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
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
  • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
  • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
• • 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
  • B01J31/20—Carbonyls
• • 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
  • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
  • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
• • 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
  • C10G35/00—Reforming naphtha
  • C10G35/16—Reforming naphtha with electric, electromagnetic, or mechanical vibrations; by particle radiation
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/10—Use of additives to fuels or fires for particular purposes for improving the octane number
• • 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
  • B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
  • B01J2231/12—Olefin polymerisation or copolymerisation
• • 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
  • B01J2231/20—Olefin oligomerisation or telomerisation
• • 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
  • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
  • B01J2531/64—Molybdenum
• • 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
  • B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
  • B01J2531/72—Manganese
• • 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
  • B01J2531/842—Iron
• • 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
• • 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
  • B01J2531/847—Nickel

Definitions

• ABSTRACT A method of refining gasoline stock in order to obtain high-octane fuels which comprises mixing the gasoline stock with complex compounds of the lower-valency transition metals selected from the group consisting of lower-valency transition metal carbonyls, the complex compounds of slats of said metals with n-type ligands, and the complex compounds of salts of said metals with strong reducing agents, followed by heating the reaction mixture in the to C temperature range and distilling off the target product.
• complex compounds of the lower-valency transition metals selected from the group consisting of lower-valency transition metal carbonyls, the complex compounds of slats of said metals with n-type ligands, and the complex compounds of salts of said metals with strong reducing agents
• This invention relates to method of refining gasolines into high-octane fuel and, more specifically, to methods of improving the antiknock rating of gasolines and for purifying gasolines sulphur compounds and dienes which favour gum formation.
• Selective hydrofining comprises treating said gasolines with hydrogen over heterogeneous catalysts under strictly specified conditions which results in saturating about 90% of the dienes present and about of the oxidation resistant olefins, however the octane rating of the thus-refined gasolines remains low.
• antiknock additives are introduced into said gasolines, and among the available antiknock additives lead-free organometallic compounds may be mentioned such as, for example, cyclopentadienyl derivatives of manganese, iron and other transition metals.
• This method of improving the gasoline octane number is, however, disadvanta' geous in that it necessitates the use of antiknock additives prepared from expensive raw materials.
• a process for refining industrial hydrocarbon mixtures such as gasolines, diesel oils, fuel oils, lubricating oils, and the like is known wherein the removal of mercaptan sulphur contained in said products, eg in gasolines, is effected by a treatment with oxygen, oxygencontaining gases, or with agents which yield oxygen, and with the process of refining being conducted in the presence of a catalyst, viz., an organometallic compound of the type Me,
• a catalyst viz., an organometallic compound of the type Me,
• Suitable metals are manganese, iron, cobalt, nickel, molybdenum and chromium.
• aromatic ligands examples include benzene and its alkylated or arylated homologues, such as toluene, xylenes, mesitylene, hexamethylbenzene, ethylbenzene, diethylbenzenes, propylbenzene, diphenyl, diphenylmethane, triphenylmethane, tetraphenylmethane, diphenylethane, tetrahydronaphthalene, anthracene, phenanthrene, pyrene, benzpyrene and coronene, and also cyclopentadiene or its alkylated or arylated homologues, such as ethylcyclopentadiene, diethylcyclopentadiene, phenylcyclopentadiene and fluorene.
• benzene and its alkylated or arylated homologues such as toluene, xylene
• the process of refining is carried out at a tempera ture of from 50 to 140C for a short period of time and in the presence of a catalyst taken in an amount of from 0.01% to 0.1% by weight, and with superatmospheric pressure being resorted to in some instances.
• This treatment yields gasolines which contain relatively harmless disulphides, while the dienes and reactive olefins undergo polymerization and condensation, with the resulting products being high boiling-point liquids or precipitates.
• the organometallic catalysts are decomposed under the effect of heat or light, as well as when the raw materials being refined are acted upon by large amounts of oxygen under elevated temperatures, so that the precipitates formed also contain, apart from the converted impurities, the decomposed organometallic catalysts, which are expensive materials.
• organometallic compounds When gasolines are refined by the present method, in order to remove the mercaptan sulphur contained therein and the organometallic catalysts used which also possess antiknock properties, said organometallic compounds need not be removed at all or removed completely from the refined gasolines. These refined gasolines may be after-treated, which step necessitates additional expenditures.
• the known refining process is disadvantageous in that it makes use of individual organometallic compounds as catalysts, i.e. of expensive materials prepared from pure starting products.
• Another disadvantage of the known process is that the mercaptans contained in the gasolines being refined are converted into relatively inert disulphides, but the total content of sulphur in the gasolines is not diminished.
• the method of the invention comprises mixing gasolines with complex compounds of the lower valency transi tion metals, viz., carbonyls of transition metals, the complex compounds of salts of said metals with n-type ligands, and the complex compounds of salts of said metals with strong reducing agents, followed by heating the resulting mixture in the to C range and subsequently distilling off the target product.
• the aforesaid treatment results in the formation of high boiling-point compounds and precipitates which contain the products of the reaction between said complex compounds of lower-valency transition metals with the sulphur compounds and dienes contained in the charge stock.
• Said high boiling-point compounds and precipitates upon distilling off the target gasolines, remains behind as still bottoms which exert practically no contamination effect on the commercial product.
• Refining the gasolines by the present method involves the formation of pi-complexes as a result of the reaction between the dienes contained in the gasolines being processed and the lower-valency transition metal compounds, said pi-complexes being an effective antiknock additive.
• the present method is superior to the known method in many aspects, particularly in that it avoids the necessity of preparing individual organometallic compounds, which are expensive, but also provides for the possibility of preparing highly efficient pi-complexes directly in the gasoline being refined due to the presence of dienes in said gasoline.
• the preferred transition metal carbonyls are iron, nickel and molybdenum carbonyls or a mixture of manganese and iron carbonyls.
• the nickel carbonyltriphenylphosphine complex is the preferred complex of the transition metal compounds with the n-type 1igands, while it is preferable to use the manganese chloride-triphenylphosphine-lithium aluminium hydride complex as the complex compound of the transition metal salts with strong reducing agents.
• the present invention provides markedly improved economical effect, in as much as the method of gasoline refining to obtain high-octain fuels involves one stage only and utilizes relatively inexpensive reagents. It is noteworthy that in the refining method, according to the present invention, the dienes contained in the charge stock are not wasted, and can be recovered as a result of decomposing the separated pi-complexes and further utilized in the petrochemical industry.
• the present method is practised as follows.
• the gasoline stock and complex compounds of a lower-valency transition metals are placed in a flask fitted with a reflux condenser. Where ultra violet irradiation is required, the flask is made of quartz and an UV radiation source is placed for example at a distance of cm. from the flask.
• the reaction mixture is heated at a temperature of from 80 to 100C for several hours, generally for a period of from 2 to hours, and followed by distilling off the refined gasoline by conventional procedures.
• the target product is a clear colourless or slightly yellow liquid which is stable when exposed to the effects of air for a prolonged period of time. this being indicative of the absence of oxidationscnsitive dienes.
• the octane numbers are determined by the motor-method test.
• EXAMPLE 1 1 litre of an unstable gasoline from a thermal cracking process (an octane rating 65.5; mercaptan. content. 0.06% by weight) and 2 g. of nickel carbonyl are heated for a period of 6 hours, followed by distilling oft the gasoline fraction whose boiling point is under 200C and which has an octane rating of 83.0. The doctor test is negative.
• a method of refining gasoline to obtain highoctane fuels comprising mixing the gasoline stock with complex compounds of lower-valency transition metals selected from the group consisting of iron, nickel, molybdenum and manganese, said complex compounds selected from the group consisting of the carbonyls of said metals, the complex compounds of the salts of said metals with triphenylphosphine ligands, and the complex compounds of the salts of said metals with lithium aluminum hydride, followed by heating the resulting mixture in the to C temperature range and dis tilling off the target product.
• complex compounds of lower-valency transition metals selected from the group consisting of iron, nickel, molybdenum and manganese
• said complex compounds selected from the group consisting of the carbonyls of said metals, the complex compounds of the salts of said metals with triphenylphosphine ligands, and the complex compounds of the salts of said metals with lithium aluminum hydride
• lowervalency transition metal carbonyls are selected from the group consisting of iron, nickel and molybdenum carbonyls or a mixture of iron and manganese carbon yls.
• a method as claimed in claim 1 wherein the complex compound of the lower-valency transition metal salt with triphenylphosphine is a cobalt carbonyltriphenylphosphine complex.
• a method as claimed in claim 1 wherein the complex compound of a lower-valency transition metal salt with lithium aluminum hydride is a manganese chloride-triphenylphosphine-lithium aluminium hydride complex.

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Citations (5)

• 0
  • BE BE793099D patent/BE793099A/xx not_active IP Right Cessation
• 1972
  • 1972-11-29 GB GB5510372A patent/GB1401828A/en not_active Expired
  • 1972-12-04 NL NL727216414A patent/NL146206B/xx not_active IP Right Cessation
  • 1972-12-12 IT IT32789/72A patent/IT974710B/it active
  • 1972-12-27 CS CS8953A patent/CS177465B1/cs unknown
  • 1972-12-27 JP JP47130162A patent/JPS49103906A/ja active Pending
  • 1972-12-28 FR FR7246644A patent/FR2173925B1/fr not_active Expired
  • 1972-12-29 US US319383A patent/US3865715A/en not_active Expired - Lifetime
  • 1972-12-29 DD DD167994A patent/DD100970A1/xx unknown

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