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US20060180501A1 - Process and device for desulphurizing hydrocarbons containing thiophene derivatives - Google Patents

Process and device for desulphurizing hydrocarbons containing thiophene derivatives Download PDF

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Publication number
US20060180501A1
US20060180501A1 US10/250,431 US25043105D US2006180501A1 US 20060180501 A1 US20060180501 A1 US 20060180501A1 US 25043105 D US25043105 D US 25043105D US 2006180501 A1 US2006180501 A1 US 2006180501A1
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process according
catalyst
oxidation
hydrocarbons
oxidizer
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Pedro Da Silva
Edmond Payen
Jean-Yves Carriat
Marc Bisson
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TotalEnergies Marketing Services SA
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Assigned to TOTAL FINA ELF FRANCE reassignment TOTAL FINA ELF FRANCE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: PAYEN, EDMOND, CARRIAT, JEAN-YVES, DA SILVA, PEDRO, BISSON, MARC
Publication of US20060180501A1 publication Critical patent/US20060180501A1/en
Assigned to FIRST-CITIZENS BANK & TRUST COMPANY reassignment FIRST-CITIZENS BANK & TRUST COMPANY SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CARBYNE LTD, CARBYNE, INC.
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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
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
    • C10G53/14—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one oxidation step
    • 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
    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
    • C10G27/12—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen with oxygen-generating compounds, e.g. per-compounds, chromic acid, chromates

Definitions

  • the present invention concerns a process and a device for desulfurizing hydrocarbons, and particularly, for desulfurizing fuel bases for gasoils, kerosenes, and gasolines.
  • it concerns the desulfurization of fuel bases containing dibenzothiophenic compounds.
  • refineries use catalytic hydrosulfurization processes to reduce the sulfur content in fuels.
  • gasoils derived directly from distillation are hydrotreated between 300° and 400° C. under pressure of hydrogen varying between 30 and 100 bars (30 to 100 ⁇ 10 5 Pa), in the presence of a catalyst on a fixed bed and composed of sulfides of metals of groups VIb and VIII deposited on aluminum oxide, for example cobalt and molybdenum sulfides or nickel and molybdenum sulfides. Because of the operating conditions and the consumption of hydrogen, these processes can be costly both in investment and in operation, particularly if fuels with very low sulfur content are to be produced.
  • the size of the reactor can be multiplied by four and the quantity of hydrogen needed for the reaction must be increased by about 20%. It is particularly difficult to eliminate traces of sulfur by such processes, especially if the sulfur belongs to refractory molecules such as alkyl dibenzothiophene in position 4, or 4 and 6.
  • gasolines are not only distilled directly from crude oil, these gasolines being then slightly sulfurous, but can also be obtained by several processes such as reforming of naphthas, isomerization of light naphthas, alkylation of butane or propane producing isooctane, methoxylation of isobutene, and the catalytic cracking of distillates under vacuum or atmospheric residue.
  • catalytic cracking provides between 20% and 60% by weight of final gasoline.
  • these gasolines contain up to 0.1% by weight of sulfur.
  • hydrodesulfurization is not only ineffective with respect to thiophenic compounds, but it is also destructive with respect to the octane index of the gasoline. Indeed, during the hydrodesulfurization reaction, there is a partial hydrogenation of the olefins contained in these cracked gasolines, their disappearance resulting in a decrease in the octane index of the gasoline and thus a deterioration in the quality of the gasoline. To compensate for this loss, it is possible to introduce other components to improve this index or to reprocess the gasoline itself to increase this index.
  • Processes for selective oxidation of sulfurous compounds are among treatment processes that can achieve this end.
  • oxidation by organic peroxides, organic hydroperoxides, hydrogen peroxide, and organic peracids has been considered either without catalyst, or by homogenous catalysis in the presence of catalysts based on organometallic compounds or metallic oxides in aqueous phase (see U.S. Pat. No. 3,668,117, U.S. Pat. No. 3,565,793, EP 0,565,324, and publications by T. A. KOCH, K. R. KRAUSE, L. EMANZER, H. MEHDIZADEH, J. M.
  • Another process consists of producing a desulfurized hydrocarbonated material in three processing steps.
  • the first step consists of at least partially oxidizing the sulfurous compounds by placing them in contact with peroxides in the presence of metallic catalysts containing metals from the group including titanium, zirconium, molybdenum, tungsten, vanadium, tantalum, chromium, and their mixtures, in liquid or solid form possibly supported, although the supports are not essential for the reaction.
  • the second step consists of placing the hydrocarbonated material containing the oxidized compounds in contact with another metallic component, metallic oxide or peroxide (metals from the group including nickel, molybdenum, cobalt, tungsten, iron, zinc, vanadium, copper, manganese, mercury, and their mixtures), at a temperature varying from 250° C. to 730° C., under hydrogen pressure.
  • metallic oxide or peroxide metal from the group including nickel, molybdenum, cobalt, tungsten, iron, zinc, vanadium, copper, manganese, mercury, and their mixtures
  • the present invention therefore proposes a process for desulfurizing hydrocarbons, particularly those used as bases for fuels containing thiophenic derivatives, without reducing the index of the octane number or of the cetane number, sometimes even increasing these indices.
  • it concerns the finish treatment of hydrotreated gasoils, kerosenes, and catalytic cracked gasolines with high concentrations of refractory thiophenic derivatives in hydrogenations.
  • the invention proposes such a process that makes it possible to reach oxidation levels that are identical if not greater than the known processes, while limiting the reaction and separation times of the oxidized sulfurous compounds from the desulfurized hydrocarbons.
  • An object of the present invention is therefore a process for selectively desulfurizing the thiophenic compounds contained in the hydrocarbons produced from the distillation of crude oil, refined or not, consisting of oxidizing the thiophenic sulfur atoms into sulfones in the presence of an oxidizing agent and a catalyst, and of separating the obtained sulfonated compounds from said hydrocarbons, this process being characterized in that it comprises at least a first step of oxidation/adsorption by heterogeneous catalysis of the sulfurous compounds, in an organic medium, at a temperature of at least 40° C., in the presence of an organic oxidizer from the family of peroxides and peracids and in the presence of a catalyst having a specific surface area greater than 100 m 2 /g and a porosity varying from 0.2 to 4 ml/g, and a second step of regeneration of the used catalyst, the regeneration step always following the oxidation/adsorption step.
  • derivatives of thiophene are understood as being benzothiophenic, polybenzothiophenic compounds and their alkyl derivatives, among which are the alkyldibenzothiophenes, particularly refractory to the conversion processes usually used by refiners.
  • the process of the invention has the advantage, on the one hand, of ensuring the oxidation at atmospheric pressure of all of the sulfur contained in the hydrocarbons, and more selectively a conversion of the thiophenic derivatives into sulfones, this by means of a simple industrial process, and on the other hand, of simultaneously adsorbing these sulfoxide compounds on the catalyst.
  • the separation of the hydrocarbons from most of the formed sulfones and sulfoxides is immediate, with the latter ending up in solid form deposited on the catalyst or deposited in a form that can be filtered by known means, in the treated hydrocarbons.
  • This catalyst on which these sulfoxide compounds have been absorbed, constitutes the “used catalyst.”
  • the sulfones that may have been dissolved in the treated hydrocarbons can be extracted.
  • this oxidation/adsorption has no effect on the olefins, which in catalytic cracked gasolines does not change the octane index, or the concentration of unsulfurous aromatic compounds.
  • the oxidation process according to the invention improves the cetane number of the gasoils.
  • the oxidation/adsorption and regeneration steps can be performed in the same reactor or simultaneously in reactors arranged in parallel and operating alternatively for one or the other of the fixed bed steps, or in at least two moving-bed reactors connected to each other by the catalytic bed, one being used for oxidation/adsorption and the other for regeneration.
  • the first reactor containing a fixed catalyst bed receives the flow of hydrocarbons and oxidizing agent and the second receives, for the regeneration of the catalyst, liquid effluents, such as a washing solvent, or oxidizing gaseous effluents like air or an air/N 2 mixture, the temperature of the catalytic bed being increased.
  • liquid effluents such as a washing solvent, or oxidizing gaseous effluents like air or an air/N 2 mixture
  • the hydrocarbons With a moving-bed, the hydrocarbons are brought into the first reactor where the oxidation takes place, the catalyst being pushed progressively toward the second reactor where it is regenerated before being returned to the oxidation/adsorption reactor.
  • the moving-bed reactors well known particularly in the area of reforming, can be used in this device.
  • a third reactor is used, placed between the first two reactors and making it possible to eliminate the hydrocarbons from the used catalyst before washing it or burning off the trapped sulfone and sulfoxide compounds.
  • the catalysts used according to the present invention are selected among the supports from the group consisting of silicas, aluminum oxides, zirconias, amorphous or crystalline aluminosilicates, aluminophosphates, mesoporous silicic and silicoaluminate solids, activated carbon and clays, these supports being used alone or in mixture.
  • these supports can be used advantageously as supports of metals of the group consisting of titanium, zirconium, vanadium, chromium, molybdenum, iron, manganese, cerium, and tungsten; these metals in oxide form can be introduced into the matrix of the support or deposited on the surface of the support.
  • the catalyst contains from 0 to 30% by weight of metal in oxide form on at least one support.
  • the catalyst contains from 0 to 20% metal in oxide form.
  • supports composed of refractory oxides, gamma-aluminum oxides, silicon oxides, silicic mesoporous solids, and silicoaluminates are preferred.
  • catalysts containing tungsten or titanium in oxide form are preferred, deposited on a support or introduced into the matrix, this support being selected from among the silicon oxides, aluminum oxides and aluminosilicates, alone or in mixture.
  • the total oxidizer/sulfur mol ratio contained in the hydrocarbons is between 2 and 20, and preferably between 2 and 6.
  • the oxidizers are selected from among the compounds with the general formula R 1 OOR 2 , in which R 1 and R 2 are identical or different, selected from among hydrogen, linear or branched alkyl groups having from 1 to 30 carbon atoms and aryl or alkylaryl groups the aryl motif of which can be replaced by alkyl groups, while R 1 and R 2 cannot be hydrogen simultaneously.
  • the oxidizer of the formula R 1 OOR 2 is selected from the group consisting of tert-butyl hydroperoxide and di-tert butyl peroxide.
  • oxidizers of the invention are selected so that R 3 is hydrogen or a linear or branched alkyl group having from 1 to 30 carbon atoms. They are preferably selected from the group consisting of peracetic acid, performic acid, and perbenzoic acid.
  • the catalyst regeneration step consists of eliminating the formed deposits by washing or combustion.
  • a solvent is used, preferably polar, from the group consisting of water, linear or branched alcanols having from 1 to 30 carbon atoms, alone or in mixture with water, alkylnitriles having from 1 to 6 carbon atoms. Water, acetonitrile, methanol, and their mixtures are preferred.
  • the catalyst is brought up to a temperature of no more than 800° C., preferably a temperature equal to or less than 650° C., under a pressure varying from 10 5 Pa to 10 6 Pa, preferably from 10 5 Pa to 2 ⁇ 10 5 Pa, in the presence of an oxidizing gas.
  • Oxidizing gas is understood as being pure oxygen and all mixtures of gas containing oxygen, particularly mixtures of oxygen and nitrogen and air itself.
  • the quantity of oxygen in the nitrogen is adjusted in order to limit the formation of water vapor, since too great a quantity of water vapor has the side effect of modifying the structure of the pores of the catalyst by decreasing their volume, specifically when it contains crystalline alumunosilicates such as zeolites or alumuninophosphates as support. Moreover, this adjustment makes it possible to control the temperature variations related to the exothermicity of the combustion.
  • a second object of the invention is a device for implementing the process defined above, this device comprising at least a first reactor containing an oxidation catalyst and having feed pipes for the hydrocarbons and the oxidizer and an outlet pipe for the desulfurized hydrocarbons, and possibly a second reactor having feed pipes for solvent or oxidizing gas of the catalyst, in order to regenerate it, and an outlet pipe for the combustion gases.
  • Oxidizing gas is understood here as oxygen/air, air/nitrogen, and oxygen/nitrogen mixtures.
  • the reactors can operate with a fixed bed or a moving bed.
  • a third object of the invention is the application of the process defined above to the specific finish treatment of gasolines produced from catalytic cracking, or the treatment of gasoils having been previously hydrotreated and kerosenes, for better economy of the process.
  • FIG. 1 is a diagram of a device with two reactors operating alternatively for oxidizing and for regenerating the catalyst;
  • FIG. 2 is a diagram of a device having two moving-bed reactors, the first corresponding to the oxidation step, the second to the catalyst regeneration step, a pipe for return of the regenerated catalyst being added to the system;
  • FIGS. 3-1 and 3 - 2 show graphs illustrating the total sulfur content, as a function of time, of the hydrocarbons treated according to the invention in the Example III below.
  • the device of FIG. 1 has two reactors 1 and 2 charged with a catalyst arranged as fixed-bed.
  • the pipe 3 takes the sulfurous hydrocarbon load, into which the oxidizer has been introduced by the pipe 4 , the three-way valve 6 a and the pipe 8 a .
  • the flow of desulfurized hydrocarbons leaves the reactor 1 by the pipe 9 a and reaches the desulfurized hydrocarbon outlet pipe 10 a via the three-way valve 7 a.
  • the pipe 5 takes to the reactor 2 either an appropriate solvent or an oxidizing gas, via the three-way valve 6 b and the pipe 8 b .
  • the temperature of the catalytic bed is held at 500° C.
  • the solvent containing the sulfones recovered on the catalyst or the combustion gases, primarily SO 2 , CO, and CO 2 are evacuated via the pipe 9 b , the three-way valve 7 b and the pipe 11 b in the pipe 11 a.
  • the solvent or the oxidizing gas arriving by the pipe 5 is sent to the reactor 1 by the pipe 3 a , the valve 6 a and the pipe 8 a .
  • the solvent or the oxidation gases are taken back in the outlet pipe 11 a via the pipe 9 a and the valve 7 a.
  • valves 6 a , 6 b , 7 a , and 7 b can be exchanged according to a common procedure, in order to allow the circulation of the proposed flows.
  • a filter can be placed advantageously on one of the pipes 9 a or 9 b , or on 10 a or 10 b , to recover the solid sulfones formed during oxidation and remaining in suspension in the hydrocarbons.
  • Sulfur traps equipped with absorbents such as silica or activated alumina can be advantageously added to these same pipes, downstream from these filters, to trap sulfones that are still dissolved in the treated hydrocarbons.
  • the device of FIG. 2 includes two reactors 20 a and 20 b , arranged in series, each containing a moving-bed catalyst, the reactor 20 a operating in oxidation mode and the reactor 20 b operating in regenerative mode, and a propulsion device 30 to allow the catalyst from the reactor 20 b to return to the reactor 20 a.
  • the hydrocarbons are taken by the pipe 40 into the reactor 20 a , after having been doped by the oxidizer via the pipe 50 .
  • the reactor 20 a can be selected from among funnel-shaped reactors, the moving bed of the catalyst being moved by gravity toward the lower part of the reactor. In this way, while the desulfurized hydrocarbons are removed by the pipe 60 , the catalyst is forced by gravity into the reactor 20 b through the pipe 70 .
  • the solvent or combustion gas is introduced via the channel 80 in the reactor 20 b . In order to effect regeneration by combustion, the temperature is increased to and held at 500° C.
  • the sulfones-containing solvent or the combustion gases are removed by the pipe 100 .
  • the regenerated catalyst is taken via the pipe 110 to the device 30 .
  • This device can be a pressurized gas propulsion device or a worm gear. It takes the regenerated catalyst back to the reactor 20 a via the pipe 120 .
  • the reactors 20 a and 20 b can be part of the same unit having two separate stages.
  • the present example describes the effectiveness of the process, according to the invention, with respect to the elimination of the derivatives of the dibenzothiophene present in the partially desulfurized bases for fuels.
  • the samples of catalyst used are of two types, the catalysts formed from a single support and those to which are combined one or more metals deposited by impregnation. Table 1 below provides the specific surface area and porosity characteristics of each of them. TABLE I Catalyst Type Specific surface Pore size sample of support area (m 2 /g) (Angströms) Metal oxides C 1 SiO 2 160 252 C 2 SiO 2 140 300 WO 3 C 3 Al 2 O 3 gamma 245 104 WO 3 C 4 Beta zeolite 470 30 TiO 2 C 5 Mesoporous 1000 85 C 6 Mesoporous 830 70 MoO 3 C 7 Al 2 O 3 ⁇ 210 95 WO 3
  • the catalysts C 2 , C 3 , and C 6 were obtained by wet impregnation with a metallic salt, respectively ammonium metatungstate and ammonium hexamolybdate, in a concentration of 140 mg of metal per gram of support, then dried and finally calcinated at a temperature of 500° C.
  • a metallic salt respectively ammonium metatungstate and ammonium hexamolybdate
  • the catalyst C 4 was obtained by treating a beta zeolite with commercially available titanium according to the procedure described in patent EP 0,842,114.
  • Example II The same process as in Example I is used, with catalysts C 1 -C 6 , and the formation is monitored of sulfones and sulfoxides with reference to the dibenzothiophene compounds, particularly the benzothiophene (BT), dibenzothiophene (DBT) and the 4,6 dimethyldibenzothiophene (DMBT), by gas chromatography equipped with a sulfur specific detector (SIEVERS process).
  • BT benzothiophene
  • DBT dibenzothiophene
  • DMBT 4,6 dimethyldibenzothiophene
  • the present example seeks to show, at the same time as the oxidation, the effect as a function of time of the adsorption of the sulfone and sulfoxide compounds on the oxidation/adsorption and regeneration sequences, and the effectiveness with reference to the oxidation/adsorption.
  • the results of FIG. 3-2 correspond to monitoring the sulfur content of these same hydrocarbons when this same catalyst C 3 , regenerated by combustion, is used.
  • the results obtained on a fresh catalyst are nearly identical to those obtained on the same regenerated catalyst.

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  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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US10/250,431 2000-12-28 2001-12-20 Process and device for desulphurizing hydrocarbons containing thiophene derivatives Abandoned US20060180501A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0017196A FR2818990B1 (fr) 2000-12-28 2000-12-28 Procede et dispositif de desulfuration d'hydrocarbures charges en derives thiopheniques
FR00/17196 2000-12-28
PCT/FR2001/004090 WO2002053683A1 (fr) 2000-12-28 2001-12-20 Procede et dispositif de desulfuration d'hydrocarbures charges en derives thiopheniques

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US (1) US20060180501A1 (fr)
EP (1) EP1346009B1 (fr)
JP (1) JP2004517193A (fr)
KR (1) KR100824422B1 (fr)
AT (1) ATE283905T1 (fr)
DE (1) DE60107602T2 (fr)
ES (1) ES2234930T3 (fr)
FR (1) FR2818990B1 (fr)
WO (1) WO2002053683A1 (fr)

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US20090200206A1 (en) * 2006-03-03 2009-08-13 Al-Shahrani Farhan M Catalytic Process for Deep Oxidative Desulfurization of Liquid Transportation Fuels
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US9598647B2 (en) 2010-09-07 2017-03-21 Saudi Arabian Oil Company Process for oxidative desulfurization and sulfone disposal using solvent deasphalting
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FR2850041B1 (fr) 2003-01-16 2006-07-07 Totalfinaelf France Catalyseur d'hydrotraitement, son procede de preparation et son utilisation dans un procede de purification d'hydrocarbures.
FR2864101B1 (fr) * 2003-12-19 2006-03-17 Total France Procede catalytique de purification des hydrocarbures legers
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FR2818990B1 (fr) 2004-09-24
ES2234930T3 (es) 2005-07-01
EP1346009B1 (fr) 2004-12-01
FR2818990A1 (fr) 2002-07-05
EP1346009A1 (fr) 2003-09-24
ATE283905T1 (de) 2004-12-15
WO2002053683A1 (fr) 2002-07-11
KR100824422B1 (ko) 2008-04-22
JP2004517193A (ja) 2004-06-10

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