EP1715026B1 - Nouveau procédé de désulfuration des essences par alourdissement des composées soufrés - Google Patents

Nouveau procédé de désulfuration des essences par alourdissement des composées soufrés Download PDF

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Publication number
EP1715026B1
EP1715026B1 EP06290373.7A EP06290373A EP1715026B1 EP 1715026 B1 EP1715026 B1 EP 1715026B1 EP 06290373 A EP06290373 A EP 06290373A EP 1715026 B1 EP1715026 B1 EP 1715026B1
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Prior art keywords
resin
sulfur
compounds
desulfurization
petroleum cut
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EP06290373.7A
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German (de)
English (en)
French (fr)
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EP1715026A1 (fr
Inventor
Florent Picard
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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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • 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
    • C10G17/00—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge
    • C10G17/095—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge with "solid acids", e.g. phosphoric acid deposited on a carrier
    • 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
    • C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
    • C10G25/03—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material with crystalline alumino-silicates, e.g. molecular sieves
    • C10G25/05—Removal of non-hydrocarbon compounds, e.g. sulfur compounds

Definitions

  • the present invention relates to a process making it possible to reduce the sulfur contents contained in gasolines.
  • the invention relates to a desulphurization scheme for a gasoline cut comprising in particular olefins.
  • the present process finds particular application in the transformation of conversion gasolines, and in particular gasolines coming from catalytic cracking, fluid bed catalytic cracking (FCC), a coking process, a visbreaking process, or a pyrolysis process.
  • FCC fluid bed catalytic cracking
  • the process which is the subject of the present invention makes it possible to efficiently valorize a gasoline cut possibly comprising hydrocarbons with two, three or four carbon atoms, by reducing the total sulfur content of said gasoline cut to very low levels, compatible with current specifications or to come, without significant reduction in gasoline yield and octane number.
  • FCC gasoline which can be translate as catalytic cracking in a fluidized bed.
  • FCC gasolines therefore constitute the preferred feedstock for the desulfurization process of the present invention.
  • the process according to the invention is applicable to any gasoline cut containing a certain proportion of olefins, and which may also contain some lighter compounds belonging to the C3 and C4 cuts.
  • the gasoline feedstock of the present process can also be mixed with alcohols of the methanol, ethanol type, or possibly heavier alcohols.
  • a first desulfurization route very commonly used in refineries consists of the hydrodesulfurization of gasolines. To achieve the standards currently required using such processes, it is however necessary to operate under severe temperature and pressure conditions, and in particular to work under high hydrogen pressure.
  • Such operating conditions generally result in at least partial hydrogenation of the olefins, and subsequently a significant reduction in the octane number of the desulfurized gasolines obtained by said processes.
  • Another route consists of using gasoline desulphurization processes based on acid catalyst treatment.
  • This type of treatment aims to weigh down the unsaturated thiophenic sulfur compounds by an addition reaction (or alkylation) on said unsaturated sulfur compounds, of the olefins present in the feed, and to a lesser extent, to oligomerize a fraction of said olefins contained in the feed.
  • the acid catalyst can be placed directly into the distillation column.
  • the heavy sulfur compounds are in this case extracted at the bottom of the column, while the desulphurized gasoline is extracted at the top of the column.
  • the acid catalysts described in the previous patents are generally solid catalysts exhibiting Brönstedt acidity, such as ion exchange resins or supported sulfuric or phosphoric acids.
  • the present invention describes a process for desulfurizing olefinic gasolines by weighing down sulfur compounds, based on an ion exchange resin catalyst, having an acidity measured by an acid capacity greater than 5.0 equivalents per kg, a specific surface area included between 25 m2/g and 50 m2/g, a pore volume of between 0.16 ml/g and 0.25 ml/g and an average pore diameter of between 20 nm and 28 nm.
  • the process consists of bringing the charge to be desulphurized into contact with the resin having the characteristics described above.
  • the feed can optionally be treated as a mixture with another hydrocarbon feed such as the C3 or C4 fractions rich in olefins, or alcohols such as methanol, ethanol, or heavier alcohols.
  • the operating conditions are adjusted so as to promote the addition of the olefinic compounds contained in the feed to the sulfur compounds.
  • the two main reactions sought are the addition reactions of olefins to thiophene and/or methylthiophenes, and possibly heavier thiophene compounds, and the addition of olefins to mercaptans.
  • oligomerization reactions of olefins generally lead to the formation of olefins generally having more than 8 carbon atoms.
  • the product collected at the outlet of the reactor is then distilled in order to recover at least a light fraction depleted in sulfur, constituting the desulphurized gasoline, and a heavy fraction which concentrates the heavy sulfur compounds.
  • the present patent therefore presents a new desulfurization process by addition of sulfur compounds to the olefins, or part of the said olefins contained in the feed to be treated, using as catalyst an acid ion exchange resin which comprises a copolymer of styrene and divinylbenzene onto which sulfonic acid groups are grafted.
  • the acid resin used in the present process is chosen to exhibit improved activity and stability compared to the acid resins used in the prior art for this type of application.
  • the light fraction generally has sufficiently low sulfur contents to be incorporated directly into the gasoline pool.
  • the heavy fraction can be incorporated into the gasoline pool after desulfurization by hydrodesulfurization for example, or be mixed with the middle distillate pool to produce a kerosene or gas oil cut.
  • the resin used in the context of the present invention notably has an acid capacity greater than 5.0 equivalents per kg.
  • the equivalents per kg correspond to the number of moles of protons per kg of resin.
  • the use of a resin in accordance with the invention made it possible, on the one hand, to significantly improve the weighting activity of the sulfur compounds, and thus to operate at a lower temperature, which is favorable to improving the lifespan of the resin, and on the other hand, to reduce the speed of deactivation by deposition of polymers.
  • the resin is used in a reactor, under conditions such that the treated hydrocarbon fraction is in liquid form.
  • Several solutions for using the resin can be considered, such as using it in a fixed bed, in a multitubular reactor, in chamber reactors, in a bubbling bed, in a moving bed or in a fluidized bed.
  • the reactions of weighting of sulfur compounds or oligomerization of olefins are exothermic. Since resins are solids that can be degraded at high temperatures, it is preferable to control the thermal profile of the reactor.
  • part of the effluent can be recycled in the reactor in order to limit the conversion rates of olefins per pass, and thus control the thermal rise in the reactor.
  • the temperature rise in the reactor is generally easier to control via exchange surfaces directly immersed in the reaction medium, which avoids the appearance of hot spots in the reactor.
  • the catalyst can be placed in a single reactor, or preferably in several reactors operated in parallel or in series. This device is advantageous for the present invention because it allows, at any time, to stop a reactor and replace the spent catalyst, while maintaining continuous operation of the unit.
  • a heat exchanger can be inserted between each reactor making it possible to adjust the inlet temperature of each reactor in the series independently.
  • the process according to the invention is particularly well suited to the treatment of gasolines containing sulfur and olefins. These compounds are present simultaneously in conversion gasolines, and in particular gasolines coming from catalytic cracking, fluid bed catalytic cracking (FCC), a coking process, a visbreaking process, a process pyrolysis. These gasolines generally contain at least 30 ppm sulfur and 10% olefins.
  • the end point of the charge is generally less than 230°C, but we will preferably treat gasolines whose boiling temperature is less than 160°C, and preferably less than 130°C.
  • the filler may also contain hydrocarbon fractions with 3 or 4 carbon atoms.
  • the treated feedstock is previously freed from light cuts which concentrate olefins with 5 carbon atoms or less, as well as sulfur compounds lighter than thiophene.
  • these light sulfur compounds are primarily mercaptans that can be removed during a specific processing step, such as extractive oxidation or thioetherification.
  • oxygenated compounds in the form of alcohols such as for example methanol or ethanol.
  • alcohols such as for example methanol or ethanol.
  • ethers which have a good octane number, and which can be incorporated into the gasoline pool.
  • the feed may optionally undergo pretreatment intended to reduce the content of nitrogen compounds. Any solution known to those skilled in the art for carrying out said reduction of nitrogen compounds can be envisaged.
  • This step may consist, for example, of washing the charge with an acidic aqueous solution, or of treating the gasoline on an acidic guard bed composed of a zeolite, an acidic resin, or any other solid capable of to retain basic nitrogen compounds.
  • a preferred solution for trapping nitrogen compounds consists of using resin in accordance with the invention partially used in a guard bed.
  • the device must comprise at least two reactors, a first reactor containing used resin, operated so as to trap at least a fraction of the nitrogen compounds, and a second reactor containing active resin used to carry out the reactions of heaviness of sulfur compounds.
  • the resin used in the second reactor does not have, or no longer has, sufficient activity, it can be used as a guard bed.
  • the nitrogen compounds extraction step is generally necessary if the feed contains more than 50 ppm of nitrogen, and even more than 20 ppm of nitrogen.
  • the feed may also undergo pretreatment to selectively hydrogenate the diolefins.
  • cracked gasolines generally contain diolefins in the amount of 1% by weight to 3% by weight. These diolefins are very reactive in polymerization, and can cause premature deactivation of the resin by polymer deposition.
  • the operating conditions of the sulfur compounds weighting stage must be optimized to produce gasolines meeting the desired specifications.
  • the VVH is between 0.2 h -1 and 5 h -1 , and preferably between 0.5 h -1 and 3 h -1 per reactor.
  • the temperature is adjusted in order to achieve the desired rate of transformation of the sulfur compounds.
  • the temperature will be adjusted so as not to exceed the targeted conversion rates, and in particular, to convert a maximum of 99% of the sulfur in thiophene form present in the feed.
  • the preferred conversion rate of thiophene is less than 99%, and preferably 98%. Higher conversion rates generally require operating the resin at high temperatures, resulting in accelerated deactivation by polymer deposition.
  • the operating temperatures are generally between 50°C and 150°C, and preferably between 60°C and 140°C.
  • the first is a resin according to the prior art, the second comparative, the third also according to the invention with a higher concentration of acid sites, and a lower specific surface area than the second.
  • the characteristics of the resins used are described in Table 1. These resins comprise a copolymer of styrene and divinylbenzene onto which sulfonic acid groups are grafted.
  • Table 1 Resin Concentration of acid sites, eq/kg Specific surface area, m2/g average pore diameter, nm Total pore volume, ml/g 1 according to the prior art 4.7 53 30 0.40 2 comparison 5.2 50 30 0.35 3 according to the invention 5.4 33 24 0.20
  • the charge A used to evaluate these catalysts is an FCC gasoline whose main characteristics are given in table 2.
  • Table 2 Load A Analysis Density 15/4 0.6937 Analysis of sulfur compounds S total, ppm weight 410 Analysis of sulfur compounds Thiophene, ppm weight 83.5 C1-Thiophene, ppm weight 162.11 Hydrocarbon analysis nParaffins, % weight 4.6 isoParaffins, % weight 32.8 Naphthene, % weight 8.2 Aromatic, % weight 5.2 Olefins, % weight 49.2 Simulated distillation 5% weight 23.3 10% weight 26.2 50% weight 69.0 95% weight 112.3 98% weight 121.4 Total nitrogen, ppm weight 14.4
  • the most active resin is resin 3 according to the invention.
  • the stabilities of resins 1 and 3 were compared during two tests of approximately 400 hours. For each test, 60 ml of resin are loaded into a reactor. The pressure and flow rates are kept constant and equal to 2 MPa and 50 ml/h respectively.
  • a sample is collected periodically and analyzed by gas chromatography equipped with a specific detector for sulfur compounds.
  • the thiophene conversion rate is thus calculated in relation to the thiophene content of the feed, which makes it possible to follow the evolution of the activity of the catalyst.
  • the temperature is adjusted during the test in order to maintain a thiophene conversion rate between 90% and 99%.
  • There figure 2 presents the evolution of the relative activity of the two resins as a function of time.
  • Resin 3 has a lower deactivation slope than resin 1.
  • the loss of activity of resin 3 observed after 300 hours is equivalent to the loss of activity of resin 1 after 150 hours. It is therefore very advantageous to use resin 3 which is approximately twice as stable as resin 1.
  • Resin 3 according to the invention is therefore better suited to weighing down sulfur compounds, and also has the best activity and the best stability.

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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)
  • Crystallography & Structural Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
EP06290373.7A 2005-04-19 2006-03-03 Nouveau procédé de désulfuration des essences par alourdissement des composées soufrés Active EP1715026B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR0503981A FR2884521B1 (fr) 2005-04-19 2005-04-19 Nouveau procede de desulfuration des essences par alourdissement des composes soufres

Publications (2)

Publication Number Publication Date
EP1715026A1 EP1715026A1 (fr) 2006-10-25
EP1715026B1 true EP1715026B1 (fr) 2023-10-11

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EP06290373.7A Active EP1715026B1 (fr) 2005-04-19 2006-03-03 Nouveau procédé de désulfuration des essences par alourdissement des composées soufrés

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US (1) US7504022B2 (enExample)
EP (1) EP1715026B1 (enExample)
JP (1) JP5270070B2 (enExample)
KR (1) KR101286805B1 (enExample)
BR (1) BRPI0601297A (enExample)
FR (1) FR2884521B1 (enExample)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011135206A1 (fr) * 2010-04-28 2011-11-03 IFP Energies Nouvelles Procede d'oligomerisation des olefines utilisant au moins un catalyseur organique possedant une forte densite de sites acides
CN116396139B (zh) * 2023-06-08 2023-08-18 新疆天利石化股份有限公司 一种于固定床反应器中催化脱除苯乙烯中噻吩类芳香杂环含硫化合物的方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6048451A (en) * 1997-01-14 2000-04-11 Bp Amoco Corporation Sulfur removal process
US5863419A (en) * 1997-01-14 1999-01-26 Amoco Corporation Sulfur removal by catalytic distillation
US6059962A (en) * 1998-09-09 2000-05-09 Bp Amoco Corporation Multiple stage sulfur removal process
US6352640B1 (en) * 2000-04-18 2002-03-05 Exxonmobil Research And Engineering Company Caustic extraction of mercaptans (LAW966)
FR2821852B1 (fr) 2001-03-12 2003-05-02 Inst Francais Du Petrole Procede de production d'une essence desulfuree a partir d'une coupe essence contenant de l'essence de conversion
FR2835530B1 (fr) * 2002-02-07 2004-04-09 Inst Francais Du Petrole Procede integre de desulfuration d'un effluent de craquage ou de vapocraquage d'hydrocarbures
FR2840620B1 (fr) 2002-06-07 2004-07-30 Inst Francais Du Petrole Procede de production d'hydrocarbures a faible teneur en soufre et en azote
JP2005068126A (ja) * 2003-08-20 2005-03-17 Rohm & Haas Co 芳香族アルキル化反応に使用するための方法、系および触媒
FR2890077B1 (fr) * 2005-08-26 2012-03-23 Inst Francais Du Petrole Procede de desulfuration d'essences olefiniques par alourdissement des composes soufres avec regeneration du catalyseur

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Publication number Publication date
US20070023324A1 (en) 2007-02-01
FR2884521A1 (fr) 2006-10-20
EP1715026A1 (fr) 2006-10-25
KR20060110226A (ko) 2006-10-24
BRPI0601297A (pt) 2007-05-15
FR2884521B1 (fr) 2009-08-21
JP2006299263A (ja) 2006-11-02
US7504022B2 (en) 2009-03-17
KR101286805B1 (ko) 2013-07-17
JP5270070B2 (ja) 2013-08-21

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