Classifications

• • 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
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
  • C01G1/04—Carbonyls
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
  • C07F5/06—Aluminium compounds
  • C07F5/061—Aluminium compounds with C-aluminium linkage
  • C07F5/066—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage)
• • 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
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/103—Liquid carbonaceous fuels containing additives stabilisation of anti-knock agents
• • 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
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
• • 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
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/12—Inorganic compounds
  • C10L1/1233—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof
  • C10L1/1241—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof metal carbonyls
• • 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
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/1814—Chelates
• • 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
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
  • C10L1/1828—Salts thereof
• • 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
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/30—Organic compounds compounds not mentioned before (complexes)
  • C10L1/301—Organic compounds compounds not mentioned before (complexes) derived from metals
• • 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
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/30—Organic compounds compounds not mentioned before (complexes)
  • C10L1/305—Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond)

Definitions

• ABSTRACT A process for stabilizing solutions of metal carbonyls in organic solvents, preferably in hydrocarbons, in which one or more aluminum-containing, organic compounds are dissolved in the solutions as stabilizers.
• the aluminum in such compounds is directly bonded to carbon and/or oxygen atoms. More specifically, the aluminum containing organic compounds are reaction products between aluminum alkoxides and one or more compounds having the formula:
• R represents hydrogen, alkyl having up to 8 carbon atoms, aryl or aralkyl having up to 10 carbon atoms, alkoxy having up to 8 carbon atoms, aryloxy or aralkoxy having up to 10 carbon atoms, or a group having the formula:
• metal carbonyls it is here intended compounds of metal atoms and carbon monoxide groups (carbonyl groups), the carbon atoms being linked to the metal atom partly by covalent bonds and partly coordinatively.
• metal carbonyls constitute complicated cyclic systems, wherein also several different metals can be included and many times linkage conditions difficult to interpret are present.
• the oldest metal carbonyls known primarily carbonyls of metals in the eighth group of the periodic table, e.g.
• nickel tetracarbonyl, iron pentacarbonyl and cobalt tetracarbonyl may be mentioned.
• These three metal carbonyls have a considerable metallurgical importance, as they have such low boiling points that they can be fractioned by distillation, which allows preparation of the respective metals in a chemically pure form.
• nickel tetracarbonyl and iron pentacarbonyl have also a great importance as catalysts, as they make possible certain key syntheses, among which, the oxo synthesis and the Reppe synthesis may be mentioned.
• these metal carbonyls have been used sporadically as they have a strong increasing effect on the octane number when added to motor fuels.
• the present invention refers to a method of stabiliz ing solutions of chemically per se very unstable metal carbonyls in gasoline hydrocarbons and especially to prevent a process wherein these metal carbonyls are converted into degradation products which are insoluble in gasoline hydrocarbons and in this way form troublesome suspensions with deposit of a slime-like sediment as a consequence.
• these metal carbonyls are converted into degradation products which are insoluble in gasoline hydrocarbons and in this way form troublesome suspensions with deposit of a slime-like sediment as a consequence.
• the solutions all according to the intended technical objects are no longer useful for purely mechanical reasons or reasons dependent on the consistency, but the degradation of course also has the consequence that the content of the solutions of metal carbonyl which presupposes their technical usefulness for certain objects will rapidly be lower and lower, and in this way they loose their desired technical properties.
• organic metal compounds especially consist of reaction products between aluminum alkoxides, which are generally characterized by the formula Al(OR) wherein R represents arbitrary alkyl groups with or without aryl substituents within the carbon chain, preferably then with up to about 10 carbon atoms, and organic compounds, whose functional atom groupings consist of carbonyl groups, either as keto groups in ketones, as aldehyde groups in aldehydes or as esterified carboxyl groups in esters.
• reaction products according to the invention can be obtained by reacting e.g. acetone with aluminum triethoxide.
• aluminum triethoxide involves certain technical difficulties, and therefore aluminum tripropoxide or aluminum tributoxide is preferred.
• acetone also ethyl methyl ketone or high-molecular ketones can be used.
• Diketones are also useful and they are especially advantageous if their carbonyl groups are in the a, 'y-positions, as in this case they enclose a so-called acidic methylene group, viz. with two easily displaceable hydrogen atoms, the simplest case being acetylacetone.
• the ketones can be of a mixed, aliphaticaromatic character so that for instance acetophenone can be used advantageously. It has been found that among the aldehydes, formaldehyde and acetaldehyde are less suitable, but their usefulness increases at larger chain lengths, for instance in propionaldehyde or particularly butyric or isobutyric aldehyde. Still longer chains do not bring any advantages. Also in the case of the aldehydes it should be mentioned that they can also be of an aromatic or mixed aromatic-aliphatic character, which means that benzaldehyde or phenylacetaldehyde are useful. Among the esters the esters of formic acid have appeared to be less advantageous.
• esters of acetic, propionic or butyric acid can be used advantageously.
• High molecular esters do not bring any special advantages. It is especially advantageous to use ethyl acetate or methyl acetate.
• aromatic esters such as phenyl ethyl methylate, cinnamic acid ethyl ester, etc., can be reacted with aluminum alkoxides.
• Ketocarboxylic acid esters preferably those wherein the keto group is in the B-position to the esterified carboxyl group, have turned out to be especially suitable for reaction with aluminum alkoxides.
• the suitable carbonyl compounds can be defined by the formula wherein R represents hydrogen, alkyl with up to 8 carbon atoms, aryl or aralkyl with up to l0 carbon atoms, alkoxy with up to 8 carbon atoms, aryloxy or aralkoxy with up to 10 carbon atoms, or a group having the formula and the groups R R R, and R independently of each other represent hydrogen, alkyl with up to 8 carbon atoms or aryl or aralkyl with up to 10 carbon atoms.
• the aluminum alkoxides can also be reacted with organic compounds, whose functional groups consist of so-called acidic methylene groups, i.e. carbon atoms with movably bonded hydrogen atoms or preferably carbon atoms with a tertiary hydrogen atom, i.e. a hydrogen atom that is bonded to a tertiary carbon atom. It has been found that the amount of metal in the reaction product directly bonded to carbon atoms can be considerably increased with such compounds. These compounds need not contain any functional groups with oxygen atoms but they can consist of hydrocarbons, provided that they contain tertiarily bonded hydrogen atoms. In an especially suitable case triphenylmethane can be used.
• diphenylethylmethane is advantageous as well as substantially all the compounds, whose general configuration is expressed by the formula T I R (3 R H to be reacted with it need not be stoichiometric. For instance, this means for a simple case, viz.
• a still less particle size results in that it will be difficult to control the process due to it being highly exothermic.
• An optical contact surface between the metal and the liquid reaction compound is preferably secured by the layer of solid metal reaching the highest liquid level of the reaction compound in the course of the process.
• Stabilizing systems prepared according to the above description are incorporated into gasoline solutions of metal carbonyls, preferably then metal carbonyls of metals included in group 8 of the periodic table. It is suitable to choose such concentrations in the first step of the mixing process that the carbonyls are not combined in a too diluted state with the aluminum compounds of the stabilizing system, this for reactionkinetical reasons. For instance it has appeared to be suitable to prepare standard stock solutions, wherein the metal carbonyls are present in an amount of 20 volume percent, the amount of organically bonded aluminum metal being about 5-30 grams of metal per litre of standard stock solution. However, this does not principally mean any restriction of the concentration conditions of the stock solutions.
• the reaction is carried out at temperatures between 80 and 300C, preferably between 120 and 200C, at a normal or elevated pressure and in the presence of composition, they can be considered as an advantageous way of storing the metal carbonyls from a dosage point of view.
• a suitable stabilizing amount of the present stabilizing system consists of one corresponding to 1 part by weight of aluminum to 50-100 parts by weight of the metal in the added metal carbonyl. Greater additions are also effective, but are economically less suitable. Smaller additions will also provide a stabilizing effect, but it is clear that this effect is reduced with decreasing contents, until it is no longer satisfactory.
• an aluminum stabilizing system does not provide any sufficiently long stabilization, especially when the additionally diluted solutions of metal carbonyls in gasoline hydrocarbons, for instance up to a carbonyl metal content of 0.2 to 0.6 gram per litre of gasoline solution, is in contact with iron surfaces, for instance in tanks, barrels etc. It is then possible to incorporate small amounts of gasoline-soluble organic salts of manganese or preferably of cobalt into these diluted readyto-use metal carbonyl solutions, the amount of these metals per litre of diluted, finished gasoline not having to exceed than 0.04 gram of metal.
• suitable acids for said metal salts it has been found that both aromatic, aliphatic or naphthenic acids can be used. It has been especially advantageous to use salts of 2-ethylhexane carboxylic acid.
• EXAMPLE 1 A type of aluminum stabilizer is prepared in the following manner in an apparatus consisting of a 4 litre flask, a reflux cooler with gas discharge and a calibrated feed tunnel. The flask has been charged with 2 kg of aluminum metal in the form of pellets of about 3-8 mm diameter and with 100 ml of n-butanol.
• the flask is heated to about 80C, at which temperature the reaction between the metal and the alcohol starts.
• the aluminum metal may be activated with iodine.
• the heat supply is continued until the temperature has reached about 120C.
• the heat supply is discontinued and a continous addition of n-butanol is started. preferably at a rate of l00ml/l0 min. This addition of alcohol is continued until the total amount of alcohol is 2 litres.
• the temperature of the reaction compound will continue to rise and finally reaches about l35145C
• a reaction system is present, wherein the reaction product is not dissolved in an excess of n-butanol, but is present in the form of a melt.
• this melt there is a certain amount of aluminum suspended colloidally, due to which the aluminum metal surface will be very large.
• Two litres of n-butanol converts about 196 grams of aluminum into aluminum tributoxide as a melt, wherein aluminum metal moreover is colloidally suspended.
• the solution obtained is here called aluminum stabilizer.
• a standard solution of iron pentacarbonyl is prepared by mixing 30 ml of stabilizer, 50 ml of common lead-free car gasoline and ml of iron pentacarbonyl, whereby 100 ml of standard solution of 20 72 of stabilized iron pentacarbonyl is obtained.
• This standard solution, variant A has the following quantitative properties:
• the standard solution according to variant A can be stored without any deposition of solid iron-containing decomposition products, such as will take place already after a few hours from a standard solution with the same iron pentacarbonyl content but without addition of organically bonded aluminum and which causes a very rapid decrease of the content of iron in solution.
• Variant B An iron pentacarbonyl standard solution of 20 content is prepared by reaction (mixture) of 10 ml of aluminum stabilizer according to this example with 20 ml of iron pentacarbonyl dissolved in ml of common lead-free car gasoline, so that ml of stabilized iron carbonyl solution with the following properties is obtained:
• This petrol mixture can be stored without any deposits from decomposition products of iron carbonyl. Nor does the addition of iron or copper filings cause any decomposition of the added iron carbonyl.
• EXAMPLE 2 1n the same apparatus as described in example 1 half the amount of n-butanol, i.e. 1 litre, is reacted with the same amount of aluminum and under the same temperature conditions as in example 1 thus forming half the amount of aluminum tributoxide. This compound is then reacted with a mixture of 500 m1 of acetone and 500 ml of ethyl acetate under the same temperature conditions. During the addition of these carbonyl compounds, the same progress of temperature is not observed as that under the conditions in example 1, where no additional heat supply was necessary. In example 2 the temperature must be raised to C after adding the carbonyl compound and must be maintained constant for 2 hours, before the reaction product is allowed to cool.
• the cooled reaction liquid is drawn off and diluted with so much of gasoline hydrocarbons that the solution has a volume of 3.2 litres. It can then be reckoned with the same amount of organically bonded aluminum metal per litre as in example 1, which amount usually is about 50 grams per litre of stabilizer. While a molar ratio of hydroxyl keto or carbonyl groups equal to 1.38421 was used in example 1, the ratio in this example is 0.692 1. It is evident that the amount of organically bonded aluminum is not proportional to the amount of butyl alcohol originally used calculated as moles of hydroxyl. In a stabilizer according to this example the amount of organically bonded aluminum, i.e. Al metal in an enolate bond and in direct carbon-bonded form, relative to hydroxyl bonded metal must be greater than in example 1.
• EXAMPLE 2 Variant A 30 ml of aluminum stabilizer according to example 2 are dissolved in 50 ml of lead-free car gasoline and this solution is mixed with 20 ml of iron pentacarbonyl so that 100 ml of stabilized standard solution is obtained. 6 ml of this standard solution are diluted with 1 litre of lead-free gasoline. This will give 0.5 grams of iron and 0.150 grams of aluminum per litre of gasoline, and the ratio Fe AI will then be 55.4:1.
• the temperature is raised to 170C and kept constant for 2 hours, after which the mixture is cooled. After draining off the cool reaction mass, it is diluted with so much lead-free car gasoline that the volume amounts to 3,500 ml.
• the amount of organically bonded aluminum is found to be 50 grams per litre.
• a process for stabilizing a solution of carbonyls of metals of Group VIII of the periodic system in liquid hydrocarbons which comprises dissolving in said solution stabilizing amounts of one or more aluminumcontaining organic compounds, the aluminum in said aluminum-containing organic compound being directly bonded to carbon atoms, oxygen atoms or both, and said aluminum-containing organic compound being the reaction product of at least one aluminum alkoxide and one or more compounds having the formula:
• each of the groups R R R and R independently of each other, is hydrogen, alkyl having up to 8 carbon atoms, aryl having up to -10 carbon atoms or aralkyl having up to 10 carbon atoms.

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Citations (4)

• 1973
  • 1973-04-24 US US354131A patent/US3880612A/en not_active Expired - Lifetime
  • 1973-04-25 DE DE2320856A patent/DE2320856C3/de not_active Expired
  • 1973-04-25 GB GB1968873A patent/GB1413559A/en not_active Expired
  • 1973-04-25 FR FR7315032A patent/FR2182100B1/fr not_active Expired
  • 1973-04-25 NL NL7305790A patent/NL7305790A/xx not_active Application Discontinuation

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