• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    The present invention relates to a process for converting petroleum feedstocks whose boiling curve is such that less than 20% by weight of the feedstock is distilled at a temperature of 343 ° C under ambient conditions, and more than 40% by weight of the feed is distilled at a temperature above 500 ° C, comprising: - a first deasphalting with a heavy solvent comprising a saturated hydrocarbon content having at least 5 carbon atoms greater than or equal to 95%, - a second deasphalting on the the deasphalted oil from the first deasphalting, with a light solvent comprising a saturated hydrocarbon content having 3 or 4 carbon atoms greater than or equal to 95%, - the deasphalted oil from the second deasphalting is converted by catalytic cracking, - the pitch resulting from the second deasphalting is converted by visbreaking.
    公开号:BE1019627A3
    申请号:E200900756
    申请日:2009-12-07
    公开日:2012-09-04
    发明作者:Helene Leroy；Didier Chombart
    申请人:Total Raffinage Marketing；
    IPC主号:
    专利说明:

    METHOD FOR ENHANCING HEAVY RAIN AND RESIDUES
    PETROLEUM
    The invention relates to the treatment of heavy crudes and petroleum residues, for example resulting from the atmospheric distillation or the vacuum distillation of a petroleum fraction. More specifically, it relates to hydrocarbon feedstocks derived from petroleum whose boiling curve is such that less than 20% by weight of the cup is distilled at the temperature of 343 ° C under ambient conditions.
    Crudes, in general, have varying levels of atmospheric residues that depend at least in part on their origin. This content typically varies between 10-50% by weight for conventional crudes, but can reach 50 to 80% by weight for heavy and extra heavy crudes such as those produced in Venezuela or the Athabasca region in northern Canada. These crudes generally have a density of less than 20 ° API.
    The heavier part of the heavy hydrocarbon feeds consists of a mixture of an oily phase and an asphaltic phase. It is usual to distinguish two families in the compounds constituting the asphaltic phase: resins and asphaltenes.
    Asphaltenes, like resins, include polycyclic aromatic structures, thiophene rings and pyridine rings. The resins include molecules having less condensed structures and lower molecular weights than structures present in asphaltenes.
    Petroleum residues contain heteroatoms. Thus, there are sulfur compounds in "large" quantity, typically: - the sulfur content (S) is 0.5 to 7% by weight relative to the total weight of the filler, - nitrogen compounds, typically the content nitrogen varies from 0.05 to 1% by weight relative to the total weight of the filler, - metals, Ni, V and possibly Fe ....
    These heteroatoms are generally not distributed uniformly in all fractions. Thus, very often metals are found mainly in the "Asphaltenes" fraction, while sulfur and nitrogen are more concentrated in the "Asphaltenes" and "Resins" fractions.
    A trend has emerged in recent years to seek to recover oil residues, which is relatively difficult. Indeed, the market is mainly requesting distillable fuels at atmospheric pressure at a temperature below 320-360 ° C. It is therefore useful, if not necessary, to convert these heavy residues to produce smaller molecules.
    The applicant has described in the patent application EP 0 246 956 the use of a deasphalting in two successive steps. The first deasphalting being carried out with a mixture of heavy solvents to precipitate the asphaltenes and the second with a mixture of light solvents to precipitate the resins. This process was aimed at producing a deasphalted oil which can be used as a filler for catalytic cracking. Indeed, a way to obtain light products from the oily phase is to submit it to a catalytic cracking. However, the catalytic cracking feedstock must not contain too many metals or have a "Conradson" residue that is too high. It may be recalled that the "Conradson" residue gives indications of the tendency of a product to form coke.
    The present invention aims to optimize the conversion of the residues in their entirety, that is to say including asphaltenes, resins, etc.. to produce light cuts and to enhance the heavy part having a boiling point higher than 500 ° C.
    Thus, according to a first aspect, the subject of the invention is a process for converting petroleum feeds whose boiling curve is such that less than 20% by weight of the feedstock is distilled at the temperature of 343 ° C. under the conditions ambient, and more than 40% by weight of the filler is distilled at a temperature above 500 ° C, comprising: - a first deasphalting of said filler with a heavy solvent comprising a content of saturated hydrocarbons having at least 5 carbon atoms higher or equal to 95%, a second deasphalting of the deasphalted oil resulting from the first deasphalting, with a light solvent comprising a saturated hydrocarbon content having 3 or 4 carbon atoms greater than or equal to 95%, the deasphalted oil resulting from the second deasphalting is converted by catalytic cracking (FCC), the pitch from the second deasphalting is converted by visbreaking.
    The petroleum feedstock according to the present invention can be for example a heavy crude oil, an atmospheric residue and / or a vacuum residue from the distillation of a crude oil.
    The combination of the process steps, that is to say the double deasphalting, the FCC and the visbreaking, can make it possible to obtain a process for the overall recovery of the residues with a greater margin compared to what was done before, while maintaining good product qualities and increasing yields of converted products.
    This invention therefore proposes a process in which the conversion is optimized by first separating the residue into different fractions, these different fractions then being converted by suitable methods. This results in a substantial gain in performance, the conversion being optimized and the yields and qualities of products in light cuts being improved.
    The successive deasphalting in two stages, the first being carried out by contacting with a heavy solvent, preferably C5-C7, and the second by a light solvent, preferably C3-C4, allows to optimize the yield in section DAO (deasphalted oil in English: DeAsphalted Oil) rich in hydrogen, in particular content greater than or equal to 11% by weight, containing few metals, in particular a content of less than or equal to 40 ppm and preferably less than or equal to 5 ppm, and precursors of coke, especially no asphaltenes.
    The initial elimination of "Asphaltenes" by contact with the heavy solvent, especially C5-C7, then allows by the implementation of a second C3-C4 deasphalting, a much more effective and selective separation between the " Resins "and the" Saturated "and" Aromatic "fractions. This results in an improvement in the yield of the DAO cut, with a similar content of metals and asphaltenes, compared to a deasphalting comprising a single step with a light solvent.
    The main advantage of the implementation of the process according to the invention is that the resin content is higher in the visbreductor charge. This may in particular allow an increase in the conversion of the visbreducer. Indeed, when the charge of the visbroeductor has a high content of resins, it may have a better crackability, and therefore a better visbreaking behavior. In the present invention, improving the stability of the visbroken effluent is improved, which may allow in order to obtain equivalent stability to work at a lower visbreaking temperature.
    In addition, the pitch resulting from the second deasphalting, intended to be used as a visor-reducing agent, has a better stability due to the elimination of the most unstable asphaltenes.
    Moreover, the amount of pitch intended for example to be used as a solid fuel, is generally lower than a sequence of processes comprising a single deasphalting.
    Preferably, the solvent of the first deasphalting is an n-paraffin having from 5 to 7 carbon atoms.
    The solvent of the second deasphalting may consist of n-paraffin having 3 or 4 carbon atoms.
    In particular, the solvent of the first deasphalting is n-pentane and the solvent of the second deasphalting is propane and / or n-butane.
    The heavy solvent of the first deasphalting may comprise a content of saturated hydrocarbons having at least 5 carbon atoms, especially an n-paraffin having 5 to 7 carbon atoms, and in particular n-pentane, greater than or equal to 95%, even be composed of such hydrocarbons.
    The light solvent of the second deasphalting may comprise a content of saturated hydrocarbons having 3 or 4 carbon atoms, in particular at least one n-paraffin having 3 or 4 carbon atoms, and in particular propane and / or n-butane, which is greater than or equal to 95%, or even consist of such hydrocarbons.
    Figure 1 illustrates the method according to the invention.
    A petroleum feedstock (10) is distilled under atmospheric conditions, in an atmospheric distillation column (1), and produces a substantial amount of a cut (11) of atmospheric residue or RAT.
    In general, the cup (11) contains less than 20% by weight of distillable molecules at 343 ° C. under these conditions and at least 40% by weight relative to the weight of the cut treated above 500 ° C. C at atmospheric pressure.
    According to a preferred embodiment of the invention, this feed is distilled under vacuum in a column (2) for collecting a vacuum distillate (12), called DSV and a vacuum residue (13) called RSV. The DSV and RSV sections are cut at a temperature varying according to the crudes in a temperature range generally ranging from 480 to 565 ° C.
    The DSV cut contains no or few Ni and V metals (<2 ppm) and the asphaltene content of the feed is less than or equal to 1% and most often 500 ppm. Its hydrogen content is greater than or equal to 11% by weight, and most often greater than or equal to 11.5% by weight.
    The RSV cut contains most of the asphaltenes and metals contained in the feed (10). Generally, the content of metals, in particular Ni + V, varies from 100 to 800 ppm depending on the charges treated. The viscosity of this section is important, especially ranging from 50 to 2000 Cst at 150 ° C, typically about 400 Cst.
    Part of the RSV (15) is then sent to the first deasphalting step (3), in which the residue is brought into contact with a heavy solvent consisting essentially of saturated hydrocarbon molecules containing from 5 to 7 carbon atoms, preferably from pentane, n-hexane or n-heptane.
    After contact, two phases are formed, one consisting of the parts of the non-soluble residue in the solvent is said phase Brai or Asphalt (17), the other consisting of the solvent and parts of the soluble residue. The solvent is distilled off from the soluble parts and recycled internally to the deasphalting process (3). It is obtained a soluble fraction (16) said phase cut DAO for cutting "DesAsphalted Oil".
    This fraction (16) is then sent to the second deasphalting step (4), in which it is brought into contact with a light solvent consisting essentially of saturated hydrocarbon molecules containing from 3 to 4 carbon atoms, preferably n-propane or n-butane.
    After contact, two phases are formed, one consisting of the parts of the non-soluble residue in the light solvent is said phase Brai or Resin (19), the other consisting of the solvent and parts of the soluble residue. The solvent is distilled off from the soluble parts and recycled internally to the deasphalting process (4). The solvent-free soluble fraction (18) is called the DAO cutting phase resulting from the second deasphalting. The DAO cut (18) contains small amounts of metals, Ni + V <35 ppm, which can vary depending on the solvents used.
    In a preferred form of the invention and according to FIG. 1, the vacuum distillate (12) originating from the vacuum distillation (2) of the crude oil is sent to catalytic cracking (5) mixed with the resulting deasphalted oil. second deasphalting (18) to produce the feedstock (20) of the fluidized bed catalytic cracking (FCC) process. In this mixture, the metal content is preferably less than 2 ppm, the asphaltenes content preferably less than 500 ppm and the hydrogen content greater than 11% by weight, preferably 11.5% by weight. The characteristics of this feed are favorable to catalytic cracking. Preferably, the deasphalted oil resulting from the second deasphalting represents up to 50%, preferably up to 30%, of the total charge of the catalytic cracking.
    It would also be possible to treat in FCC only DAO, the DSV cut being treated in other processes.
    According to another mode, the DSV (12) is partially treated with FCC mixed with the DAO (18), the other part being treated elsewhere.
    The catalytic cracking is carried out in a reaction zone containing a reaction chamber and a catalyst regeneration chamber between which the catalyst circulates continuously. The filler (20) is vaporized on contact with hot regenerated catalyst and reacts with the catalyst in the reactor. The reaction temperature is typically between 500 and 600 ° C, preferably 520-540 ° C, the ratio between the catalyst flow and the feed rate being between 4 and 15, preferably between 5 and 8. The products of reaction are then separated by distillation downstream of the reactor. The catalyst is regenerated by combustion with air to remove coke deposited during the reaction and heat the catalyst. All the coke produced by cracking is therefore consumed by combustion during regeneration.
    On the other hand, the resin or pitch fraction resulting from the second deasphalting (19) is sent to the visbreaking unit (5).
    In a preferred form of the invention and according to FIG. 1, the vacuum residue (14) resulting from the vacuum distillation (2) of the crude oil is sent to the visor reducer (6) in mixture with the pitch resulting from the second deasphalting (19) to produce the charge (21) of the visbreaking unit (5).
    Preferably, when the vacuum residue is sent into the visbreductor in mixture with the pitch resulting from the second deasphalting, the pitch resulting from the second deasphalting represents up to 50%, preferably up to 30%, of the total charge of the visbreaking agent.
    According to a preferred embodiment of the invention, the pitch resulting from the first deasphalting is used as a solid fuel.
    Examples
    We have evaluated the performance of the conversion scheme according to the invention, to evaluate the vacuum residues A and B whose properties are reported in Table 1 below.
    Table 1: Properties of
    vacuum residues studied
    We have studied the performances, in particular in visbreaking, that are obtained through two ways: According to the first way, known to those skilled in the art, a vacuum residue B is sent to the visbreducer.
    According to the second channel according to the invention (for example see FIG. 1), a vacuum residue A undergoes two successive deasphalting operations. The first deasphalting is carried out in the presence of n-pentane. The deasphalted oil from the first deasphalting undergoes a second deasphalting with n-propane. Then, the pitch resulting from this second deasphalting is sent, mixed with a portion of the vacuum residue B, to the visbreaking agent.
    Deasphalting tests:
    An autoclave configured in deasphalting mode is used. The feedstock is introduced into the autoclave in the presence of the deasphalting solvent according to the desired level of solvent volume. The temperature and pressure of the test are adjusted according to the type of solvent chosen and the quality of the desired DAO.
    The mixture is kept stirred under the same conditions for at least one hour and then allowed to settle for another hour. The upper phase "DAO" is removed by the quilting of the medium until the solvent appears. The lower "pitch" phase is then withdrawn by the bottom quill until the remaining DAO appears (mixture DAO / pitch, said intermediate phase). The determination of the densities of the DAO, the pitch and this intermediate phase makes it possible to calculate precisely the yields in DAO and pitch.
    Visbreaking tests
    The methodology is to use an autoclave configured in visbreaking mode. Viscoreduction of the charge is carried out in the stirred autoclave and heated at two different temperatures.
    The gases generated by the cracking are condensed and recovered at the main condenser cooled to -10 ° C and the secondary condenser cooled to -80 ° C. The remaining gases are counted and collected (manual piston) in the middle and end of the test.
    The liquid effluent is recovered and analyzed (stability, sediments, density and viscosity at 100 ° C).
    The stability measurement is measured by the stability limit, also called S-value according to ASTM D7157. When the S-value of the visbroken effluent is higher, it is considered to be more stable.
    1st deasphalting
    The first deasphalting is carried out on the vacuum residue A, of which Table 1 groups the properties. The solvent used is n-pentane, under the following conditions: • Solvent content: 2.75 v / v.
    • Pressure: 40 bar
    • Temperature: 170 ° C
    The characteristics of the DAO cut obtained after this first deasphalting with n-pentane are collated in Table 2.
    Table 2: Properties of the DAO cut resulting from the 1st deasphalting with n-oentane
    from RSV A
    2nd deasphalting
    The second deasphalting is carried out with n-propane, on the DAO obtained during the first deasphalting, under the following conditions: • Solvent content: 6 v / v.
    • Pressure: 40 bar
    • Temperature: 60 ° C
    The characteristics of the DAO and pitch cuts obtained after this second deasphalting with n-propane are collated in Table 3.
    Table 3: Properties of DAO cuts and pitch from 2nd deasphalting
    n-propane
    The second deasphalting with n-propane makes it possible to concentrate the resins in the pitch. This cut is also very aromatic, and has a low proportion of saturated compounds.
    visbreaking
    The visbreaking is carried out for each of the channels at two different cracking temperatures: 434 ° C. and 436 ° C.
    The cracking temperature is defined as being the temperature found in the autoclave configured in vis-reduction mode.
    Table 4 below indicates the composition of the charge of the visbreaking process in the two routes envisaged. It can be seen that the load is lighter when C3 pitch from the second deasphalting of the residue under vacuum (track 2) is integrated, as shown by the CCR (ConRadson Carbon section) which goes from 19.81 to 18.84. This will result in a decrease in coke production.
    Table 4: Properties of the visor-reduction charge according to the chosen route
    Table 5 below summarizes the yields of the visbreaking process and the properties of the visbred effluent according to the chosen route.
    Table 5: Visor Reducer Yields and Visu-Duct Effluent Properties by Selected Route
    The incorporation of the resin cut into the visbreaking charge makes it possible, at iso cracking temperature, to gain conversion. Thus at 434 ° C the conversion gain obtained is of the order of 26%. At 436 ° C, the conversion gain is of the order of 15%.
    In addition, the implementation of the invention leads to an improvement in the stability of the visbroken effluent. Indeed, the stability limit (S-value) at iso-cracking temperature is higher for the visbred effluent obtained by the channel 2. The improvement in the stability results in an increase in the stability limit of about 8 to 9% in both cases.
    权利要求:
    Claims (8)
    [1]
    A process for the conversion of petroleum feeds having a boiling point such that less than 20% by weight of the feedstock is distilled at a temperature of 343 ° C under ambient conditions and more than 40% by weight of the feedstock. is distilled at a temperature above 500 ° C, comprising: - a first deasphalting with a heavy solvent comprising a content of saturated hydrocarbons having at least 5 carbon atoms greater than or equal to 95%, - a second deasphalting on the deasphalted oil after the first deasphalting, with a light solvent comprising a saturated hydrocarbon content having 3 or 4 carbon atoms greater than or equal to 95%, the deasphalted oil resulting from the second deasphalting is converted by catalytic cracking, the pitch from the second deasphalting is converted by visbreaking, a vacuum residue being sent to the viscor reducer in mixture with said pitch from the second deasphalted ge.
    [2]
    2. Process according to claim 1 characterized in that the petroleum feedstock is selected from heavy crudes, atmospheric residues and / or vacuum residues of crude distillations.
    [3]
    3. Method according to one of claims 1 or 2, characterized in that the solvent of the first deasphalting is constituted by an n-paraffin having 5 to 7 carbon atoms and / or the solvent of the second deasphalting is constituted by at least an n-paraffin having 3 or 4 carbon atoms.
    [4]
    4. Method according to one of claims 1 to 3, characterized in that the solvent of the first deasphalting is n-pentane and the solvent of the second deasphalting is propane and / or n-butane.
    [5]
    5. Method according to one of claims 1 to 4, characterized in that a vacuum distillate is sent to the catalytic cracking mixture with said deasphalted oil from the second deasphalting.
    [6]
    6. Process according to claim 5, characterized in that the deasphalted oil resulting from the second deasphalting represents up to 50%, preferably up to 30%, of the total charge of the catalytic cracking.
    [7]
    7. Method according to one of claims 1 to 6, characterized in that the pitch resulting from the second deasphalting represents up to 50%, preferably up to 30%, of the total charge of the visbreducer.
    [8]
    8. Method according to any one of claims 1 to 7, characterized in that the pitch from the first deasphalting is used as a solid fuel.
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    同族专利:
    公开号 | 公开日
    FR2939804A1|2010-06-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4454023A|1983-03-23|1984-06-12|Alberta Oil Sands Technology & Research Authority|Process for upgrading a heavy viscous hydrocarbon|
    FR2598716B1|1986-05-15|1988-10-21|Total France|PROCESS FOR DEASPHALTING A HEAVY HYDROCARBON LOAD|
    FR2864103B1|2003-12-23|2006-03-17|Inst Francais Du Petrole|PROCESS FOR TREATING A HYDROCARBONATED LOAD INCLUDING RESIN REMOVAL|
    FR2910487B1|2006-12-21|2010-09-03|Inst Francais Du Petrole|PROCESS FOR CONVERTING RESIDUES INCLUDING 2 SERIES DISASPHALTAGES|FR2983088A1|2011-11-24|2013-05-31|Total Raffinage Marketing|PROCESS FOR TREATING GASEOUS EFFLUENT AT ATMOSPHERIC DISTILLATION HEAD|
    FR2984917B1|2011-12-23|2014-01-10|Total Raffinage Marketing|METHOD FOR OPTIMIZING THE PRODUCTION OF DISTILLATES COMPRISING A CATALYTIC CRACKING STEP.|
    法律状态:
    2012-06-30| RE| Patent lapsed|Effective date: 20111231 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR0858471|2008-12-11|
    FR0858471A|FR2939804A1|2008-12-11|2008-12-11|Converting petroleum charges , comprises deasphalting oil with heavy solvent and light solvent comprising saturated hydrocarbon, converting deasphalted oil by catalytic cracking and converting pitch by visbreaking|
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