EP1508609B1 - Verfahren zur Aufbereitung einer Zwischenfraktion von Dampfspaltungsströmen - Google Patents

Verfahren zur Aufbereitung einer Zwischenfraktion von Dampfspaltungsströmen Download PDF

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Publication number
EP1508609B1
EP1508609B1 EP20040291954 EP04291954A EP1508609B1 EP 1508609 B1 EP1508609 B1 EP 1508609B1 EP 20040291954 EP20040291954 EP 20040291954 EP 04291954 A EP04291954 A EP 04291954A EP 1508609 B1 EP1508609 B1 EP 1508609B1
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Prior art keywords
cut
unit
weight
process according
aromatics
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EP20040291954
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French (fr)
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EP1508609A1 (de
Inventor
Vincent Coupard
Denis Uzio
Denis Guillaume
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C10G65/06—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a selective hydrogenation of the diolefins
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C10G65/08—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a hydrogenation of the aromatic hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/14—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only
    • C10G65/16—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only including only refining steps
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of thermal cracking in the absence of hydrogen

Definitions

  • the present invention relates to a process for treating hydrocarbon steam cracking effluents.
  • the steam cracking process is a well-known petrochemical process, which is the basis of the production of the major intermediates, in particular ethylene and propylene.
  • Steam cracking produces, in addition to ethylene and propylene, significant quantities of less valuable co-products, especially aromatic pyrolysis gasoline, which is found in significant quantities when cracking propane or butane, and even more so. when you crack naphtha or diesel.
  • the crude pyrolysis gasoline is often hydrotreated in two stages, with intermediate fractionation to typically produce a C5 cut, a C6-C7-C8 cut, and a C9 + cut.
  • a section Cn is a section consisting essentially of hydrocarbons with n carbon atoms
  • a Cn + section is a section composed essentially of hydrocarbons with at least n carbon atoms.
  • Pyrolysis gasolines also typically have high sulfur contents, especially that of the C9 + cut, which is often of the order of 300 ppm. weight. However, this sulfur content becomes incompatible with the evolution of standards on the maximum sulfur content of gasoline which tends to fall below 50 ppm, or 30 ppm or 10 ppm weight.
  • the high sulfur content of the pyrolysis gasoline thus poses a delicate technical problem for the steam cracking industry, for the valorization of these species.
  • the object of the invention is to find a technically simple solution to the aforementioned problem, and this by requiring a minimum or no modification of existing units, and allowing a high valuation of products.
  • the feed rate of the unit HD3, and / or the degree of saturation of the aromatics in this unit are limited so that the hydrogen consumption in HD3 is less than or equal to the quantity of excess hydrogen produced.
  • the hydrogen feeding HD3 (and preferably hydrogen feeding HD1, HD2 and HD3) is provided in full by this excess hydrogen.
  • the invention thus makes it possible, by departing from the conventional technical philosophy of preserving the aromatics of the pyrolysis gasoline, to use the excess hydrogen of the steam cracker to change the spectrum of co-products of the steam cracker, and to produce a or several new products of high recovery, which are no longer gasoline, and which eliminate the technical problem related to the amount of sulfur contained in the pyrolysis gasoline.
  • a solvent or a solvent base having at least 60% by volume of naphthenes, at most 5%, and preferably at most 3% by volume of aromatics, and at most 10 ppm by weight of sulfur. It is also possible to produce, at the outlet of HD3, a kerosene or a light gas oil or a kerosene or diesel base, having less than 30%, or less than 20% of aromatics, at most 300 ppm by weight of sulfur, and an interval distillate (ASTM) within the range [120 ° C-310 ° C].
  • ASTM interval distillate
  • a domestic fuel of aromatic content generally less than 50% by volume, or at 30% by volume or even at 20% by volume, with a sulfur content typically of less than 300 ppm by weight, typically having an ASTM distillation range. within the range [120 ° C-310 ° C].
  • the unit HD3 uses at least one catalyst comprising platinum and palladium deposited on a support. It has indeed been found that such catalysts, used in the refinery, but not in the steam-cracking industry, prove to be effective and compatible with the specific compounds present in the pyrolysis gasolines.
  • the unit HD3 uses at least one catalyst comprising from 0.1 to 0.30% by weight of platinum, and from 0.2 to 1% and preferably from 0.4 to 0.7% by weight of platinum. palladium, deposited on a fluorinated alumina, comprising from 1 to 5% by weight of fluorine.
  • This catalyst makes it possible to operate at high hourly space velocities (VVH), notably comprised between 1 and 6 on these charges of pyrolysis gasolines.
  • a conventional catalyst for example LD 145, a NiMo (nickel / molybdenum) catalyst marketed by Axens, can optionally be optionally used in the guard bed or in the first reactor in the same unit HD3.
  • hydrorefining catalysts for example of the Ni-Mo, Co-Mo type (for example the CoMo HR406, HR306C type catalysts ( sold by Axens) with a NiMo LD145 type catalyst guard bed (marketed by Axens) or a catalyst which is at least partially saturating the olefins, for example a CoMo type hydrosulfurization catalyst on a guard bed, can also be used in a guard bed.
  • Ni-Mo, Co-Mo type for example the CoMo HR406, HR306C type catalysts ( sold by Axens) with a NiMo LD145 type catalyst guard bed (marketed by Axens)
  • a catalyst which is at least partially saturating the olefins for example a CoMo type hydrosulfurization catalyst on a guard bed
  • At least 70%, or at least 90%, or at least 95% by weight or more of the olefins present in the feedstock of HD3 can be saturated, for example, the residual olefin content of the products derived from HD 3, according to the invention.
  • solvent, or kerosene, or diesel, or domestic fuel, or base of one of these products can be reduced to less than 5% by weight, or preferably less than 1% by weight, or very preferably less than 0.5% by weight, v substantially zero.
  • the intermediate fraction produced in step a), and the charge of the unit HD3 are not limited to the pyrolysis gasoline, and may have an ASTM endpoint. between 230 and 310 ° C, and preferably between 250 and 280 ° C.
  • the figure 1 represents the main part of an installation according to the method of the invention, this main part representing the pyrolysis gasoline treatment plant, or the intermediate fraction comprising pyrolysis gasoline.
  • the upstream part allowing the primary fractionation of the steam cracking effluents is not represented.
  • the figure 1 is also a simplified representation, including hydrotreating units that have not been detailed (including possible hydrotreated load recycling, and hydrogen backups are not shown).
  • the figure 2 represents a more detailed representation of a hydroprocessing unit of the installation of the figure 1 .
  • the feed also called intermediate fraction, according to the invention, is fed by the line 1 and treated in a hydrotreating unit HD1 to achieve in particular a prior dedienization.
  • the dedionnesée charge circulates by the line 2 and is fractionated in a distillation column 3 in a fraction C5 circulating by the line 4, typically recycled to steam-cracking, and a C6 + cut flowing through the line 5.
  • This C6 + cut is fractionated in the column of distillation 6 in a C6-C8 fraction (C6-C7-C8), feeding via line 7 a second hydrotreating unit HD2 which performs a thorough desulfurization of the C6-C8 cut, and a deep conversion of olefins.
  • the treated C6-C8 cut discharged via line 9 can have, for example, less than 1 ppm by weight of sulfur and less than 50 ppm by weight of olefins. It is generally sought to minimize the loss of aromatics in the unit HD2, to maximize their subsequent recovery.
  • the C9 + cut leaving the bottom of the column 6 via the line 8 then feeds a third hydrotreating unit HD3 to produce a desulfurized cut with a low aromatic content evacuated via the line 11.
  • the cut produced is, according to the invention, typically either a kerosene or a diesel fuel (or a base of kerosene or diesel fuel), the aromatic content of which is less than 30% by volume, generally less than 20% by volume, ie a solvent or a solvent base, with an aromatic content of less than 5% volume.
  • a solvent or solvent base
  • the cut produced at the output of HD3 can also be a domestic fuel, or a domestic fuel oil base, typically less than 50% aromatic content, usually less than 30% volume, or even less than 20% volume.
  • the C9 + cut fed by line 8 is supplemented with a recycled fraction of hydrotreated product, circulating in line 8f, and with a stream of recycling gas rich in hydrogen, circulating in line 8c.
  • This stream comprises makeup hydrogen fed by a line not shown.
  • the overall stream from the mixture then feeds the hydrotreating reactor R3.
  • the effluent of R3 circulates in the line 8a or it is cooled by means not shown, and enters the separator tank S3.
  • the gas separated in S3 is mainly recycled via line 8c, a fraction being purged by line 8d.
  • the liquid product from S3 circulates in line 8b, to be partially recycled by line 8e and partially discharged via line 11.
  • the unit HD3 comprises at least one catalyst making it possible to very efficiently achieve, in a single unit, the desired sulfur and aromatic specifications.
  • the catalyst of the unit HD3 comprises in particular at least one platinum / palladium catalyst bed on a fluorinated alumina support.
  • the support may be composed essentially of gamma-alumina and comprise from 1 to 10, preferably from 1 to 7, and very preferably from 3 to 5% by weight of fluorine.
  • the unit HD3 may therefore comprise such a fluorinated alumina support catalyst, arranged in one or more beds, and optionally a first bed or guard bed with a conventional Ni / Mo type catalyst acting pretreatment.
  • This platinum / palladium catalyst may preferably comprise between 0.10 and 0.30%, preferably between 0.15 and 0.30%, and very preferably between 0.20 and 0.30% by weight of platinum. as well as generally from 0.2 to 1.0%, and preferably from 0.4 to 0.7% by weight of palladium.
  • the molar ratio of palladium to platinum may especially be between 3 and 8, preferably between 3.5 and 6.
  • the end point of the treated section is modified, and increased with respect to a conventional cut of pyrolysis gasoline, whose end point is often between 205 and 220 ° C.
  • the end point of the processed section may, in this variant of the invention, be higher because the C9 + cut is typically intended to be converted into other products than gasoline. Indeed, some solvents, as well as kerosene, diesel or domestic fuel oil fractions may have final distillation points (ASTM distillation) greater than 220 ° C.
  • the fraction treated can therefore be a long fraction going beyond petrol, having a final point of distillation greater than 220 ° C, for example between 230 and 310 ° C, especially between 240 and 280 ° C.
  • This can be obtained by modifying, during the fractionation of the steam cracking effluents in the primary distillation, the cutting point between the gasoline fraction and the fuel fraction of pyrolysis, to leave fractions boiling above about 220 ° C. in the so-called fraction.
  • "gasoline” which becomes an intermediate fraction "gasoline + middle distillate”.
  • Naphtech steam-cracking effluents are fractionated in a treatment plant for these effluents, comprising a primary distillation, in particular to produce a pyrolysis gasoline cut, comprising the C5 cut and heavier hydrocarbons up to an ASTM endpoint of 210 ° C.
  • This pyrolysis gasoline feedstock is treated according to the process scheme described in figure 1 .
  • the feed fed to the hydrotreating unit HD3 is the C9 + feed, without C6 / C8 cutting input from HD2, the line 10 not being used.
  • Catalyst Palladium catalyst on alumina, comprising 0.30% by weight of palladium.
  • Hydrogen content (total reactor inlet gas): 90 Nm 3 of hydrogen / m 3 of feedstock.
  • the unused gas is separated and sent as an add-on to the second unit HD2.
  • Recycle rate of the load 2 (two volumes of hydrotreated product leaving HD1 are recirculated for a volume of fresh feed supplied with HD1, to limit the increase in temperature due to the exothermicity of the reaction).
  • Recycling rate of the unit 5 (recycling of liquid effluent in mass ratio relative to the load). 90% of the recycle is mixed with the feed, and 10% is injected in inter-catalytic beds to adjust the thermal profile. The recycling of liquid is in fact made necessary by the heat released during the hydrogenation.
  • Example 1 is repeated but with a long charge, end point ASTM 250 ° C. This is achieved by modifying the operating parameters of the treatment of steam cracking effluents, so that the fractionation leaves with the pyrolysis gasoline fractions a little heavier than gasoline.
  • Recycle hydrogen content including make-up hydrogen (hydrogen-rich total gas: inlet + quench): 400 Nm 3 / m 3 of charge of unit HD3.
  • Recycling rate (recycling of liquid effluent with the load and between beds in order to adjust the thermal profile): 3 en masse, of which 0.45 in inter-beds.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Claims (9)

  1. Verfahren zur Aufbereitung von Dampfcrackströmen, umfassend:
    a) die Trennung dieser Ströme, um eine Zwischenfraktion zu produzieren, die mindestens den größten Teil des Pyrolysebenzins umfasst, den diese Ströme umfassen, und zum größten Teil aus Verbindungen besteht, die mindestens 5 Kohlenstoffatome und einen Endsiedepunkt von weniger als 310°C aufweisen,
    b) eine erste Hydroaufbereitung dieser Zwischenfraktion in einer HD1-Einheit,
    c) eine Fraktionierung mindestens eines Teils des Abflusses aus der HD1-Einheit, um einen C5-Schnitt und einen C6+-Schnitt zu produzieren,
    d) eine Fraktionierung mindestens eines Teils des C6+Schnitts, um einen C6-C8-Schnitt und einen C9+-Schnitt zu produzieren,
    e) eine zweite Hydroaufbereitung mindestens eines Teils des C6-C8-Schnitts in einer HD2-Einheit, um einen hydroaufbereiteten C6-C8-Schnitt zu produzieren,
    f) eine dritte Hydroaufbereitung einer Beschickung, die mindestens einen Teil des C9+-Schnitts und optional mindestens einen Teil des C6-C8-Schnitts oder des hydroaufbereiteten 6-C8-Schnitts umfasst, in einer HD3-Einheit, um mindestens 20 Vol.-% der Aromaten, die die Beschickung der HD3-Einheit umfasst, mit einem Teil oder dem gesamten überschüssigen Wasserstoff zu sättigen, der durch das Dampfcracken produziert wird,
    und am Ausgang von HD3 mindestens ein Endprodukt Gruppe, bestehend aus Lösemitteln, die weniger als 5 % Aromaten umfassen, Kerosin- oder Diesel- oder Haushaltsbrennstoffschnitten, oder den Grundstoffen zur Fertigung dieser Produkte zu produzieren
  2. Verfahren nach Anspruch 1, wobei die Durchflussmenge der Beschickung der HD3-Einheit und/oder der Sättigungsgrad der Aromaten in dieser Einheit begrenzt wird, damit der Wasserstoffverbrauch in HD3 kleiner oder gleich der überschüssigen Wasserstoffmenge ist, die durch das Dampfcracken produziert wird, und wobei der Wasserstoff, mit dem HD3 versorgt wird, vollständig aus diesem überschüssigen Wasserstoff besteht.
  3. Verfahren nach einem der Ansprüche 1 und 2, wobei Ausgang von HD3 ein Lösemittel oder ein Lösemitkelgrundstoff produziert wird, der mindestens 60 Vol.-% Naphtene, höchstens 5 Vol.-% Aromaten und höchstens 10 Gew.-ppm Schwefel aufweist.
  4. Verfahren nach einem der Ansprüche 1 und 2, wobei am Ausgang von HD3 ein Kerosin oder ein Diesel oder ein Kerosin- oder Dieselgrundstoff produziert wird, das/der mindestens 30 Vol.-% Aromaten, höchstens 300 Gew.-ppm Schwefel und einen ASTM-Destillationsbereich innerhalb des Bereichs [120°C - 310°C] aufweist.
  5. Verfahren nach einem der Ansprüche 1 und 2, wobei am Ausgang von HD3 ein Haushaltsbrennstoff oder Haushaltsbrennstoffgrundstoff produziert wird, der mindestens 50 Vol.-% Aromaten, höchstens 300 Gew.- ppm Schwefel und einen ASTM-Destillationsbereich innerhalb des Bereichs [120 °C - 310°C] aufweist. 1
  6. Verfahren nach einem der Ansprüche 1 bis 6, wobei die HD3-Einheit mindestens einen Katalysator verwendet, der Platin und Palladium umfasst, die auf einem Träger abgelagert sind.
  7. Verfahren nach Anspruch 6, wobei die HD3-Einheit mindestens einen Katalysator verwendet, der 0,10 bis 0,30 Gew.-% Platin und 0,2 bis 1 Gew.-% Palladium umfasst, die auf einem fluorierten luminiumoxid abgelagert sind, das 1 bis 5 Gew.-% Fluor umfasst.
  8. Verfahren nach einem der Ansprüche 1 bis 6, wobei die Zwischenfraktion, die in Schritt a) produziert wurde, und die Beschickung der HD3-Einheit einen ASTM-Endpunkt im Bereich zwischen 230 und 310 °C aufweisen.
  9. Verfahren nach einem der vorhergehenden Ansprüche, wobei das Endprodukt einen Olefingehalt von weniger als 1 Gew.-% aufweist.
EP20040291954 2003-08-19 2004-07-29 Verfahren zur Aufbereitung einer Zwischenfraktion von Dampfspaltungsströmen Expired - Fee Related EP1508609B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0310028A FR2858981B1 (fr) 2003-08-19 2003-08-19 Procede de traitement d'une fraction intermediaire issue d'effluents de vapocraquage
FR0310028 2003-08-19

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EP1508609A1 EP1508609A1 (de) 2005-02-23
EP1508609B1 true EP1508609B1 (de) 2008-10-22

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FR (1) FR2858981B1 (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1948441B (zh) * 2006-10-08 2010-05-12 广东省茂名华粤集团有限公司 石油烃裂解碳九馏分加氢工艺
FR2913692B1 (fr) 2007-03-14 2010-10-15 Inst Francais Du Petrole Procede de desulfuration de fractions hydrocarbonees issues d'effluents de vapocraquage

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1183072B (de) * 1960-12-15 1964-12-10 Bayer Ag Verfahren zur thermischen Spaltung fluessiger Kohlenwasserstoffe zu Olefinen
FR1315477A (fr) * 1961-02-20 1963-01-18 Exxon Research Engineering Co Procédé de conversion des hydrocarbures
US4138325A (en) * 1977-12-22 1979-02-06 Gulf Research & Development Company Process for conversion of gas oil to ethylene and needle coke
DE2840986A1 (de) * 1978-09-21 1980-04-03 Linde Ag Verfahren zur aufarbeitung der bei der spaltung von kohlenwasserstoffen entstehenden ueber 200 grad siedenden kohlenwasserstoff-fraktion
US20030141220A1 (en) * 2002-01-31 2003-07-31 O'rear Dennis J. Upgrading fischer-tropsch and petroleum-derived naphthas and distillates

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EP1508609A1 (de) 2005-02-23
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FR2858981B1 (fr) 2006-02-17

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