EP1666568A1 - Procédé de désulfuration d'une coupe hydrocarbonée en lit mobile simulé - Google Patents

Procédé de désulfuration d'une coupe hydrocarbonée en lit mobile simulé Download PDF

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Publication number
EP1666568A1
EP1666568A1 EP05292374A EP05292374A EP1666568A1 EP 1666568 A1 EP1666568 A1 EP 1666568A1 EP 05292374 A EP05292374 A EP 05292374A EP 05292374 A EP05292374 A EP 05292374A EP 1666568 A1 EP1666568 A1 EP 1666568A1
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EP
European Patent Office
Prior art keywords
sulfur
desorbent
zone
point
charge
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP05292374A
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German (de)
English (en)
French (fr)
Inventor
Alexandre Nicolaos
Thorsten Burkhardt
Luc Wolff
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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
    • 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 is meant a cut resulting from the distillation of the crude or from a conversion unit such as catalytic cracking, and whose distillation range is between 150 ° C. and 450 ° C.
  • the process according to the invention thus makes it possible to produce a desulfurized cut at contents of less than or equal to 10 ppm by weight of sulfur (S), or even 5 ppm by weight of sulfur, or even less than 1 ppm by weight of sulfur, and this starting from a charge to be treated whose sulfur content may be equal to a few tens of ppm by weight and may be up to 2, or even 3% by weight.
  • the ppm weight notation means part per million by weight and is equivalent to 10 -6 kg / kg.
  • the diesel yield of this process is significantly higher than that of a process operating in a fixed bed.
  • Future specifications on automotive fuels provide for a sharp decrease in the sulfur content in fuels, including diesel fuels. This reduction is intended to limit the content of sulfur oxide and nitrogen in automobile exhaust.
  • European legislation specifies the diesel fuel specifications which have been 350 ppm by weight since 2000, and in 2005 will be 50 ppm by weight of sulfur, and in 2009 by 10 ppm by weight of sulfur.
  • US Pat. No. 4,337,156 recommends the use of a KX type zeolite, and a 1-octanol desorbent for separating polar compounds (sulfur, nitrogen, oxygenated) by Simulated Mobile Bed (LMS). of a naphtha cut (term of the skilled person designating a petrol cut of initial boiling point about 70 ° C and end boiling point about 220 ° C).
  • LMS Simulated Mobile Bed
  • the sulfur compounds present in the naphtha section are of the thiophene type and not of the benzo or dibenzothiophene type which are the sulfur compounds the most difficult to eliminate in the case of a distillate, ie those which will be encountered in the context of the present invention.
  • US Pat. No. 5,454,933 describes a process for the desulphurisation of diesel fuel, which consists in linking a conventional hydrotreatment to eliminate sulfur compounds known as "easy sulfur” according to the English terminology (which can be translated as sulfur compounds which are easy to remove) with a process. adsorption of difficult sulfur compounds on activated carbon having a specific surface area of between 800 and 1200 m 2 / gram and having a certain porous structure. These sulfur compounds difficult to eliminate (so-called "hard sulfur” according to the English terminology) correspond to beta-substituted dibenzothiophene type aromatics.
  • the adsorption process described in this patent is not designed to fully treat the diesel fuel feedstock, but necessarily requires prior hydrotreatment.
  • Patent FR 02/03314 proposes a process for desulfurizing a hydrocarbon feedstock on a complexing solid based on ⁇ electron acceptors. This process can be preceded by a fractionation column which allows to produce a light effluent to the specifications and a heavy effluent that must be desulphurized. In the case of fixed bed operation, the losses of the product to be desulphurized are not negligible because of the physical filling of the porous volume of the adsorbent. To remedy this, it is proposed in said patent to use different washing fluids with varying adsorption forces thus reducing hydrocarbon losses without, however, avoid them entirely.
  • Figure 1 shows a diagram of the method according to the invention in its most general design.
  • FIG. 2 represents a variant of the process diagram according to the invention.
  • the sulfur content of the gas oil obtained will generally be less than 10 ppm by weight, preferably less than 5 ppm by weight, and even more preferably less than 1 ppm by weight, with a weight yield relative to the incoming charge generally greater than 97% and preferably greater than at 99%.
  • the feedstock to be treated may be previously sent to a distillation column located upstream of the simulated moving bed adsorption unit, from which a head stream is extracted which is used at least partly as a feedstock. desorbent, and a bottom stream that is introduced as a charge of the simulated moving bed adsorption unit.
  • the feedstock (1) enters the adsorption desulfurization unit operating in a simulated moving bed (2).
  • This adsorption desulphurization unit consists of at least one adsorption column containing a plurality of adsorbent beds, interconnected with one another and having a selectivity in favor of the sulfur-containing compounds with respect to the chemical families of the charge (alkanes and aromatics). ) that one wishes to purify.
  • Said adsorption column comprises at least four zones delimited on the one hand by the injections of the mixture (1) constituting the adsorption charge and the desorbent (9b), on the other hand by the withdrawals of a raffinate (3) containing the desulphurized gas oil mixed with desorbent, and an extract (4) containing predominantly sulfur compounds removed in mixture with desorbent.
  • the desorption zone 1 of the sulfur compounds is between the injection of the desorbent (9b) and the extraction of the extract (4).
  • Zone 2 desorption of alkanes and aromatics is between the withdrawal of the extract (4) and the injection of the adsorption charge (1).
  • the zone 3 for adsorption of the sulfur compounds is between the injection of the feedstock (1) and the withdrawal of the raffinate (3).
  • Zone 4 is between the raffinate withdrawal (3) and the injection of the desorbent (9b) and allows to adsorb the alkanes and aromatics.
  • the step of separating the streams (3) and (4) is carried out by means of two distillation columns (5) and (6) fed respectively by the raffinate (3) and the extract (4) which make it possible to eliminate substantially all the desorbent at the bottom of the column, for example.
  • This mixture can itself be advantageously mixed with a flow from the refinery whose sulfur specifications allow it, and whose boiling temperatures are compatible with those of the product mixture, such as for example fuel oil.
  • This mixture can also be recycled to a conventional hydrotreating unit which will make it possible to eliminate the recycled sulfur compounds by an effect of increasing the sulfur content of the feedstock, since the catalytic activity of the hydrodesulfurization process is directly linked. at the sulfur input concentration to be treated.
  • desorbents (9) and (11) are recovered at the bottom of the columns (5) and (6) to form the stream (9a) which is returned to the simulated moving bed desulfurization unit (LMS) (2) with a possible addition of desorbent (12) corresponding to the possible losses of desorbent undergone in the distillation columns (5) and (6).
  • LMS simulated moving bed desulfurization unit
  • the different streams (9), (11) and (12) form the addition of desorbent (9b) which is introduced into the simulated moving bed column (2).
  • the flow (7) constitutes the recirculation flow necessary for the operation of a simulated moving bed column. It consists of regeneration solvent and diesel in varying proportions over time.
  • FIG. 2 describes a variant of the invention in which a distillation step corresponding to the unit (1c) is placed upstream of the diagram described in FIG.
  • This distillation step consists of sending the feedstock (1) into a distillation tower (1e) which produces a sulfur-containing heavy hydrocarbon fraction (1b) which is sent to the LMS adsorption unit (2) as described. in FIG. 1, and a light hydrocarbon fraction (1a) whose sulfur content is less than or equal to the required specifications.
  • This desulphurized section (1a) can also be used as a desorbing agent in the LMS adsorption unit (2), in which case once the permanent pseudo regime is reached, the portion (1d) of the stream (1a) will be used. as a desorbent booster and mixed with the stream (9a) to form the desorbent stream (9b) of the adsorption column (2).
  • the remaining part (1c) of light desulphurized hydrocarbons is already to the required specifications and can therefore be used as a base in commercial diesel.
  • the diesel produced by this unit will have a variable sulfur content depending on the operating conditions of the hydrotreatment. Diesel fuel thus produced, the sulfur content of which may vary between 10 ppm by weight and 1000 ppm by weight, can be treated with one or other of the variants of the method according to the invention corresponding to Figures 1 and 2.
  • the adsorbent used in the LMS adsorption unit is generally chosen from the following families of conventional adsorbents: activated carbon, zeolites, silicas, aluminas, silica-aluminas, spent catalysts, resins, clays, bridged clays, reduced metals or oxides and any possible mixture between these different families of adsorbents.
  • the adsorbent used in the LMS adsorption unit in the active carbon family will be chosen, since these solids have a sufficient selectivity between the sulfur-containing molecules and the remainder of the diesel fuel matrix.
  • the adsorbent used in the LMS adsorption unit in the active carbon family will be chosen, since these solids have a sufficient selectivity between the sulfur-containing molecules and the remainder of the diesel fuel matrix.
  • preference will be given to those having a specific surface area greater than 1200 m 2 / gram, and a total pore volume greater than 0.5 cm 3 / gram, the precursor being which type, and the type of activation used to create porosity can be either physical or chemical, or a combination of both.
  • the total pore volume is preferably greater than or equal to 0.5 cm 3 / gram, and the pore volume fraction included in the microporosity of said adsorbent solid is preferably greater than or equal to 0.2 cm 3 / gram.
  • Microporosity is defined as the category of pores whose diameter is less than 20 angstroms (2 nanometers, ie 2 10 -9 meters).
  • the number of adsorbent beds constituting the simulated moving bed adsorption unit is generally less than 24, and preferably less than 15.
  • the desorbent may be selected from the following chemical families: nitrogen compounds, alcohols, ethers, aromatics, light desulfurized cut, or any other refinery stream and their mixture.
  • the aromatics may be chosen.
  • the volume ratio of the desorbent on charge in the simulated moving bed separation unit is generally between 0.5 and 2.5, and preferably between 0.7 and 2.0.
  • the working temperature may be between ambient temperature and the final boiling temperature of the hydrocarbon fraction to be treated, knowing that it is necessary to ensure operation in the liquid phase. It will generally work between 50 ° C and 350 ° C, and more preferably between 50 ° C and 250 ° C.
  • the working pressure will be between the bubble point of the lightest compound and 15 bars absolute (1.5 MPa), so as to guarantee the existence of a liquid phase throughout the LMS adsorption unit, knowing that the performance of the process depends little on this parameter. However, it can affect the cost of fitting.
  • zone 1 3 beds
  • zone 2 5 beds
  • zone 3 5 beds
  • zone 4 2 beds
  • the permutation time of the valves (or period) is 152.0 seconds.
  • the raffinate obtained delivers a gas oil at a content of 1.5 ppm by weight of pure sulfur with a yield of 99.5%.
  • the productivity of the unit expressed as the volume of gas oil produced per volume of adsorbent and per time unit is equal to 1.31 m 3 / (m 3 h).
  • the purification of diesel fuel containing 1.5% sulfur (by mass) is carried out in simulated moving bed, on a pilot unit comprising 15 beds of 609.6 cm 3 each, divided into 4 zones according to the following configuration: zone 1: 3 beds , zone 2: 5 beds, zone 3: 5 beds and zone 4: 2 beds.
  • the permutation time of the valves (or period) is 152.0 seconds.
  • the raffinate obtained delivers a gas oil at a content of 3.5 ppm by weight of sulfur of purity with a yield of 99.5%.
  • the productivity of the unit expressed as a volume of diesel fuel produced per volume of adsorbent and per time unit is equal to 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)
EP05292374A 2004-11-23 2005-11-08 Procédé de désulfuration d'une coupe hydrocarbonée en lit mobile simulé Withdrawn EP1666568A1 (fr)

Applications Claiming Priority (1)

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

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EP1666568A1 true EP1666568A1 (fr) 2006-06-07

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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106244225A (zh) * 2016-08-12 2016-12-21 中国昆仑工程公司 实现重芳烃高效分离的模拟移动床吸附分离方法

Families Citing this family (10)

* Cited by examiner, † Cited by third party
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EP2792406A1 (en) * 2006-01-30 2014-10-22 Advanced Technology Materials, Inc. A fluid storage and dispensing apparatus
US9315733B2 (en) * 2006-10-20 2016-04-19 Saudi Arabian Oil Company Asphalt production from solvent deasphalting bottoms
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
EP2640811B1 (en) * 2010-11-19 2021-07-14 Indian Oil Corporation Ltd. A process for desulfurization of diesel with reduced hydrogen consumption
US8679231B2 (en) 2011-01-19 2014-03-25 Advanced Technology Materials, Inc. PVDF pyrolyzate adsorbent and gas storage and dispensing system utilizing same
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
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
CN105542835B (zh) * 2015-12-11 2017-08-25 中国海洋石油总公司 一种模拟移动床吸附分离多环芳烃的方法
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
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

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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
FR2837212A1 (fr) 2002-03-18 2003-09-19 Total Raffinage Distribution Procede de deazotation de charges hydrocarbonees en presence d'une masse polymerique
EP1454976A1 (fr) * 2003-03-07 2004-09-08 Institut Francais Du Petrole Procédé de desulfuration, de deazotation et/ou de desaromatisation d'une charge hydrocarbonée par adsorption sur un solide adsorbant usé

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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
WO2003097771A1 (fr) * 2002-05-22 2003-11-27 Japan Energy Corporation Agent de desulfuration par adsorption utile pour desulfurer la coupe petroliere et procede de desulfuration comprenant ledit agent

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
FR2837212A1 (fr) 2002-03-18 2003-09-19 Total Raffinage Distribution Procede de deazotation de charges hydrocarbonees en presence d'une masse polymerique
EP1454976A1 (fr) * 2003-03-07 2004-09-08 Institut Francais Du Petrole Procédé de desulfuration, de deazotation et/ou de desaromatisation d'une charge hydrocarbonée par adsorption sur un solide adsorbant usé

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Title
HJ BART, U VON GEMMINGEN: "Ullmann's Encyclopedia of Industrial Chemistry - Adsorption", 15 January 2005, WILEY VCH VERLAG GMBH & CO, ONLINE, XP002346887 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106244225A (zh) * 2016-08-12 2016-12-21 中国昆仑工程公司 实现重芳烃高效分离的模拟移动床吸附分离方法

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Publication number Publication date
US20060131217A1 (en) 2006-06-22
JP2006144020A (ja) 2006-06-08
FR2878252B1 (fr) 2008-08-22
CN1800309A (zh) 2006-07-12
FR2878252A1 (fr) 2006-05-26
KR20060057510A (ko) 2006-05-26

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