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
  • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
• • 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
  • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
• • 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
  • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
  • C10G29/06—Metal salts, or metal salts 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
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/02—Gasoline
• • 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
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/04—Diesel oil

Definitions

• the present invention relates to a process for purifying light hydrocarbons containing sulfur compounds and / or nitrogen compounds refractory to conventional catalytic hydrotreatments, such as thiophene compounds and pyrrole-type compounds, by oxidative polymerization of these compounds. It also relates to the regeneration and reactivation of the oxidizing agent used in this process. This process is intended more particularly for the treatment of gasolines, in particular gasoline from catalytic cracking, and hydrocarbons from steam cracking naphthas containing refractory compounds.
• thiophene By compounds refractory to conventional catalytic hydrotreating is meant thiophene, benzothiophene and their alkyl derivatives, as well as pyrrole and its derivatives, benzopyrrole and carbazole, optionally alkylated.
• these refractory compounds are well known to industry for the difficulty of eliminating them. It is, however, increasingly necessary to eliminate these compounds from light hydrocarbons because, especially for refractory sulfur compounds, environmental restrictions, both in Europe, the USA and Japan, and even elsewhere, sulfur to the atmosphere, become more and more drastic.
• the maximum permissible limit in gasolines is 150 ppm in total sulfur.
• international organizations are calling for a limit of sulfur in gasoline to less than 50 ppm of total sulfur by 2005 and provide for a limitation of less than 10 ppm of total sulfur by 2009 for all productions.
• thiophene hydrocarbons for example gasolines or naphthas, these contents are much higher than 100 ppm and, in general, they are between 100 and 1000 ppm of total sulfur.
• tetraalkylammonium salts are used, such as fluoroborates, fluorophosphates or halides.
• fluoroborates such as fluoroborates, fluorophosphates or halides.
• the Applicant has studied a process for the purification of light hydrocarbons containing sulfur compounds and / or nitrogen compounds refractory to catalytic hydrotreatments, which aims to increase the weight of these compounds by oxidative polymerization thereof, in order to extract them more easily from these hydrocarbons. .
• the Applicant aims at both the desulphurization and the denitrogenation, but also the regeneration of the activity of the oxidizing agent used, by combining the oxidation reaction with a regeneration and activation process. the oxidizing agent used.
• the metal cations are introduced in liquid form, dispersed or dissolved in an aqueous or organic liquid or supported on a solid.
• the process according to the invention is therefore a two or three-phase polyphasic process. phases, depending on whether or not the metal cations are deposited on a solid support before the start of the reaction carried out in this process, namely a polymerization of the sulfur and / or nitrogen compounds.
• the polymerization reaction is carried out at ambient temperature, under atmospheric pressure, at a space velocity (vvh) of less 0.1h -1 .
• the oxidizing metal cation must have a redox potential greater than that of the molecule to be oxidized / polymerized in the reaction medium.
• the metal cation is chosen from among the metal element cations of the group consisting of iron, copper, molybdenum, cerium, manganese and vanadium, each of these metals to be present in the reaction with a degree of oxidation of at least 2.
• These metal cations are used in the form of salts of the group consisting of halides, nitrates, citrates, carboxylates, phosphates, sulfates, persulfates, borates, perborates and bi- and polydentate complexes in linear or cyclic form, comprising nitrogen, sulfur and / or oxygen atoms as a coordination element.
• bi- and polydentate complexes is meant, but not limited to, phthalocyanines, porphyrins, cyclams, bi-pyridines and salt complexes.
• the polymerization reaction is biphasic liquid / liquid (organic / aqueous), and the polymers formed and the oxidizing cations can be removed by decantation of separate phases. , by filtration and / or extraction according to techniques known per se to those skilled in the art.
• the process is carried out in the presence of a solid selected from the group consisting of coal, clays, zeolites, molecular sieves, amorphous silica aluminas, alkali silicates , borate silicas, magnesium silicas, and aluminophosphates.
• a solid selected from the group consisting of coal, clays, zeolites, molecular sieves, amorphous silica aluminas, alkali silicates , borate silicas, magnesium silicas, and aluminophosphates.
• the protons initially present on the support have been exchanged for the metal cations, and then these metal cations have been oxidized before use, which makes it possible to obtain an oxidation state of these higher or lower metals. equal to two.
• This oxidation state is essential for the polymerization reaction to occur in hydrocarbons, as already observed by Mr Bein for less complex media than the hydrocarbons derived from the distillation of petroleum, in his article. Studies in Surface Science and Catalysis, vol. 102, 1996, pp. 295-319 .
• the advantage of a process using the metal cation in the form of counter-ion of a solid support is to be able to carry out the polymerization reaction under usual refining conditions, that is to say with a catalytic bed. of the type used in refining.
• Another advantage is to be able to envisage the regeneration in situ or ex situ of the metal cations used as oxidizing agent.
• crystalline or amorphous solids cation exchangers, containing at least one metal of the group of elements constituted by silicon, aluminum, zirconium, titanium, germanium, gallium and boron, taken alone or in combination, and having a specific surface area of at least 10 cm 2 / g.
• these supports are chosen from clays, including bentonites, and zeolites, including Sapo, Alpo and Beta, and mesoporous, for example of the MCM 41 type, molecular sieves, amorphous silica aluminas, alkali silicates , borate silicas, magnesium silicas, these solids having a pore size of between 1.5 nm and 200 nm.
• metal cation salts in the form of an aqueous or organic solution, the salts being chosen from nitrates, carboxylates, sulphates, persulfates, citrates, phosphates, borates, perborates and halides of metals, including iron, copper, molybdenum, manganese, vanadium and cerium.
• Preferred salts are selected from ferric chloride, cuprous chloride, molybdenum chloride, vanadium oxychloride and cerium chloride.
• the amount of metal cation present on the support can vary from 0.1% to 30% by weight of the metal corresponding to said cation.
• Such supported cations can act in a fixed bed, moving bed, fluidized bed or liquid suspension process.
• the polymers formed are suspended in the hydrocarbon or deposited on the solid. They can be extracted, decanted, filtered or even distilled, in order to be eliminated from the hydrocarbon thus purified.
• the elimination step consists in extracting the polymers deposited on the support by washing with the solvent, in particular by the filler, by desorption by a stream of inert gas chosen from helium, nitrogen, carbon dioxide and water vapor, at a temperature above 100 ° C, and / or by combustion by injection of air or oxygen, preferably after removal of the light hydrocarbons still present on the particles of support.
• This step of oxidation of the metal cation consists of returning the metal cations in an oxidation state of at least 2, by oxidation, by injecting air or liquids containing peroxides or other more oxidizing metal cations, possibly simultaneously increasing the temperature of the oxidizing agent.
• steps taken alone or in combination combine in a continuous or batch process.
• the oxidized metal cation is directly reused for a new oxidative polymerization step.
• Another object of the invention is the application of this process to the finishing treatment of industrial streams containing sulfur and / or nitrogen-containing refractory compounds. More particularly, this process can be used for the desulfurization / denitrogenation of gasolines produced by catalytic cracking and steam cracker effluents, especially pyrolysis gasolines. This process can also be applied as a finishing treatment of aromatic effluents of benzene, toluene and xylene type.
• the present example describes several embodiments of the process of the invention, using various oxidizing cations, and their efficiency vis-à-vis the desulphurization and / or denitrogenation.
• FeCl 3 powder is suspended in a catalytic cracking gasoline or LCCS by mixing at a temperature of 25 ° C.
• the Fe / S ratio total sulfur in LCCS is 16 Fe atoms per sulfur atom (16 atoms / atom).
• Anhydrous FeCl 3 is deposited on silica: the supported cation thus formed is mixed with LCCS at 40 ° C.
• the Fe / S ratio is 13 atoms / atom.
• Anhydrous FeCl 3 is deposited on activated charcoal: the supported cation thus formed is mixed with LCCS at 40 ° C.
• the Fe / S ratio is 13 atoms / atom.
• a sodium zeolite ⁇ in the form of particles of 0.15 to 0.5 mm, exchanged with copper acetate, is charged to a reactor tubular, and circulates LCCS at a space velocity of 1.2h -1 hour and at a temperature of about 25 ° C at atmospheric pressure. Sulfur and / or nitrogen analyzes on the effluent are carried out after 3 hours of circulation and after 15 hours.
• a sodium zeolite ⁇ is charged in the form of particles of 0.15 to 0.5 mm, exchanged with copper acetate, in a tubular reactor, and LCCS is circulated at a space velocity of 1, 2 h -1 and at a temperature of about 150 ° C under atmospheric pressure. Sulfur and / or nitrogen analyzes on the effluent are carried out after 1h30 of circulation and after 14 hours.
• Test V is repeated four times, each test lasting 7 hours.
• the supported cation is reactivated according to steps 2 and 3 described above, these steps being simultaneous and carried out under air circulation, for 5 hours, at 350 ° C.
• the zeolite ⁇ is charged to the copper II-exchanged sodium thus reactivated in a tubular reactor and the LCCS is again circulated at a space velocity of 1.2 h -1 and at a temperature of about 150 ° C., under pressure. atmospheric. Sulfur and / or nitrogen analyzes on the effluent are carried out after 1h30 of circulation and after 3.5 hours.
• the Cu / S ratio is 0.96 atom / atom.
• Sulfur and / or nitrogen analyzes on the effluent are carried out after 7 hours.
• a sodium zeolite ⁇ is mixed in the form of particles of 0.15 to 0.5 mm, exchanged with copper acetate, with LCCS at 40 ° C.
• the Cu / S ratio is 10.3 atoms / atom.
• Sulfur and / or nitrogen analyzes on the effluent are carried out after 6 hours.
• a sodium zeolite ⁇ in the form of particles of 0.15 to 0.5 mm, exchanged with copper acetate, is mixed with LCCS. 40 ° C.
• the Cu / S ratio is 30.8 atoms / atom.
• Sulfur and / or nitrogen analyzes on the effluent are carried out after 5 hours 30 minutes.
• a sodium zeolite ⁇ in the form of particles of 0.15 to 0.5 mm, exchanged with copper acetate, is mixed at 40 ° C. with a model fluid containing, in% by weight, 0.5% by weight. thiophene, 0.5% dodecane and 99% toluene.
• the Cu / S ratio is 1.5 atoms / atom.
• the thiophene and mercaptan analyzes on the effluent are carried out after 6 hours 30 minutes.
• anhydrous FeCl 3 in powder form are dispersed in 183 g of a solution containing, in% by weight, 99.25% toluene, 0.5% thiophene and 0.25% dodecane, at 30 ° C. vs.
• the Fe / S ratio is 2.45 atoms / atom.
• the total sulfur analyzes are made after 2 hours.
• a zeolite ⁇ initially in protonated form, in powder, is exchanged with copper acetate, then is mixed with 200 g of a solution containing, in% by weight, 99.25% toluene, 0.5% thiophene and 0.25% dodecane at a temperature of about 40 ° C and at atmospheric pressure.
• the Cu / S ratio is 0.8 atom / atom.
• the total sulfur analyzes are made after 4 hours.

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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)
• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Catalysts (AREA)

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• 2003
  • 2003-12-19 FR FR0315048A patent/FR2864101B1/fr not_active Expired - Fee Related
• 2004
  • 2004-12-15 EP EP04805711A patent/EP1702029B1/fr not_active Not-in-force
  • 2004-12-15 CA CA002548885A patent/CA2548885A1/fr not_active Abandoned
  • 2004-12-15 WO PCT/FR2004/003232 patent/WO2005061674A1/fr active IP Right Grant
  • 2004-12-15 CN CNA2004800378306A patent/CN1894363A/zh active Pending
  • 2004-12-15 KR KR1020067014338A patent/KR20060130106A/ko not_active Application Discontinuation
  • 2004-12-15 AT AT04805711T patent/ATE386095T1/de not_active IP Right Cessation
  • 2004-12-15 DE DE602004011831T patent/DE602004011831D1/de not_active Withdrawn - After Issue
  • 2004-12-15 US US10/583,258 patent/US20070131588A1/en not_active Abandoned

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