Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
  • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
  • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
  • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
  • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
  • C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
  • C07C319/24—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides by reactions involving the formation of sulfur-to-sulfur bonds
• • 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
  • C10G27/10—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen in the presence of metal-containing organic complexes, e.g. chelates, or cationic ion-exchange resins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/18—Carbon
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
  • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
  • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
  • B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
  • B01J2531/16—Copper
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
  • B01J2531/56—Vanadium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
  • B01J2531/84—Metals of the iron group
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
  • B01J2531/84—Metals of the iron group
  • B01J2531/845—Cobalt

Definitions

• a process for converting sulfur compounds in petroleum cuts to disulfides comprises contacting the petroleum cut with molecular oxygen and with a solid catalytic mass insoluble in the liquid petroleum cut and consisting essentially of at least one solid phthalocyanine of a transition metal, a solid carrier and a solid alkali metal oxide or hydroxide, the amount of the transition metal phthalocyanine being between 0.05% and 50% by Weight with respect to the carrier weight and the amount of the alkaline metal oxide or hydroxide being between 10% and 50% by weight with respect to the total weight of the catalytic mass.
• the heretofore conventional pretreatment step of mixing the petroleum cut with an alkaline aqueous phase is no longer necessary.
• This invention has for object the oxidation of sulfur compounds and particularly mercaptans in the presence of solid catalytic masses.
• This refining includes mercaptan removal, also called sweetening.
• the treatment is carried out in two stages: extraction of the mercaptans followed with an oxidation, or oxidation of the mercaptans followed with an extraction of the disulfides.
• the oxidation of mercaptans to disulfides is generally carried out in the presence of an aqueous solution of alkali (sodium hydroxide or potash), by means of gaseous oxygen or, more generally, air, in the presence of a catalyst.
• alkali sodium hydroxide or potash
• the catalysts which were previously recommended are sulfonated derivatives of phthalocyanines of transition metals, particularly of cobalt and vanadium.
• These derivatives may be deposited on carriers such as alumina, bauxite or coal, the latter being the most frequently used.
• the phthalocyanine of the metal itself instead of a sulfonated derivative thereof, on the coal.
• the so-obtained catalyst is 3,686,694 Patented Aug. 22, 1972 then completely insoluble in the feedstock subjected to the sweetening treatment and in the alkaline phase.
• oxidation of mercaptans to disulfides may be carried out by means of oxygen, in the presence of a catalyst but in the absence of an alkaline aqueous solution.
• the process according to this invention for oxidizing sulfur compounds and more particularly mercaptans contained in the petroleum cuts or issued therefrom is char acterized in that said sulfurized products are contacted in the liquid phase with (a) a gas containing or able to supply molecular oxygen and (b) a solid catalytic mass prepared by admixing at least one solid phthalocyanine of a transition metal with a carrier having a specific surface between 50 and '500 mF/g. and with an alkali metal oxide or hydroxide, the amount of transition metal phthalocyanine being in the range of 0.05% to 50% by weight with respect to the carrier, the amount of alkali metal oxide or hydroxide being between 10' and 50% by weight with respect to the total weight of the catalytic mass.
• the carrier may be for instance coal (active carbon, animal charcoal, carbon black, coke, ordinary coal as such or treated, or any other coal obtained by the known methods or manufacture), alumina or silica.
• coal active carbon, animal charcoal, carbon black, coke, ordinary coal as such or treated, or any other coal obtained by the known methods or manufacture
• alumina or silica Preferably coal is used.
• the transition metal contained in the phthalocyanine compound is preferably selected from cobalt, vanadium, copper, iron and/or nickel.
• the phthalocyanines used may be prepared by any one of the conventional methods.
• the phthalocyanines available on the market are generally suitable.
• the alkali metal is generally potassium or sodium.
• the mixture of the components of the catalytic mass may be prepared in different ways.
• One way consists of admixing the carrier (coal for instance) and the phthalocyanine, thereafter impregnating said mixture, under dry condition with a solution of alkali metal hydroxide. There is thus obtained a paste which can be shaped in usual manner: for example by extrusion, compression or pellet forming. The shaped product is then dried in an oven at a convenient temperature, in most cases between 40 and C.
• Another way comprises impregnating the carrier, under dry condition, with the solution of alkali metal hydroxide, drying it and then admixing it with phthalocyanine.
• the shaping step is then more difficult to carry out and it may be advantageous to add a binding agent such as graphite, bentonite, magnesia or calcium oxide.
• a binding agent such as graphite, bentonite, magnesia or calcium oxide.
• the proportions of transition metal phthalocyanine and carrier used to form the catalytic mass may be varied. Very small amounts of phthalocyanine may be used but, in order to obtain a good homogenization of the mixture it is advantageous to use it in a proportion of at least 0.05% by weight with respect to coal.
• the catalytic mass of this invention is preferably used in the wet state. Its water content will depend on the operating conditions and on the feedstock subjected to oxidation. Good results have been obtained with proportions between 1 and 40% and preferably between 5 and 25% by weight of water with respect to the total catalytic mass.
• the so-defined catalytic mass provides for the direct oxidation, by means of molecular oxygen, air or any other oxygen-containing or supplying gas, such as a nitrogen oxide, hydrogen peroxide or any other peroxide, of mercaptans or salts thereof to disulfides, and, contrarily to the usual catalysts, said catalytic mass makes possible the operation in the absence of aqueous phase.
• the mercaptans to be oxidized according to the process of this invention are those contained in various media, particularly in solvents or petroleum products such as gasolines, kerosenes, gas-oils, naphthas and the like.
• the mercaptans oxidized according to the process of the invention may be either of the alkyl or cycloalkyl type or of the aryl type and contain for example up to 30 carbon atoms in their molecule.
• the catalyst may be used in any usual manner: for instance in a moving bed, a fixed bed or according to a percolation method. It can also be used inside the storage tank for the feedstock which has to be subjected to the sweetening treatment. It is often preferable to make use of a percolation system.
• mercaptans content and the composition of the feedstock subjected to the sweetening treatment here can be used oxygetn in a dissolved state or an oxygen-containing gas which is bubbled therethrough.
• the reaction is conducted at a temperature generally in the range of to 70 C., preferably between and C.
• the catalyst used according to the present invention is completely insoluble in and does not change the color or the stability to color of petroleum feedstocks. It is in some cases recommended to add to the reaction medium small amounts of alcohol or ketone which may significantly favor the reaction.
• EXAMPLE 1 This example relates to the manufacture of a catalyst containing 13% by weight of cobalt phthalocyanine, 36% of coal and 45% of potash. 19 g. of cobalt phthalocyanine are admixed with 57 g. of coal. The resulting mixture is impregnated with 100 cc. of a saturated potash solution. The so-obtained paste is extruded and dried for 4 hours at 50 C.
• EXAMPLE 2 The catalyst of Example 1 has been used for oxidizing nbutyl mercaptan to disulfide.
• a percolator wherein are placed 5 g. of the catalyst having a volume of about 10 cc.
• the mercaptan containing liquid 350 cc. of toluene and 0.1 mole of n-butylmercaptan
• Air is simultaneously injected at atmospheric pressure through a fritted glass, at a rate of 4 liters per hour.
• the catalyst is maintained at 23 C. by means of a jacket for thermal regulation by a fluid circulating therein.
• EXAMPLE 3 The catalyst of Example 1 has been used for sweetening a highly aromatic straight-run gasoline having an initial boiling point of C. and containing 500 p.p.m. of sulfur in the form of mercaptans.
• EXAMPLE 4 A catalyst has been prepared by admixing 24 g. of activated vegetal coal with 0.024 g. of cobalt phthalocyanine. This mixture has been impregnated with 23 cc. of a saturated potash solution and has been extruded and dried for 3 hours at 60 C.
• EXAMPLE 5 The catalyst of Example 4 has been used for sweetening a feedstock consisting of toluene containing 465 p.p.m. of sulfur in the form of n-butyl mercaptan and 47 p.p.m. of sulfur in the form of t-butyl mercaptan.
• Example 7 The catalyst of Example 6 has been used in the experimental conditions of Example 5.
• the feedstock of Example 5 further contained 45 p.p.m. of sulfur in the form of thiophenol. After passage through the percolator at a VVH of 50, the feedstock was issuing in a completely sweetened state. 15 liters of this feedstock were so sweetened without any loss of activity of the catalyst.
• EXAMPLE 8 A catalyst has been prepared by admixing 25 g. of active carbon with 0.025 g. of cobalt phthaloeyanine. The resulting mixture after impregnation with 23 cc. of a saturated sodium hydroxide solution, has been extruded and dried for 3 hours at 60 C.
• EXAMPLE 9 The catalyst of Example 8 has been used for sweetening the same feedstock as in Example 5 and under the same operating conditions. The feedstock outflow was completely sweetened (negative Doctor test).
• EXAMPLE 10 A catalyst has been prepared by impregnating 30 g. of activated vegetal coal with 30 cc. of a 70% potash aqueous solution. The resulting paste has been mixed with 0.15 g. of copper phthalocyanine and then extruded and dried for 3 hours at 60 C.
• EXAMPLE 11 The catalyst of Example has been used for sweetening the same feedstock as in Example 5 under the same operating conditions as in Example 5. The feedstock recovered at the outlet was completely sweetened (negative Doctor test).
• a process for oxidizing mercaptans or salts thereof to disulfides comprising contacting said mercaptans or salts thereof contained in a petroleum cut liquid with molecular oxygen and with a solid catalytic mass insoluble in said liquid petroleum cut and consisting essentially of at least one solid phthalocyanine of a transition metal a solid carrier and a solid alkali metal oxide or hydroxide, the amount of the transition metal phthalocyanine being between 0.05% and 50% by weight with respect to the carrier weight and the amount of the alkaline metal oxide or hydroxide being between 10% and 50% by weight with respect to the total weight of the catalytic mass, said process being conducted in the absence of a pretreatment step of mixing said petroleum cut with an alkaline aqueous phase.
• alkaline metal is selected from potassium and sodium.
• catalytic mass further contains from 5 to by weight of water.
• liquid media being a petroleum cut
• process being conducted in the absence of a subsequent step of decanting said petro leurn cut from said alkaline aqueous phase.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Inorganic Chemistry (AREA)
• Materials Engineering (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• General Chemical & Material Sciences (AREA)
• Catalysts (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

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Cited By (8)

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• 1968
  • 1968-12-31 FR FR183002A patent/FR1602191A/fr not_active Expired
• 1969
  • 1969-12-12 CH CH1821669A patent/CH503001A/fr not_active IP Right Cessation
  • 1969-12-23 LU LU60087D patent/LU60087A1/xx unknown
  • 1969-12-24 BE BE743654D patent/BE743654A/xx unknown
  • 1969-12-27 DE DE19691965177 patent/DE1965177A1/de active Pending
  • 1969-12-29 US US888972A patent/US3686094A/en not_active Expired - Lifetime
  • 1969-12-29 BG BG013656A patent/BG17627A3/xx unknown
  • 1969-12-30 ES ES375072A patent/ES375072A1/es not_active Expired
  • 1969-12-31 GB GB63566/69A patent/GB1260030A/en not_active Expired
  • 1969-12-31 NL NL6919643A patent/NL6919643A/xx unknown

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