Classifications

• • 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
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
• • 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
  • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
  • C10G49/22—Separation of effluents
• • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1037—Hydrocarbon fractions
  • C10G2300/1048—Middle distillates
  • C10G2300/1059—Gasoil having a boiling range of about 330 - 427 °C
• • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1074—Vacuum distillates
• • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/201—Impurities
  • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
• • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/201—Impurities
  • C10G2300/207—Acid gases, e.g. H2S, COS, SO2, HCN
• • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/30—Physical properties of feedstocks or products
  • C10G2300/301—Boiling range
• • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/4081—Recycling aspects
• • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/4093—Catalyst stripping
• • 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
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/06—Gasoil

Definitions

• Conventional hydrodesulfurization processes for gas oils or vacuum distillates include an oven generally located between the H2S stripper and the main fractionation column.
• This oven makes it possible to raise the temperatures after stripping and to obtain effective fractionation in the fractionation column located downstream.
• the presence of this oven generates significant energy consumption and represents a significant investment and operating cost both in absolute terms and in relation to the whole process.
• the present invention relates to a process for hydrodesulfurization of diesel or vacuum distillate, preferably of vacuum diesel and / or vacuum distillates, comprising at least one hydrodesulfurization reaction section, at least one stripping section and at least a fractionation section in which the main fractionation column is operated under a moderate vacuum.
• the method according to the invention makes it possible to reduce the amount of heat to be supplied to the load of the fractionation section and therefore to operate said section at moderate temperature levels.
• the process according to the invention therefore makes it possible to desulfurize a gas oil and or a vacuum distillate without it being necessary to set up an oven between the stripping section and the fractionation section, which represents a significant economic advantage compared to prior art methods.
• the present invention relates to a process and an installation for hydrodesulfurization of diesel or vacuum distillate, preferably of vacuum diesel and / or vacuum distillates, comprising at least one hydrodesulfurization reaction section, at least one stripping section and at least one fractionation section in which the main fractionation column is operated under a moderate vacuum.
• the installation according to the invention also comprises a hot separator tank.
• the hydrodesulfurization reaction section can comprise one or more reactors arranged in series or in parallel, for example two reactors arranged in series.
• Each reactor in the reaction section comprises at least one bed of catalyst.
• the catalyst can be used in a fixed bed or in an expanded bed, or even in a bed bubbly. In the case of a catalyst used in a fixed bed, it is possible to have several catalyst beds in at least one reactor.
• Any catalyst known to a person skilled in the art can be used in the process according to the invention, for example a catalyst comprising at least one element chosen from the elements of Group VIII of the periodic table (groups 8, 9 and 10 of the new periodic classification) and possibly at least one element chosen from the elements of Group VIB of the periodic classification (group 6 of the new periodic classification).
• the temperature is typically between about 200 and about 460 ° C.
• the total pressure is typically between approximately 1 MPa and approximately 20 MPa, generally between 2 and 20 MPa, preferably between 2.5 and 18 MPa, and very preferably between 3 and 18 MPa.
• the overall hourly space velocity of liquid charge for each catalytic step is typically between approximately 0.1 and approximately 12, and generally between approximately 0.4 and approximately 10.
• the purity of the hydrogen used in the process according to the invention is typically between 50 and 99.9.
• the amount of hydrogen relative to the liquid charge is typically between about 50 and about 1200 Nm3 / m3.
• the fractionation and stripping sections can be equipped with any type of stripping column at any pressure or fractionation under moderate vacuum known to those skilled in the art.
• the stripping can be carried out by means of any stripping gas such as for example a gas containing hydrogen or steam.
• a gas containing hydrogen or steam Preferably, steam is used to carry out said stripping.
• the vacuum column is also preferably supplied with any stripping gas, preferably steam.
• the additional heat necessary for this vaporization can possibly be provided by the increase in the temperature of said separator tank compared to current practice which corresponds to a temperature generally between 240 ° C and 280 ° C. Generally, this increase is less than 60 ° C, preferably less than 50 ° C, more preferably less than 40 ° C.
• This operating mode also differs notably from that of the prior art in which the temperature of the hot flask is fixed for the operation of the H2S stripper column.
• the temperature of said separator flask when the latter is present, is therefore generally between 280 ° C and 350 ° C, preferably between 300 ° C and 340 ° C and very preferably between 300 ° C and 330 ° C.
• the temperature of the vacuum system is generally governed by the condensation temperature of the water coming from the stripping vapor from the column.
• the complete condensation of hydrocarbons and water vapor makes it possible to use a very simple vacuum system which consumes little energy.
• this process therefore generally makes it possible to save around 2/3 of the energy consumption of the oven used in the processes of the prior art. The remaining 1/3 is transferred to the furnace of the reaction loop.
• this process saves the oven as well as many of the cooling exchangers usually required before collecting products from the process.
• Another notable simplification is the preferred possibility of removing the lateral strippers from this column, since the extraction of a large quantity of naphtha in the stripper provides kerosene and diesel fuel cuts with the correct flash point specification, generally between 50 and 70 ° C.
• Figure 1 describes one of the possible embodiments of the method according to the invention. This embodiment is particularly well suited to the case where the conversion of the feedstock in the hydrodesulfurization reaction section is limited to less than 50% (that is to say that less than 50% by weight of the feedstock is converted in this section), preferably less than 30%.
• the feed for example a vacuum gas oil comprising hydrocarbons with boiling points between 370 and 565 ° C
• the hydrogen preferably in excess relative to the load, is supplied via line 3 and the compressor 4 then line 5, and mixed with the load 1 before being admitted into a charge-effluent exchanger (6) via line 2.
• the exchanger 6 makes it possible to preheat the load by means of Peffluent from the hydrodesulfurization reactor 10. After this exchange, the charge is brought via line 7 into an oven making it possible to reach the temperature level necessary for the hydrodesulfurization reaction, then the hot charge is sent, via line 9, in the hydrodesulfurization section 10, consisting of at least one hydrodesulfurization reactor comprising at least one hydrodesulfurization catalyst.
• the effluent from reactor 10 is then sent to exchanger 6, then via line 12 to the separator flask 13.
• a gaseous fraction is separated in this flask and recovered via line 14.
• the desulfurized liquid fraction is recovered at the bottom via line 27.
• Said gaseous fraction comprises unreacted hydrogen, hydrogen sulphide (H2S) formed during the reaction, as well as generally light hydrocarbons resulting from the conversion of hydrocarbons from the feed into the reaction section hydrodesulfurization.
• H2S hydrogen sulphide
• the liquid hydrocarbon phase is recycled via lines 20 and 26 to the liquid effluent from the flask 13 and mixed with this liquid effluent before being sent via line 28 to the stripping column (stripper) 29.
• the gaseous fraction from the flash balloon 19 is sent via line 21 to an amine absorber or a washing column 22 making it possible to remove at least part of I ⁇ 2S, then the gaseous fraction containing hydrogen is recycled via the lines 23 and 25 to the hydrodesulfurization reactor, after compression by means of compressor 24 and mixing with feed 1.
• the stripper 29 is preferably supplied with stripping steam via line 32.
• a gaseous fraction (generally called acid gas) is recovered via line 30 and via line 31 a naphtha having a final boiling point usually more than 100 ° C.
• the liquid recovered at the bottom of the stripper via line 33 is sent via the fractionation column 34, without it being necessary to reheat it in an oven or an exchanger.
• the fractionation column 34 is operated under vacuum. This is generally a moderate vacuum (for example around 0.25 bar in the flash zone). The operation of the column under a moderate vacuum makes it possible to considerably reduce the heat to be supplied to the charge of this column to vaporize the fraction having a boiling point below 370 ° C.
• the additional heat is preferably provided by an increase in the temperature of the hot separator tank (13) relatively moderate compared to current practice (for example around 310 ° C instead of 270 ° C).
• This vacuum column is also supplied with stripping steam via line 44.
• the vacuum separation and maintenance section 37 In the vacuum separation and maintenance section 37, the details of which are not shown since they are known to a person skilled in the art, it is possible to separate an aqueous liquid fraction and a hydrocarbon fraction which it is not desired to recover. via line 38.
• the product obtained line 38 consists for example of naphtha and / or kerosene and / or diesel cuts having an initial boiling point greater than 100 ° C.
• Said section 37 also includes the equipment making it possible to generate a partial vacuum and to maintain it in the column, any equipment known to those skilled in the art can be used, for example an ejector and a condenser or a vacuum pump.
• the intermediate fraction from the fractionation column via line 39 is cooled for example by means of an exchanger (40) and an air condenser (42), then recovered via line 43.
• This is for example of a diesel cut having a final boiling point below 370 ° C.
• the heavy fraction from the fractionation column via line 45 is also cooled by means, for example, of the exchanger 46 and the air condenser 48.
• the fraction thus obtained via line 49 is a hydrotreated vacuum diesel fuel having points of cuts close to the initial charge (for example initial and final boiling points of 370 ° C and 565 ° C respectively).

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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)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

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• 2001
  • 2001-10-12 FR FR0113151A patent/FR2830869B1/fr not_active Expired - Lifetime
• 2002
  • 2002-09-09 AT AT02774912T patent/ATE392460T1/de not_active IP Right Cessation
  • 2002-09-09 EP EP02774912A patent/EP1436362B2/de not_active Expired - Lifetime
  • 2002-09-09 ES ES02774912T patent/ES2305303T5/es not_active Expired - Lifetime
  • 2002-09-09 WO PCT/FR2002/003051 patent/WO2003042332A1/fr active IP Right Grant
  • 2002-09-09 US US10/492,368 patent/US7959794B2/en not_active Expired - Fee Related
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