a heavy load of hydrocarbons containing a fraction of at least 50% having a boiling temperature of at least 300 ° C, and containing sulfur, Conradson carbon, metals, and nitrogen, comprising the following successive stages: - an initial hydroconversion stage (a ^ of at least part of said heavy hydrocarbon charge in the presence of hydrogen in an initial hydroconversion section (A ^, carried out under conditions making it possible to obtain a liquid effluent with a reduced sulfur, Conradson carbon, metal, and nitrogen content; - (n-1) additional hydroconversion step (s) (a, ·) in (n-1) additional hydroconversion section (s) (A, ·), in the presence of hydrogen, at least part or all of the liquid effluent from the hydroconversion step previous (ar1) or possibly a heavy fraction from an optional step of interm separation ediary (by) in an intermediate separation section (By) between two consecutive hydroconversion steps separating part or all of the liquid effluent from the previous hydroconversion step (a / .i) to produce at least a heavy fraction boiling mainly at a temperature greater than or equal to 350 ° C., the (n-1) additional hydroconversion step (s) (al) being carried out so as to obtain a hydroconverted liquid effluent with reduced content sulfur, Conradson carbon, metals, and nitrogen, n being the total number of hydroconversion steps, with n greater than or equal to 2, / 'being an integer ranging from 2 to n and y being an integer ranging from 1 to (n-1), and the initial hydroconversion sections (A ^ and additional (s) (A, ·) each comprising at least one three-phase reactor containing at least one hydroconversion catalyst; - a first fractionation stage (c) in a first fractionation section (C) of part or all of the hydroconverted liquid effluent from the last additional hydroconversion stage (an) producing at least one heavy cut boiling mainly at a temperature greater than or equal to 350 ° C, said heavy cut containing a residual fraction boiling at a temperature greater than or equal to 540 ° C; - a deasphalting step (d) in a deasphalting machine (D) of part or all of said heavy cut resulting from the fractionation step (c), with at least one hydrocarbon solvent, in order to obtain a DAO deasphalted oil and residual asphalt; - optionally a second fractionation step (e) in a second fractionation section (E) of part or all of the DAO resulting from the deasphalting step (d) into at least one heavy fraction of DAO and a light fraction of DAO; a recycling step (f) of at least part of the DAO from step (d) and / or at least part of the heavy fraction of the DAO from step (e) to an additional hydroconversion step (a, ·) and / or an intermediate separation step (b /).
[2" id="c-fr-0002]
2. The method of claim 1, wherein said heavy hydrocarbon feed has a sulfur content of at least 0.1% by weight, a Conradson carbon content of at least 0.5% by weight, an asphaltenes content C7 of at least 1% by weight, and a metal content of at least 20 ppm by weight.
[3" id="c-fr-0003]
3. Method according to any one of the preceding claims, in which said heavy hydrocarbon charge is crude oil or consists of atmospheric residues and / or vacuum residues resulting from atmospheric distillation and / or under vacuum of a crude oil, and preferably consists of vacuum residues from the vacuum distillation of crude oil.
[4" id="c-fr-0004]
4. Method according to any one of the preceding claims, in which said three-phase reactor containing at least one hydroconversion catalyst is a three-phase reactor operating in a bubbling bed, with an updraft of liquid and gas.
[5" id="c-fr-0005]
5. Method according to any one of the preceding claims, in which said three-phase reactor containing at least one hydroconversion catalyst is a three-phase reactor operating in a hybrid bed, said hybrid bed comprising at least one catalyst maintained in said three-phase reactor and at least a catalyst driven out of said three-phase reactor.
[6" id="c-fr-0006]
6. Method according to any one of the preceding claims, in which the initial hydroconversion step (ai) is carried out under an absolute pressure of between 2 and 38 MPa, at a temperature between 300 ° C and 550C, at a hourly space velocity WH with respect to the volume of each three-phase reactor of between 0.05 h "1 and 10 h" 1 and with an amount of hydrogen mixed with the heavy hydrocarbon charge of between 50 and 5000 normal cubic meters (Nm3) per cubic meter (m3) of heavy hydrocarbon load.
[7" id="c-fr-0007]
7. Method according to any one of the preceding claims, in which the additional hydroconversion step or steps (an) are carried out at a temperature between 300 ° C and 550 ° C, and higher than the temperature operated in step initial hydroconversion (a ^, in an amount of hydrogen mixed with the heavy hydrocarbon charge between 50 and 5,000 normal cubic meters (Nm3) per cubic meter (m3) of heavy hydrocarbon charge, and less than the amount d hydrogen operated in the initial hydroconversion stage (ai), under an absolute pressure between 2 and 38 MPa, and at an hourly space speed WH relative to the volume of each three-phase reactor between 0.05 h'1 and 10:01 a.m.
[8" id="c-fr-0008]
8. Method according to any one of the preceding claims, in which the intermediate separation section (B /) comprises one or more flash balls arranged in series, and / or one or more columns of stripping with steam and / or hydrogen, and / or an atmospheric distillation column, and / or a vacuum distillation column, and is preferably constituted by a single flash balloon.
[9" id="c-fr-0009]
9. Method according to any one of the preceding claims, in which the first fractionation section (C) comprises one or more flash flasks arranged in series, and / or one or more columns of steam stripping and / or hydrogen, and / or an atmospheric distillation column, and / or a vacuum distillation column, and is preferably constituted by a set of several flash flasks in series and atmospheric and vacuum distillation columns.
[10" id="c-fr-0010]
10. Method according to any one of the preceding claims, in which the second fractionation section (E) comprises one or more flash balls arranged in series, and / or one or more columns of stripping with steam and / or hydrogen, and / or an atmospheric distillation column, and / or a vacuum distillation column, and is preferably constituted by a set of several flash flasks in series and a vacuum distillation column.
[11" id="c-fr-0011]
11. Method according to any one of the preceding claims, in which the deasphalting step (d) is carried out in an extraction column at a temperature between 60 ° C and 250 ° C with at least one hydroarbon solvent having 3 to 7 carbon atoms, and a solvent / charge ratio (volume / volume) of between 3/1 and 16/1, and preferably between 4/1 and 8/1.
[12" id="c-fr-0012]
12. Method according to any one of the preceding claims, in which a part of the heavy hydrocarbon charge is sent into at least one additional hydroconversion section (A, ·) and / or into at least one intermediate separation section. (By) and / or in the first fractionation section (C) and / or in the deasphalter (D).
[13" id="c-fr-0013]
13. Process according to any one of the preceding claims, in which an external hydrocarbon charge is sent to the process in the initial hydroconversion section (A ^ and / or in at least one additional hydroconversion section (A, · ) and / or in at least one intermediate separation section (By) and / or in the first fractionation section (C) and / or in the deasphalter (D).
[14" id="c-fr-0014]
14. Method according to any one of the preceding claims, further comprising at least one following recycling step: - recycling (n) part or all of the light fraction of the DAO resulting from step ( e) in the initial hydroconversion section (A ^ and / or in at least one additional hydroconversion section (A, ·) and / or in at least one intermediate separation section (By) and / or in the first section fractionation (C); - recycling (r2) of part of the heavy fraction of the DAO from step (f) in the first fractionation section (C); - recycling (r3) of a part of the DAO from step (d) in the first fractionation section (C); - recycling (r4) of part or all of the residual asphalt from step (d) in the initial hydroconversion section (A ^ and / or in at least one additional hydroconversion section (A, ·); - recycling ( r5) of part of the hydroconverted liquid effluent from an additional hydroconversion section (A, ·) given: - in the initial hydroconversion section (A ^, and / or - in another hydroconversion section additional (A, ·) positioned upstream of said given section (A, ·), and / or - in an intermediate separation section (By) positioned upstream of said given section (A, ·); - recycling (r6) of part of the heavy fraction and / or part or all of one or more intermediate fractions from a given intermediate section (By): - in the hydroconversion section initial (A ^, and / or - in an additional hydroconversion section (A, ·) positioned upstream of said given intermediate section (By), and / or - in another intermediate separation section (By) positioned upstream of said given section (By); - recycling (r7) of part of the heavy fraction and / or part or all of one or more intermediate fractions from the first fractionation section (C) : - in the initial hydroconversion section (A ^, and / or - in an additional hydroconversion section (A, ·), and / or - in an intermediate separation section (By).
[15" id="c-fr-0015]
15. Conversion process according to any one of the preceding claims, in which n is equal to 2, and comprising the following successive steps: - an initial hydroconversion step (a ^ of at least part of said heavy charge d hydrocarbons in the presence of hydrogen in an initial hydroconversion section (A ^, carried out under conditions making it possible to obtain a liquid effluent with reduced sulfur, Conradson carbon, metal and nitrogen content; - a step d additional hydroconversion (a2) in an additional hydroconversion section (A *), in the presence of hydrogen, of at least some or all of the liquid effluent from the initial hydroconversion step (ar) or possibly a heavy fraction from an optional intermediate separation step (bj) in an intermediate separation section (B,) between the initial (a ) and additional (a2) hydroconversion steps separating part or all of the liquid effluent from the initial hydroconversion stage (a ) into at least one light fraction boiling mainly at a temperature below 350 ° C and at least one heavy fraction boiling mainly at a temperature greater than or equal to 350 ° C., the additional hydroconversion epile (a2) being produced so as to obtain a hydroconverted liquid effluent with reduced sulfur, Conradson carbon, metals, and nitrogen content, the hydroconversion sections initial (A ^ and additional (A2) each comprising at least one three-phase reactor containing at least one hydroconversion catalyst; a first fractionation step (c) in a first fractionation section (C) of part or all of the hydroconverted liquid effluent from the additional hydroconversion step (a2) producing at least one heavy cut boiling mainly at a temperature greater than or equal to 350 ° C, said heavy cut containing a residual fraction boiling at one at a temperature greater than or equal to 540 ° C; - a deasphalting step (d) in a deasphalting machine (D) of part or all of said heavy cut resulting from the fractionation step (c), with at least one hydrocarbon solvent, in order to obtain a DAO deasphalted oil and residual asphalt; - optionally a second fractionation step (e) in a second fractionation section (E) of part or all of the DAO resulting from the deasphalting step (d) into at least one heavy fraction of DAO and a light fraction of DAO; a recycling step (f) of at least part of the DAO from step (d) and / or at least part of the heavy fraction of the DAO from step (e) to an additional hydroconversion step (a2) and / or an intermediate separation step (b,).
[16" id="c-fr-0016]
16. Method according to any one of the preceding claims, comprising the recycling (f) of all of the DAO resulting from stage (d) or of all of the heavy fraction resulting from the second fractionation stage (e) in the last additional hydroconversion step (a, ·), and preferably in the additional hydroconversion step (a2) when n is equal to 2 and that in addition all of the liquid effluent from the step (a ^ is sent to step (b ^, all of the heavy fraction from step (b ^ is sent to step (a2), all of the hydroconverted liquid effluent from step (a2) is sent in step (c), and the entire heavy cut from step (c) is sent to step (d).
[17" id="c-fr-0017]
17. A method according to any one of claims 1 to 15, comprising recycling (f) all of the DAO from step (d) or all of the heavy fraction from the second fractionation step ( e) at an intermediate separation step (by), and preferably at the intermediate separation step (bi) between the initial hydroconversion step (ai) and the additional hydroconversion step (a2) when n is equal to 2 and that in addition all of the liquid effluent from step (ai) is sent to step (bi), all of the heavy fraction from step (bi) is sent to step (a2), all of the hydroconverted liquid effluent from step (a2) is sent to step (c), and all of the heavy cut from step (c) is sent in step (d).
[18" id="c-fr-0018]
18. Method according to any one of claims 1 to 15, not comprising an intermediate separation step (by) and comprising recycling (f) of all of the DAO from step (d) to the last additional hydroconversion step (a, ·), and preferably in the additional hydroconversion step (a2) when n is equal to 2 and that in addition all of the liquid effluent from step (a ^ is sent to step (a2), all of the hydroconverted liquid effluent from step (a2) is sent to step (c), and all of the heavy cut from step ( c) is sent to step (d).
[19" id="c-fr-0019]
19. Method according to any one of claims 1 to 18, in which said hydroconversion catalyst of said at least one three-phase reactor of the initial hydroconversion section (A ^ and of the additional hydroconversion section (s)) (A /) contains at least one non-noble group VIII metal chosen from nickel and cobalt and at least one group VIB metal chosen from molybdenum and tungsten, and preferably comprising an amorphous support.

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EP3728518A1|2020-10-28|

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FR3075809B1|2020-09-11|

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US20200339894A1|2020-10-29|

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RU2020123948A|2022-01-21|

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US11149217B2|2021-10-19|

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CN111819268A|2020-10-23|

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RU2020123948A3|2022-01-21|

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FR3033797B1|2015-03-16|2018-12-07|IFP Energies Nouvelles|IMPROVED PROCESS FOR CONVERTING HEAVY HYDROCARBON LOADS|FR3101082B1|2019-09-24|2021-10-08|Ifp Energies Now|Integrated fixed bed hydrocracking and bubbling bed hydroconversion process with improved gas / liquid separation|

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法律状态:
2018-12-19| PLFP| Fee payment|Year of fee payment: 2 |

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2019-06-28| PLSC| Publication of the preliminary search report|Effective date: 20190628 |

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2019-12-23| PLFP| Fee payment|Year of fee payment: 3 |

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2020-12-29| PLFP| Fee payment|Year of fee payment: 4 |

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2021-12-27| PLFP| Fee payment|Year of fee payment: 5 |

优先权:

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申请号 | 申请日 | 专利标题

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FR1762868|2017-12-21|

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FR1762868A|FR3075809B1|2017-12-21|2017-12-21|PROCESS FOR CONVERTING HEAVY LOADS OF HYDROCARBONS WITH RECYCLE OF A DESASPHALTED OIL|FR1762868A| FR3075809B1|2017-12-21|2017-12-21|PROCESS FOR CONVERTING HEAVY LOADS OF HYDROCARBONS WITH RECYCLE OF A DESASPHALTED OIL|

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EP18814904.1A| EP3728518A1|2017-12-21|2018-12-07|Method for converting heavy hydrocarbon feedstocks with recycling of a deasphalted oil|

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CN201880090040.6A| CN111819268A|2017-12-21|2018-12-07|Process for converting heavy hydrocarbon feedstocks with recycled deasphalted oil|

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RU2020123948A| RU2020123948A3|2017-12-21|2018-12-07|

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PCT/EP2018/084052| WO2019121073A1|2017-12-21|2018-12-07|Method for converting heavy hydrocarbon feedstocks with recycling of a deasphalted oil|

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US16/957,078| US11149217B2|2017-12-21|2018-12-07|Method for converting heavy hydrocarbon feedstocks with recycling of a deasphalted oil|