US20060131217A1 - Process for desulphurizing a hydrocarbon cut in a simulated moving bed - Google Patents

Process for desulphurizing a hydrocarbon cut in a simulated moving bed Download PDF

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Publication number
US20060131217A1
US20060131217A1 US11/284,406 US28440605A US2006131217A1 US 20060131217 A1 US20060131217 A1 US 20060131217A1 US 28440605 A US28440605 A US 28440605A US 2006131217 A1 US2006131217 A1 US 2006131217A1
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Prior art keywords
process according
sulphur
feed
desorbant
deep desulphurization
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US11/284,406
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English (en)
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Alexandre Nicolaos
Thorsten Burkhardt
Luc Wolff
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IFP Energies Nouvelles IFPEN
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Assigned to INSTITUT FRANCAIS DU PETROLE reassignment INSTITUT FRANCAIS DU PETROLE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BURKHARDT, THORSTEN, NICOLAOS, ALEXANDRE, WOLFF, LUC
Publication of US20060131217A1 publication Critical patent/US20060131217A1/en
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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
    • 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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/06—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with moving sorbents or sorbents dispersed in the oil
    • C10G25/08—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with moving sorbents or sorbents dispersed in the oil according to the "moving bed" method

Definitions

  • distillate type cut means a cut from distilling crude or from a conversion unit such as catalytic cracking, with a distillation range in the range 150° C. to 450° C.
  • this cut a “gas oil” cut, but such a designation is not restricting in nature. Any hydrocarbon cut containing sulphur and with a distillation range similar to that of a gas oil cut may be used in the process of the present invention.
  • the process of the invention can thus be used to produce a desulphurized cut with 10 ppm by weight of sulphur (S) or less, or even 5 ppm by weight of sulphur, or even less than 1 ppm by weight of sulphur, starting from a feed to be treated with a sulphur content which may be several tens of ppm by weight up to 2% or even 3% by weight.
  • ppm by weight means parts per million by weight and is equivalent to 10 ⁇ 6 kg/kg.
  • gas oil yield of said process is substantially higher than that of a fixed bed process.
  • Gas oil desulphurization methods include processes for purification by adsorption of sulphur-containing compounds on a selective adsorbant and provide an advantageous alternative to conventional hydrodesulphurization processes.
  • United States patent U.S. Pat. No. 4,337,156 recommends the use of a KX type zeolite and a 1-octanol type desorbant to separate polar compounds (sulphur-containing, nitrogen-containing, oxygen-containing) by simulated moving bed (SMB) separation of a naptha cut (term used by the skilled person to designate a gasoline cut with an initial boiling point of about 70° C. and an end point of about 220° C.).
  • SMB simulated moving bed
  • the sulphur-containing compounds present in the naphtha cut are of the thiophene type and not of the benzo or dibenzothiophene type as they constitute the sulphur-containing compounds which are the most difficult to eliminate in the case of a distillate, i.e. those which are encountered in the context of the present invention.
  • U.S. Pat. No. 5,454,933 describes a gas oil desulphurization process which consists of linking a conventional hydrotreatment to eliminate sulphur-containing compounds, known as an “easy sulphur” process, with a process for adsorbing difficult sulphur-containing compounds over an activated carbon with a specific surface area in the range 800 to 1200 m 2 /g and having a specific pore structure.
  • Said sulphur-containing compounds which are difficult to eliminate termed “hard sulphur” compounds, correspond to beta-substituted dibenzothiophene type aromatics.
  • French patent application FR-A-02/03314 proposes a process for desulphurizing a hydrocarbon feed on a complexing solid based on ⁇ electron acceptors. Said process may be preceded by a fractionation column which can produce a light effluent to specifications and a heavy effluent which has to be desulphurized. In the case of fixed bed operation, the losses of product to be desulphurized are not negligible due to physical filling of the pore volume of the adsorbent. That patent proposes a remedy by employing different washing fluids having variable adsorption forces that can thus reduce the hydrocarbon loss without, however, avoiding them entirely.
  • FIG. 1 shows a flowchart of the process of the invention in its most general scope.
  • FIG. 2 shows a variation of the flowchart of the process according to the invention.
  • the invention can be defined as a process for deep desulphurization of a gas oil type hydrocarbon feed with a distillation range in the range 150° C. to 450° C. which may contain up to 3% of sulphur, the process comprising the following steps in succession:
  • the sulphur content in the gas oil obtained is generally less than 10 ppm by weight, preferably less than 5 ppm by weight, and more preferably less than 1 ppm by weight, with a yield with respect to the inlet feed which is generally more than 97% by weight and preferably more than 99%.
  • the feed to be treated may be sent in advance to a distillation column located upstream of the simulated moving bed adsorption unit, from which an overhead stream is withdrawn at least part of which is used as a desorbant, and a bottom stream is withdrawn which is introduced as the feed to the simulated moving bed adsorption unit.
  • the feed ( 1 ) enters the adsorption desulphurization unit operating as a simulated moving bed ( 2 ).
  • This adsorption desulphurization unit is constituted by at least one adsorption column containing a plurality of interconnected adsorbent beds having a selectivity in favour of sulphur-containing compounds over the chemical families of the feed (alkanes and aromatics) which are to be purified.
  • Said adsorption column comprises at least four zones delimited by injections for a mixture ( 1 ) constituting the adsorption and desorbant feed ( 9 b ), and by withdrawals for a raffinate ( 3 ) containing the desulphurized gas oil mixed with desorbant, and an extract ( 4 ) mainly containing sulphur-containing compounds eliminated as a mixture with desorbant.
  • Zone 1 for desorption of sulphur-containing compounds is included between the desorbant injection ( 9 b ) and the extract withdrawal ( 4 ).
  • Zone 2 for desorbing alkanes and aromatics is between the extract withdrawal ( 4 ) and the adsorption feed injection ( 1 ).
  • Zone 3 for adsorbing sulphur-containing compounds is between the feed injection ( 1 ) and the raffinate withdrawal ( 3 ).
  • Zone 4 is between the raffinate withdrawal ( 3 ) and the desorbant injection ( 9 b ) and can adsorb the alkanes and aromatics.
  • the step for separating streams ( 3 ) and ( 4 ) is carried out by means of two distillation columns ( 5 ) and ( 6 ) respectively supplied with the raffinate ( 3 ) and the extract ( 4 ) which can eliminate substantially all of the desorbant at the bottom of the column, for example.
  • This mixture may itself advantageously be mixed with a refinery stream with suitable sulphur specifications, with boiling points which are compatible with those of the mixture produced, such as a fuel oil, for example.
  • This mixture may also be recycled to a conventional hydrotreatment unit which can eliminate the recycled sulphur-containing compounds by increasing the sulphur content of the feed, as the catalytic activity of the hydrodesulphurization process is directly linked to the inlet concentration of sulphur to be treated.
  • Desorbants ( 9 ) and ( 11 ) are recovered from the bottom of columns ( 5 ) and ( 6 ) to form the stream ( 9 a ) which is returned to a simulated moving bed (SMB) desulphurization unit ( 2 ) with optional makeup of desorbant ( 12 ) corresponding to any losses of desorbant suffered in the distillation columns ( 5 ) and ( 6 ).
  • SMB simulated moving bed
  • the various streams ( 9 ), ( 11 ) and ( 12 ) form the addition of desorbant ( 9 b ) which is introduced into the simulated moving bed column ( 2 ).
  • the stream ( 7 ) constitutes the recirculation stream which is indispensable to the operation of a simulated tnoving bed column. It is constituted by regeneration solvent and gas oil in proportions which vary with time.
  • FIG. 2 describes a variation in the invention in which a distillation step corresponding to the unit ( 1 e ) is placed upstream of the flowchart described in FIG. 1 .
  • This distillation step consists of sending the feed ( 1 ) to a distillation tower ( 1 e ) which produced a heavy sulphur-containing hydrocarbon cut ( 1 b ) which is sent to the SMB adsorption unit ( 2 ) as described in FIG. 1 , and a light hydrocarbon cut ( 1 a ) the sulphur content of which is equal to or below the required specifications.
  • Said desulphurized cut ( 1 a ) may also be used as a desorption agent in the SMB adsorption unit ( 2 ), in which case, once a pseudo steady state has been reached, the portion ( 1 d ) of the stream ( 1 a ) is used as a makeup desorbant and mixed with the stream ( 9 a ) to form the stream ( 9 b ) of desorbant of the adsorption column 2 .
  • the remaining portion ( 1 c ) of desulphurized light hydrocarbons has already satisfied the required specifications and could thus act as a base in the commercial gas oil
  • the sulphur content of the gas oil produced by said unit will vary depending on the hydrotreatment operating conditions.
  • the adsorbent used in a SMB adsorption unit is generally selected from the following classes of conventional adsorbents: activated charcoal, zeolites, silicas, aluminas, silica-aluminas, used catalysts, resins, clays, pillaxed clays, reduced metals or oxides and any possible mixture between these different families of adsorbents.
  • the adsorbent used in the SMB adsorption unit is selected from the activated charcoal class, as said solids have sufficient selectivity between the sulphur-containing molecules and the remainder of the gas oil matrix.
  • Preferred activated charcoal types are those which have a specific surface area of more than 1200 m 2 /gram and a total pore volume of more than 0.5 cm 3 /gram, the precursor possibly being of any type, and the type of activation used to create the porosity possibly being either physical, or chemical, or a combination of the two.
  • the total pore volume is preferably 0.5 cm 3 /gram or more, and the fraction of pore volume included in the microporosity of said solid adsorbent is preferably 0.2 cm 3 /gram or more.
  • the microporosity is defined as the category of pores with a diameter of less than 20 angstroms (2 nanometers, i.e. 2 ⁇ 10 ⁇ 9 metres).
  • the number of adsorbent beds constituting the simulated moving bed adsorption unit is generally less than 24, and preferably less than 15.
  • the desorbant may be selected from the following chemical classes: nitrogen-containing compounds, alcohols, ethers, aromatics, desulphurized light cuts, or any other refinery stream or mixture thereof.
  • aromatics may preferably be selected.
  • the ratio of the desorbant to the feed in the simulated moving bed separation unit is generally in the range 0.5 to 2.5 by volume, preferably in the range 0.7 to 2.0.
  • the operating temperature may be between ambient temperature and the end point of the hydrocarbon cut to be treated, knowing that liquid phase operation is required.
  • a temperature of 50° C. to 350° C. is used, preferably in the range 50° C. to 250° C.
  • the operating pressure may be between the bubble point of the lightest compound and 15 bars absolute (1.5 MPa), to guarantee the existence of a liquid phase throughout the SMB adsorption unit, knowing that the performance of the process is less dependent on this parameter. However, it may have an influence on the equipment cost.
  • aromatics mono-, di- and tri-;
  • the valve permutation time was 152.0 seconds.
  • the raffinate obtained delivered a gas oil with 1.5 ppm by weight sulphur content in a purity of 99.5%.
  • the productivity of the unit expressed as the volume of gas oil produced per volume of adsorbent and per unit time, was 1.31 m 3 /m 3 .h).
  • the valve permutation time was 152.0 seconds.
  • the raffinate obtained delivered a gas oil with 3.5 ppm by weight of sulphur in a purity of 99.5%.
  • the productivity of the unit expressed as the volume of gas oil produced per volume of adsorbent and per unit time, was 0.67 m 3 /(m 3 .h).

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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)
  • Dispersion Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
US11/284,406 2004-11-23 2005-11-22 Process for desulphurizing a hydrocarbon cut in a simulated moving bed Abandoned US20060131217A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR04/12.415 2004-11-23
FR0412415A FR2878252B1 (fr) 2004-11-23 2004-11-23 Procede de desulfuration d'une coupe hydrocarbonee en lit mobile simule

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US20060131217A1 true US20060131217A1 (en) 2006-06-22

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US (1) US20060131217A1 (enExample)
EP (1) EP1666568A1 (enExample)
JP (1) JP2006144020A (enExample)
KR (1) KR20060057510A (enExample)
CN (1) CN1800309A (enExample)
FR (1) FR2878252B1 (enExample)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090301931A1 (en) * 2006-10-20 2009-12-10 Omer Refa Koseoglu Asphalt production from solvent deasphalting bottoms
WO2012066574A3 (en) * 2010-11-19 2012-09-27 Indian Oil Corporation Ltd. A process for desulfurization of diesel with reduced hydrogen consumption
US20120305450A1 (en) * 2006-01-30 2012-12-06 Advanced Technology Materials, Inc. Nanoporous articles and methods of making same
US9468901B2 (en) 2011-01-19 2016-10-18 Entegris, Inc. PVDF pyrolyzate adsorbent and gas storage and dispensing system utilizing same
US10619108B2 (en) 2015-12-11 2020-04-14 Cnooc Tianjin Chemical Research & Design Institute Co. Ltd. Method for simulated moving bed to adsorb and separate polycyclic aromatic hydrocarbons

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2910457B1 (fr) * 2006-12-22 2009-03-06 Inst Francais Du Petrole Procede de purification par adsorption d'hydrogene avec cogeneration d'un flux de co2 en pression
CN105368482B (zh) * 2015-12-11 2017-07-28 中海油天津化工研究设计院有限公司 一种多塔并联吸附脱除柴油中多环芳烃的方法
CN105542849B (zh) * 2015-12-11 2017-06-23 中国海洋石油总公司 一种由劣质柴油生产清洁柴油和轻质芳烃的方法
CN105349175B (zh) * 2015-12-11 2018-03-13 中海油天津化工研究设计院有限公司 一种同时吸附脱除柴油中的硫化物和芳烃的方法
CN106244225B (zh) * 2016-08-12 2018-12-14 中国昆仑工程有限公司 实现重芳烃高效分离的模拟移动床吸附分离方法
WO2020174610A1 (ja) * 2019-02-27 2020-09-03 日揮グローバル株式会社 炭素系吸着材の再生方法及び炭素系吸着材の再生システム

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2985589A (en) * 1957-05-22 1961-05-23 Universal Oil Prod Co Continuous sorption process employing fixed bed of sorbent and moving inlets and outlets
US4337156A (en) * 1980-09-23 1982-06-29 Uop Inc. Adsorptive separation of contaminants from naphtha
US5454933A (en) * 1991-12-16 1995-10-03 Exxon Research And Engineering Company Deep desulfurization of distillate fuels
US5710092A (en) * 1993-10-25 1998-01-20 Westvaco Corporation Highly microporous carbon
US6482316B1 (en) * 1999-06-11 2002-11-19 Exxonmobil Research And Engineering Company Adsorption process for producing ultra low hydrocarbon streams

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2837212B1 (fr) 2002-03-18 2004-10-01 Total Raffinage Distribution Procede de deazotation de charges hydrocarbonees en presence d'une masse polymerique
EP1514917A4 (en) * 2002-05-22 2007-05-23 Japan Energy Corp ADSORPTION SULFURISING AGENTS FOR THE DESOLUTION OF A PETROLEUM DISPERSION AND DECOMPOSITION METHOD WHERE IT APPLIES
FR2852019B1 (fr) * 2003-03-07 2007-04-27 Inst Francais Du Petrole Procede de desulfuration, de deazotation et/ou de desaromatisation d'une charge hydrocarbonee par adsorption par un solide adsorbant use

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2985589A (en) * 1957-05-22 1961-05-23 Universal Oil Prod Co Continuous sorption process employing fixed bed of sorbent and moving inlets and outlets
US4337156A (en) * 1980-09-23 1982-06-29 Uop Inc. Adsorptive separation of contaminants from naphtha
US5454933A (en) * 1991-12-16 1995-10-03 Exxon Research And Engineering Company Deep desulfurization of distillate fuels
US5710092A (en) * 1993-10-25 1998-01-20 Westvaco Corporation Highly microporous carbon
US6482316B1 (en) * 1999-06-11 2002-11-19 Exxonmobil Research And Engineering Company Adsorption process for producing ultra low hydrocarbon streams

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120305450A1 (en) * 2006-01-30 2012-12-06 Advanced Technology Materials, Inc. Nanoporous articles and methods of making same
US20090301931A1 (en) * 2006-10-20 2009-12-10 Omer Refa Koseoglu Asphalt production from solvent deasphalting bottoms
US9315733B2 (en) 2006-10-20 2016-04-19 Saudi Arabian Oil Company Asphalt production from solvent deasphalting bottoms
WO2012066574A3 (en) * 2010-11-19 2012-09-27 Indian Oil Corporation Ltd. A process for desulfurization of diesel with reduced hydrogen consumption
US9468901B2 (en) 2011-01-19 2016-10-18 Entegris, Inc. PVDF pyrolyzate adsorbent and gas storage and dispensing system utilizing same
US10619108B2 (en) 2015-12-11 2020-04-14 Cnooc Tianjin Chemical Research & Design Institute Co. Ltd. Method for simulated moving bed to adsorb and separate polycyclic aromatic hydrocarbons

Also Published As

Publication number Publication date
FR2878252A1 (fr) 2006-05-26
KR20060057510A (ko) 2006-05-26
CN1800309A (zh) 2006-07-12
FR2878252B1 (fr) 2008-08-22
JP2006144020A (ja) 2006-06-08
EP1666568A1 (fr) 2006-06-07

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