EP1346009A1 - Verfahren und vorrichtung zur entschwefelung von thiophenderivate enthaltenden kohlenwasserstoffen - Google Patents

Verfahren und vorrichtung zur entschwefelung von thiophenderivate enthaltenden kohlenwasserstoffen

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Publication number
EP1346009A1
EP1346009A1 EP01994923A EP01994923A EP1346009A1 EP 1346009 A1 EP1346009 A1 EP 1346009A1 EP 01994923 A EP01994923 A EP 01994923A EP 01994923 A EP01994923 A EP 01994923A EP 1346009 A1 EP1346009 A1 EP 1346009A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
oxidation
hydrocarbons
regeneration
chosen
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.)
Granted
Application number
EP01994923A
Other languages
English (en)
French (fr)
Other versions
EP1346009B1 (de
Inventor
Pédro DA SILVA
Edmond Payen
Jean-Yves Carriat
Marc Bisson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TotalEnergies Marketing Services SA
Original Assignee
TotalFinaElf France SA
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Filing date
Publication date
Application filed by TotalFinaElf France SA filed Critical TotalFinaElf France SA
Publication of EP1346009A1 publication Critical patent/EP1346009A1/de
Application granted granted Critical
Publication of EP1346009B1 publication Critical patent/EP1346009B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • 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 relates to a process and a device for the desulfurization of hydrocarbons, in particular for the desulfurization of fuel bases for gas oils, kerosene and gasolines. It relates in particular to the desulfurization of fuel bases loaded with dibenzothiophene compounds.
  • refineries use catalytic hydrodesulfurization processes to lower the sulfur content of fuels.
  • the gas oils coming directly from the distillation are hydrotreated between 300 and 400 ° C, under a hydrogen pressure varying between 30 and 100 bars (30 to 100.10 5 Pa), in the presence of a catalyst placed in a fixed bed and constituted metal sulfides of groups VIb and VIII deposited on alumina, for example cobalt and molybdenum sulfides or nickel and molybdenum sulfides.
  • these processes can be costly in investment and in operation, in particular if it is sought to produce fuels with a very low sulfur content.
  • to desulfurize a fuel initially containing 1% by weight of sulfur up to a sulfur content of between
  • the size of the reactor can be multiplied by 4 and the quantity of hydrogen necessary for the reaction must be increased by approximately 20%. It is particularly difficult, by such methods, to remove traces of sulfur, especially if the sulfur belongs to refractory molecules such as dibenzothiophene alkylated in position 4, or 4 and 6.
  • gasolines do not only come from the direct distillation of crude oil, these gasolines being then slightly sulfur-containing, but can also be obtained by several processes such as the reforming of naphthas, the isomerization of light naphthas, alkylation butane or propane producing Tisooctane, the methoxylation of isobutene and the catalytic cracking of distillates under vacuum or atmospheric residues.
  • catalytic cracking provides between 20 and 60% by weight of the final gasoline. These essences 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 number of l petrol.
  • hydrodesulfurization reaction there is partial hydrogenation of the olefins contained in these cracked gasolines, their disappearance resulting in a drop in the octane number of the gasoline and therefore a deterioration in the quality of gasoline.
  • Adding an additive or reprocessing to improve the quality of the gasoline strikes its cost price, and it is therefore advantageous to have a treatment process allowing direct elimination refractory sulfur compounds, such as benzothiophenic derivatives, by limiting the use of hydrogen.
  • the operation is carried out at temperatures above 60 ° C. and there is overconsumption of peroxide. hydrogen, part of this oxidant being broken down by the catalyst used.
  • the peracids used very powerful oxidants, obtained by reaction of hydrogen peroxide and a carboxylic acid such as formic acid or acetic acid, are generally less effective than hydrogen peroxide and less selective with respect to -vis sulfur compounds and can oxidize in particular olefins.
  • the first step is to oxidize at least partially the sulfur-containing compounds by contacting with peroxides, in the presence of metal catalysts containing metals from the group comprising titanium, zirconium, molybdenum, tungsten, vanadium, tantalum, chromium and their mixtures, in liquid form or solid possibly supported, the supports not being essential for the reaction.
  • the second step consists in bringing the hydrocarbon material containing these oxidized compounds into contact with another metallic component, metallic oxide or peroxide (metals of the group comprising nickel, molybdenum, cobalt, tungsten, iron, zinc, vanadium , copper, manganese, mercury and their mixtures), at a temperature varying from 250 to 730 ° C, under hydrogen pressure.
  • the third step is to recover the desulfurized hydrocarbon material
  • the thiophene derivatives are transformed into their sulfonated and / or sulfonic form.
  • the present invention therefore aims to propose a process for the desulfurization of hydrocarbons, in particular those used as fuel bases containing thiophenic derivatives, without reducing the octane number index or the cetane number, sometimes even with an increase in these indices. It particularly relates to the finishing treatment of hydrotreated gas oils, kerosene and catalytic cracking gasolines, highly concentrated in thiophenic derivatives refractory to hydrogenations.
  • the invention further aims to propose such a process which makes it possible to reach oxidation levels identical, if not superior, to the known processes, while limiting the reaction and separation times of the sulfur-containing compounds oxidized from the desulfurized hydrocarbons.
  • the subject of the present invention is therefore a process for the selective desulfurization of the thiophenic compounds contained in the hydrocarbons from the distillation of crude oil, refined or not, consisting in oxidizing thiophenic sulfur atoms to sulfonates in the presence of an oxidizing agent and a catalyst, and in separating the sulfonated compounds obtained from said hydrocarbons, this process being characterized in that it comprises at least a first oxidation / adsorption step by heterogeneous catalysis of the sulfur-containing compounds, in an organic medium, at a temperature of at least 40 ° C., in the presence of an organic oxidant from the family of peroxides and peracids and in the presence of a catalyst with a specific surface greater than 100 m 2 / g and a porosity varying from 0.2 to 4 ml / g, and a second stage of regeneration of the spent catalyst, the stage of regeneration always following the oxidation / adsorption step.
  • thiophene derivatives means benzothiophenic, polybenzothiophenic compounds and their alkylated derivatives, among which the alkyldibenzothiophenes, which are particularly refractory to the conversion processes usually used by refiners.
  • the method according to the invention has the advantage, on the one hand, of ensuring at atmospheric pressure an oxidation of all the sulfur contained in the hydrocarbons and more selectively a conversion of the thiophenic derivatives into sulfonates, and this in the context of 'a simple industrial process, and, on the other hand, to simultaneously adsorb these sulfoxide compounds on the catalyst.
  • the separation of the hydrocarbons from most of the sulfonates and sulfoxides formed is immediate, the latter being found in solid form deposited on the catalyst or in the form of filterable deposit by means known per se, in the treated hydrocarbons.
  • the oxidation / adsorption and regeneration steps can be carried out in the same reactor or simultaneously in reactors arranged in parallel and operating alternately for one or other of the fixed bed stages, or in at least two moving bed reactors connected to each other by the catalytic bed, one being dedicated to oxidation / adsorption, the other to regeneration.
  • the first reactor containing a fixed bed of catalyst receives the flows of hydrocarbons and oxidant and the second receives, for the regeneration of the catalyst, liquid effluents, for example a washing solvent, or oxidizing gaseous effluents , like air or an air / N2 mixture, the temperature of the catalytic bed being raised.
  • liquid effluents for example a washing solvent, or oxidizing gaseous effluents , like air or an air / N2 mixture, the temperature of the catalytic bed being raised.
  • the hydrocarbons are brought into the first reactor where the oxidation takes place, the catalyst being progressively pushed towards the second reactor, where it is regenerated before being returned to the oxidation / adsorption reactor.
  • Movable bed reactors well known in particular in the field of reforming, can be used in this device.
  • a third reactor is used, disposed between the first two reactors and making it possible to remove the hydrocarbons from the used catalyst before washing it or carrying out the combustion of the trapped sulfonated and sulfoxidized compounds.
  • the catalysts used according to the present invention are chosen from the supports of the group consisting of silicas, aluminas, zirconia, amorphous or crystalline aluminosilicates, aluminophosphates, silicic and silicoaluminated mesoporous solids, active carbon and clays, these supports being used alone or as a mixture.
  • these supports can be advantageously used as metal supports from the group consisting of titanium, zirconium, vanadium, chromium, molybdenum, iron, manganese, cerium and tungsten, these metals in the form of oxides which can be introduced into the network of the support or deposited on the surface of the support.
  • the catalyst contains from 0 to
  • the catalyst contains from 0 to 20% of metal in the form of oxide.
  • supports made up of refractory oxides gamma aluminas, silicas, mesoporous silicic and silicoaluminous solids are preferred.
  • catalysts containing tungsten or titanium in the form of oxide deposited on a support or introduced into the network preference is given to catalysts containing tungsten or titanium in the form of oxide deposited on a support or introduced into the network, this support being chosen from silicas, aluminas and aluminosilicates, alone or as a mixture.
  • the oxidizing molar / total sulfur ratio contained in the hydrocarbons is between 2 and 20, and preferably between 2 and 6.
  • the oxidants are chosen from the compounds of general formula R1OOR2, in which R1 and R2 are identical or different, chosen from hydrogen, linear or branched alkyl groups, comprising from 1 to 30 carbon atoms and the aryl or alkylaryl groups, the aryl unit of which is optionally substituted by alkyl, Ri and R 2 groups which cannot simultaneously be hydrogen.
  • the oxidant of formula R10OR2 is chosen from the group consisting of tert-butyl hydroperoxide and ditertiobutylperoxide.
  • the peracids of formula R3COOOH are chosen such that R3 is hydrogen or a linear or branched alkyl group comprising from 1 to 30 carbon atoms. They are preferably chosen from the group consisting of peracetic acid, performic acid and perbenzoic acid.
  • the regeneration step of the catalyst consists in removing, by washing or by combustion, the deposits formed.
  • a preferably polar solvent from the group consisting of water is used, the linear or branched alkanols comprising from 1 to 30 carbon atoms, alone or in mixture with water, the alkyl nitriles comprising from 1 to 6 carbon atoms. Water, acetonitrile, methanol and mixtures thereof are preferred.
  • the catalyst is brought to a temperature of at most 800 ° C, preferably to a temperature less than or equal to 650 ° C, under a pressure varying from 10 5 Pa to 10 6 Pa, and preferably from 10 5 Pa at 2.10 5 Pa, in the presence of an oxidizing gas.
  • oxidizing gas is meant pure oxygen and all mixtures of gases containing oxygen, in particular mixtures of oxygen and nitrogen and the air itself.
  • the amount of oxygen in the nitrogen is adjusted so as to limit the formation of water vapor, an excessively large amount of water vapor having the secondary effect of modifying the structure of the pores of the catalyst with reduction in their volume, especially when it contains crystalline aluminosilicates as support, such as zeolites or aluminophosphates. This adjustment also makes it possible to control the temperature variations linked 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 comprising inlet pipes for the hydrocarbons and the oxidant and an outlet pipe for desulphurized hydrocarbons, and optionally a second reactor comprising inlet pipes for solvent or oxidizing gas from the catalyst, with a view to regenerating the latter, and a combustion gas outlet pipe.
  • oxidizing gas is meant here the oxygen / air, air / nitrogen and oxygen / nitrogen mixtures.
  • a third object of the invention is the application of the process defined above to the specific finishing treatment of gasolines from catalytic cracking or also to the treatment of gas oils which have been previously hydrotreated and of kerosene, for a better economy of the process.
  • FIG. 1 is a diagram of a device with two reactors operating alternately in oxidation and in regeneration of the catalyst
  • FIG. 2 is a diagram of a device comprising two moving bed reactors, the first corresponding to the oxidation step, the second to the catalyst regeneration step, a return line of the regenerated catalyst being added to the system ;
  • Figures 3-1 and 3-2 show curves illustrating the total sulfur content, as a function of time, of the hydrocarbons treated according to the invention in Example III below.
  • the device of FIG. 1 comprises two reactors 1 and 2 loaded with a catalyst arranged in a fixed bed.
  • the line 3 brings to the reactor 1 the sulfur-containing hydrocarbon charge, into which the oxidant has been introduced via the line 4, the three-way valve 6a and the line 8a .
  • the stream of desulphurized hydrocarbons leaves the reactor 1 via line 9a and rejoins the line 10a for evacuating desulphurized hydrocarbons via the three-way valve 7a.
  • line 5 brings to reactor 2 either an appropriate solvent or an oxidizing gas, via the three-way valve 6b and line 8b.
  • the temperature of the catalytic bed is maintained at 500 ° C.
  • the solvent containing the sulfonates recovered from the catalyst or the combustion gases, mainly SO 2 , CO and CO 2 are removed via the line 9b, the three-way valve 7b and line 11b in line l ia.
  • the hydrocarbon / oxidant mixture takes the line 3a and the valve 6b to enter the reactor 2.
  • the desulphurized hydrocarbons are evacuated through the line 9b and are directed to the evacuation line 10a via the valve 7b and the line 10b.
  • the solvent or the oxidizing gas arriving via line 5 is directed into the reactor 1 via line 3a, valve 6a and line 8a.
  • the solvent or the oxidation gases are brought back into the evacuation pipe 1a via the pipe 9a and the valve 7a.
  • valves 6a, 6b, 7a and 7b can be exchanged according to a common process to allow the circulation of the proposed flows.
  • the device of FIG. 2 comprises two reactors 20a and
  • reactor 20a can be chosen from funnel reactors, the moving bed of the catalyst moving by gravity towards the lower part of the reactor.
  • the catalyst is pushed by gravity into reactor 20b via line 70.
  • the solvent or the combustion gas are introduced via channel 80 into reactor 20b.
  • the temperature is increased and maintained at 500 ° C.
  • the solvent loaded with sulphonates or the combustion gases are evacuated via line 100.
  • these moving beds operate intermittently, the catalyst not moving continuously, it is advantageous to have on the reactor 20b a solvent or nitrogen purge allowing the elimination of the hydrocarbons before washing, and / or elimination of combustion gases by nitrogen stripping.
  • the regenerated catalyst is led via the line 110 to the device 30.
  • This device can be a device powered by pressurized gas or a worm. It returns the regenerated catalyst via line 120 to reactor 20a.
  • the reactors 20a and 20b can be part of the same unit having two separate stages.
  • the examples below aim to illustrate the effectiveness of the process of the invention, without limiting its scope.
  • the present example aims to describe the effectiveness of the process according to the invention with regard to the elimination of the dibenzothiophene derivatives present in the bases for partially desulfurized fuels.
  • the catalyst samples used are of two types, the catalysts formed from a single support and those with one or more metals deposited by impregnation. Table 1 below gives the specific surface and porosity characteristics of each of them.
  • Catalysts C2, C3 and Ce were obtained by wet impregnation of a metal salt, respectively ammonium metatungstate and ammonium hexamolybdate, at a content of 140 mg of metal per gram of support, then dried and finally calcined at a temperature of 500 ° C.
  • Catalyst C 4 was obtained by treatment of a commercial titanium beta zeolite according to the procedure described in patent EP 0 842 114. To test the activity of these catalysts in oxidation as a function of time, the following was introduced into a 150 ml micropilot 20 ml of catalyst. A charge of middle distillates is circulated on the catalyst after hydrotreatment, containing 212 ppm of residual sulfur refractory to hydrotreatment, doped with 1800 ppm of tert-butyl hydroperoxide (tBHP), at an hourly space speed (WH) of 1 h -1 - under atmospheric pressure, at a temperature of 70 ° C. Samples are taken regularly during the oxidation to measure the activity of the catalyst over time. A comparative sample called Ti, corresponding to the use of catalyst alone without peroxide, is also followed.
  • tBHP tert-butyl hydroperoxide
  • the efficiency of the catalyst is measured as a function of the oxidation of the compounds.
  • Example I The procedure is as in Example I, with the catalysts Ci - Ce and the formation of sulfones and sulfoxides is monitored with respect to the dibenzothiophene compounds, in particular benzothiophene (BT), dibenzothiophene (DBT) and 4.6 dimethyldibenzothiophene (DMBT). ), by gas chromatography equipped with a specific sulfur detector (SIEVERS method).
  • BT benzothiophene
  • DBT dibenzothiophene
  • DMBT dimethyldibenzothiophene
  • the present example aims to show, in parallel with the oxidation, the effect as a function of time of the adsorption of the sulfonated and sulfoxidized compounds on the oxidation / adsorption and regeneration sequences, and the efficiency of the regeneration operation with respect to to oxidation / adsorption.
  • the operation is carried out with the catalyst C3 under the operating conditions described in Example I on a middle distillate containing 44 ppm of sulfur after hydro treatment, and in the presence of 600 ppm of tBHP.

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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)
  • Catalysts (AREA)
  • Saccharide Compounds (AREA)
EP01994923A 2000-12-28 2001-12-20 Verfahren zur entschwefelung von thiophenderivate enthaltenden kohlenwasserstoffen Expired - Lifetime EP1346009B1 (de)

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
FR0017196 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

Publications (2)

Publication Number Publication Date
EP1346009A1 true EP1346009A1 (de) 2003-09-24
EP1346009B1 EP1346009B1 (de) 2004-12-01

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EP01994923A Expired - Lifetime EP1346009B1 (de) 2000-12-28 2001-12-20 Verfahren zur entschwefelung von thiophenderivate enthaltenden kohlenwasserstoffen

Country Status (9)

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

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US20060180501A1 (en) 2006-08-17
KR20030065585A (ko) 2003-08-06
DE60107602T2 (de) 2005-11-24
FR2818990B1 (fr) 2004-09-24
WO2002053683A1 (fr) 2002-07-11
DE60107602D1 (de) 2005-01-05
FR2818990A1 (fr) 2002-07-05
EP1346009B1 (de) 2004-12-01
ATE283905T1 (de) 2004-12-15
ES2234930T3 (es) 2005-07-01
KR100824422B1 (ko) 2008-04-22
JP2004517193A (ja) 2004-06-10

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