WO2013103459A1 - Microwave process for preparing stable metal oxide dispersions - Google Patents
Microwave process for preparing stable metal oxide dispersions Download PDFInfo
- Publication number
- WO2013103459A1 WO2013103459A1 PCT/US2012/067699 US2012067699W WO2013103459A1 WO 2013103459 A1 WO2013103459 A1 WO 2013103459A1 US 2012067699 W US2012067699 W US 2012067699W WO 2013103459 A1 WO2013103459 A1 WO 2013103459A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metal
- dispersion
- process according
- oxide
- hydroxide
- Prior art date
Links
- 239000006185 dispersion Substances 0.000 title claims abstract description 62
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 37
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000000203 mixture Substances 0.000 claims abstract description 48
- 239000002270 dispersing agent Substances 0.000 claims abstract description 36
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 21
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 19
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 6
- 238000009835 boiling Methods 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 20
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- -1 alkylaryl carboxylate Chemical class 0.000 claims description 16
- 238000004821 distillation Methods 0.000 claims description 15
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- 239000004215 Carbon black (E152) Substances 0.000 claims description 14
- 229930195733 hydrocarbon Natural products 0.000 claims description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims description 14
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 14
- 150000004692 metal hydroxides Chemical class 0.000 claims description 14
- 229910052749 magnesium Inorganic materials 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- 150000007942 carboxylates Chemical class 0.000 claims description 9
- 239000003208 petroleum Substances 0.000 claims description 9
- 125000003367 polycyclic group Chemical group 0.000 claims description 9
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 9
- 150000001735 carboxylic acids Chemical class 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 7
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- 239000000314 lubricant Substances 0.000 claims description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 5
- 239000000347 magnesium hydroxide Substances 0.000 claims description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 5
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- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
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- 150000008055 alkyl aryl sulfonates Chemical group 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 23
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- 239000000292 calcium oxide Substances 0.000 abstract description 2
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- 238000010992 reflux Methods 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
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- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 3
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- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 241001133760 Acoelorraphe Species 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
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- 239000012141 concentrate Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
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- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
-
- 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/12—Inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/02—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic oxygen-containing compound
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
-
- 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- 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
-
- 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/188—Carboxylic acids; metal 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
- C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
- C10L1/2437—Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/055—Particles related characteristics
- C10N2020/06—Particles of special shape or size
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/52—Base number [TBN]
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/015—Dispersions of solid lubricants
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2070/00—Specific manufacturing methods for lubricant compositions
Definitions
- Stable dispersions of small particle metal oxides such as magnesium oxide and calcium oxide, with an average particle size of one micron or less, often from 1-100 nm, are prepared by microwave irradiation of a composition prepared from a mixture comprising an oxide, hydroxide or carbonate of the metal, a carrier, a sulfonic or carboxylic acid dispersant, and typically a low MW carboxylic acid and water.
- Fine particle metal oxides have a variety of commercial uses.
- overbased detergents e.g., compositions comprising overbased alkaline metal or alkaline-earth metal compounds such as metal oxides and often complexed with an organic dispersant, are well known additives for lubricating oil compositions and petroleum fuels.
- the metal oxide is most conveniently added and used as a dispersion in a carrier.
- Petroleum fuels such as residual fuel oils contain large amounts of impurities which result in corrosive deposits in the equipment.
- crude oil usually contains 1- 500 ppm of vanadium in the form of a porphyrin complex depending on the source. Because of its origin as a concentrate from the refining process, residual oil contains several times more vanadium than the crude from which it was derived. The combustion of these vanadium-containing fuels produces very corrosive deposits which can destroy a metal part, such as a gas turbine blade, in a matter of hours.
- the presence of sodium in fuel can also have catastrophic consequences.
- the sodium level can be increased because of the introduction of sodium chloride through the air intake and contamination of the fuel by sea water.
- the sodium can react with sulfur in the fuel to form a sulfate which is deposited in turbine parts.
- Overbased detergents perform a variety of functions including anti-corrosion, deposit control, acid scavenger functions
- overbased magnesium compounds complexed with sulfonate and carboxylate dispersants have long been used as anti- corrosion and acid neutralization additives for lubricating oils and greases, anti-corrosion and acidic neutralization additives during the combustion of fuels such as residual fuel, pulverized sulfur-containing coal, corrosion inhibitors in fuels containing vanadium etc.
- fuels such as residual fuel, pulverized sulfur-containing coal, corrosion inhibitors in fuels containing vanadium etc.
- overbased magnesium detergents to, for example, boiler fuels or gas turbine fuels, is known to reduce corrosion, presumably by forming magnesium complexes with the vanadium or sodium.
- Overbased metal detergents are also added to lubricating oils to prevent or remove deposits of oil-insoluble sludge, varnish, carbon and lead compounds which otherwise form on internal combustion engine parts and for combating severe rust conditions which may be encountered during shipping or storage of machinery or exposure to out-door weather.
- Detergent additives for automotive and diesel engine oils also chemically react with the highly acidic by-products of combustion that find their way into the lubricating oil system.
- a useful dispersion of metal oxide must be stable during storage and the overbased metal must stay well dispersed in the lubricant or fuel.
- a variety of parameters will affect the stability and activity of these dispersions such as the dispersants and carriers employed, particle size of the solid components, and the relationship between metal and dispersant.
- the process by which the overbased metal compounds and complexes are prepared will greatly influence the actual physical make up and properties of the overbased metal dispersion, impacting particle size and distribution of the metal compound throughout the dispersion, the viscosity and stability of the dispersion, the amount of the metal within the dispersion etc.
- Overbased metal additives for example, overbased MgO dispersions are often added as a dispersion in a high boiling liquid hydrocarbon.
- high boiling carriers i.e., carriers with boiling points over 200 °C, often greater than 250 °C or 280 °C, and even much greater than 300 °C is due to the manner in which the dispersions are made.
- overbased stable MgO dispersions with fine particle sizes and good flowcharacteristics are typically produced, even when starting with MgO as a starting material, through thermal decomposition of Mg(OH) 2 or Mg(OH) 2 derived intermediates which require high temperature (300-350°C).
- the use of high boiling point solvents as carriers is dictated by practical processing considerations.
- US Pat. 4,163,7208 discloses magnesium-containing dispersions prepared by high temperature decomposition of magnesium salts of carboxylic acids to MgO in a dispersant-containing fluid.
- Mg(OH) 2 an organic carboxylic acid or sulfonic acid surfactant such as naphthenic acid, acetic acid and water are heated in a high boiling hydrocarbon to temperatures up to 350 °C, which is above the
- magnesium acetate decomposition point of magnesium acetate, 323 °C. It is believed that magnesium acetate is formed in situ and decomposes at the high temperatures used. Water is also removed at the elevated temperatures.
- US Pat. 4,293,429 discloses a variation of US Pat. 4,163,728 which begins with MgO instead of Mg(OH) 2 .
- the bulk MgO is converted to magnesium acetate which forms suspended MgO particles of less than 5 microns, and preferably less that 1 micron.
- the coarse MgO particles are converted into a dispersion of stabilized MgO microparticulates.
- Lower temperatures fail to provide the fine particle size MgO.
- US 4,129,589 discloses a process for preparing an over-based oil-soluble magnesium salt of a sulfonic acid by contacting carbon dioxide gas with a mixture comprising an oil- soluble magnesium salt of a sulfonic acid, magnesium oxide, water, and a promoter system comprising a carboxylic acid of 1 to 5 carbons in an inert solvent for lowering the viscosity of said mixture to facilitate mixing.
- the products of US 4,129,589 had acceptably low viscosity but the magnesium content was typically 9-10% and no more than 14%.
- US 6,197,075 discloses an overbased magnesium sulfonate, carboxylate or phenate product containing at least 14% and up to about 18% by weight of magnesium, useful as a deposit control additive for residual fuel oils and turbine fuels prepared by contacting a mixture of i) a sulfonic acid, phenol or carboxylic acid or salt thereof, ii) a magnesium oxide, iii) a co-promoter comprising a lower carboxylic acid, a lower alcohol, a succinic anhydride and water, and iv) a solvent and/or oil, with an acidic gas such as carbon dioxide at 50 °F up to the reflux temperature of the mixture to overbase the reaction mixture.
- an acidic gas such as carbon dioxide
- overbased metal compositions described above and elsewhere are best described as products by process as there is typically no simple chemical formula which adequately correlates to the essential material makeup and the physical properties of the product.
- the molecular structures of the metal complexes are not fully known and are not a critical aspect of the invention.
- two compositions containing compounds with the same chemical formula in the same amounts and differing only by the manner in which they were prepared can have very different physical properties.
- MgO dispersions with a higher magnesium content are desirable.
- simple modification of known procedures to prepare overbased detergents with high metal content can lead to unforeseen drawbacks including unacceptably high viscosities and gelling.
- attempts to concentrate the dispersion by distillation to get higher Mg content must be carried out at very high temperatures or reduced pressure.
- microwave irradiation can be used to advantage in the preparation of stable, small particle size metal oxide dispersions, such as those used as overbased metal oxide lubricant and fuel additives.
- Stable dispersions of sub-micron particles are obtained, typically while avoiding the very high temperatures that are otherwise required.
- the present invention provides a method for preparing stable dispersions of small particle size metal oxides, for example, overbased metal oxide dispersions, said method comprising subjecting a preliminary composition or preliminary dispersion formed from a mixture comprising a metal hydroxide, oxide or carbonate, a sulfonic or carboxylic acid dispersant, and an organic carrier, e.g., a high boiling hydrocarbon carrier to microwave irradiation resulting in a dispersion of metal oxide particles having an average particle size of one 1 micron or less, often having an average particle size of from 1-100 nm.
- a preliminary composition or preliminary dispersion formed from a mixture comprising a metal hydroxide, oxide or carbonate, a sulfonic or carboxylic acid dispersant, and an organic carrier, e.g., a high boiling hydrocarbon carrier to microwave irradiation resulting in a dispersion of metal oxide particles having an average particle size of one 1 micron or less, often having an average particle size of from 1-100
- the preliminary composition which is subjected to microwave irradiation is a preliminary dispersion formed by heating to a temperature of 85 °C, typically higher, e.g., from 100 to 220 °C, a mixture comprising a metal hydroxide, oxide or carbonate, a sulfonic or carboxylic acid dispersant, a high boiling hydrocarbon carrier, a low MW carboxylic acid, i.e., a C 1-5 carboxylic acid and water, optionally in the presence of an organic solvent. Often, water and other volatiles are removed, e.g., by distillation, before subjecting the resulting preliminary dispersion to microwave irradiation.
- the dispersions of the invention can be used as formed or may be further modified and are effective additives in fuels, lubricating oils, such as petroleum based fuels and lubricants, anti corrosive paints, and as part of any formulation containing similar materials.
- lubricating oils such as petroleum based fuels and lubricants, anti corrosive paints, and as part of any formulation containing similar materials.
- the stable metal oxide dispersion of the invention is added to fuels and lubricants used in gas turbine, boiler, cracking and engine operations etc.
- a preliminary composition e.g., a preliminary dispersion is prepared from a mixture comprising
- a high boiling hydrocarbon carrier selected from mineral oils, alkylated benzenes, oligomers or polymers of alpha olefins, polycyclic aromatics, alkylated derivatives of polycyclic aromatics and waxes,
- the percentages are by weight based on the total weight of the mixture, and then subjected to microwave irradiation to yield a metal oxide dispersion with average particle size of less than 1 micron.
- the microwave irradiation may be performed with or without external heating, however it is likely that even without additional heating the temperature of the reaction mixture will increase.
- the type of reaction vessel used There is no specific limitation on the type of reaction vessel used, however, if a sealed vessel is used, common provisions must be made to account for the build up in pressure, whereas if the vessel is "open", either exposed to the atmosphere or under an inert atmosphere at ambient pressure, common provisions must be made to account for any byproducts, starting materials or solvents that may evaporate.
- the preliminary dispersion is prepared by subjecting the mixture of a) through f) to a preliminary heating step.
- the mixture of a) through f) is subjected to a preliminary heating step and distillation to remove volatiles.
- the distillation may be a separate from the preliminary heating step, may occur during the preliminary heating step, or partial distillation may occur during preliminary heating followed by a second step to complete distillation, for example, a separate vacuum distillation step or distillation under higher temperatures or while using certain distillation equipment such as a thin film evaporator, distillation column etc may be used.
- a mixture comprising a), b), c) and any optional d), e) and f) above is heated, to temperatures of from about 85 °C to about 220 °C, for example from about
- the mixture is then distilled, or further distilled, at a temperature of from about 125 °C to about 240 °C, for example from about 150 °C to about 220 °C, or from about 165 °C to about 240 °C, optionally under vacuum;
- the time required for microwave irradiation is subject to various parameters including the intensity and wavelength of irradiation.
- the metal of the hydroxide, oxide or carbonate is an alkaline metal or alkaline-earth metal, i.e., Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba or Ra, typically selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr and Ba.
- the metal is an alkaline-earth metal selected from Mg, Ca and Ba, for example, Mg.
- the sulfonate or carboxylate dispersant is an alkylarylsulfonate or alkylaryl carboxylate dispersant, for example, an alky! benzene sulfonate.
- both water and a C 1-5 carboxlic acid are added to the mixture from which the preliminary composition is formed.
- the mixture is subjected to the preliminary heating step above and volatile distillates are removed, i.e., distilled, prior to microwave irradiation. Reaction, or complex formation, involving water, C 1-5 carboxylic acetic acid, metal compound and / or dispersant may occur during this heating step and volatiles, including water, may be removed.
- the organic solvent f) is optional and in general is removed or greatly reduced by distillation before microwave irradiation.
- the organic solvent is described in more detail below, has a with a boiling point below 280 °C, generally has a with a boiling point below 220 °C, for example a boiling point ranging from about 80 °C to about 210 °C, and is not the same as the high boiling hydrocarbon carrier.
- a high boiling hydrocarbon carrier selected from mineral oils, alkylated benzenes, oligomers or polymers of alpha olefins, polycyclic aromatics, alkylated derivatives of polycyclic aromatics and waxes,
- the dispersion obtained may be used as is, or further purified, concentrated, diluted or otherwise modified.
- the original reaction mixture from which the preliminary dispersion is prepared typically contains at least 8%, often at least 10% by weight of water, based on the total weight of the mixture, and in many embodiments 12% or more.
- the amount of water is comparable by weight to the amount of metal hydroxide, oxide or carbonate, and in some particular embodiments, the weight of water is higher.
- the reaction mixture contains from about a 5:1 to 1 :1 molar ratio of water to metal compound, for example, from about 3:1 to 1 :1.
- Ratios of from 2.5:1 to 1 :1 , or from 2:1 to 1 :1 are common, such as 1.5, 1.8, 2, 2.2 and 3 molar equivalents of water relative to metal compound can be employed.
- the process can also be used to prepare metal oxide dispersions starting with metal hydroxides, but in that case, less water is typically added due to the hydroxy groups present in the starting metal compound.
- the C 1-5 carboxylic acid can be any such acid, for example, acetic acid, propionic acid, butyric acid, pentanoic acid; excellent results have been obtained using acetic acid.
- a small amount of this acid relative to MgO is generally employed in the reaction, for example, the molar ratio of MgO to C 1-5 carboxylic acid is from about 100:1 to 2:1 , for example, from about 50:1 to about 5:1 , or from about 30 to 1 to 10:1 , such as a molar ratio of MgO to C 1-5 carboxylic acid of about 20:1.
- the dispersant is a sulfonic acid or carboxylic acid.
- Mixtures of dispersants may be used including mixtures of sulfonic acids, mixtures of carboxylic acids or mixtures including both sulfonic and carboxylic acids. Excellent results have been obtained using sulfonic acid dispersants widely known by those skilled in the art as oil-soluble sulfonic acids.
- sulfonic acid dispersants be derived from natural petroleum fractions or various synthetically prepared sulfonated compounds.
- Typical oil-soluble sulfonic acids which may be used include: alkane sulfonic acids, aromatic sulfonic acids, alkaryl sulfonic acids, aralkyl sulfonic acids, petroleum sulfonic acids such as mahogany sulfonic acid, petroleum sulfonic acid, paraffin wax sulfonic acid, petroleum naphthene sulfonic acid, polyalkylated sulfonic acid, and other types of sulfonic acids which may be obtained by fuming sulfuric acid treatment of petroleum fractions.
- an alkaryl sulfonic acid i.e., an alkylbenzene sulfonic acid
- Carboxylic acid dispersants which may be used are also well known in the art.
- the carboxylic add dispersants are not the same as the C 1-5 carboxylic acid required for the invention, as the dispersants have more than 5 carbon atoms, typically much more than 5 carbon atoms.
- Some examples include, lauric, myristic, palmitic, stearic, isostearic, archidic, behenic and lignoceric acids; aromatic acids such as alkyl salicylic acids.
- carboxylic acids include commercial grades containing a range of acids, including both saturated and unsaturated acids. Such mixtures may be obtained synthetically or may be derived from natural products, for example, tall, cotton, ground nut, coconut, linseed, palm kernel, olive, corn, palm, castor, soybean, sunflower, herring and sardine oils and tallow.
- the dispersant is a naturally occurring or synthetic sulfonic acid. Excellent results have been obtained using, for example, alkyated arylsulfonic acids, for example, alkylated benzenesulfonic acids.
- the sulfonic acid dispersant will have a MW of 300 or higher, often 350 or higher, for example 400 or higher.
- alkylated benzene sulfonic acids may be mono-alkylated, di-alkylated or mixtures of mono- and di- alkylated compounds may be used and in some embodiments, benzene sulfonic acid may be alkylated by alkyl chains of varying lengths.
- the MW is the number average molecular weight. For example, excellent results have been obtained using alkyated benzene sulfonic adds with an average MW of from about 350 to 1000.
- a molar ratio of MgO to dispersant of from about 10:1 to 200:1 is employed in the reaction, frequently the ratio is from about 20:1 to 200:1.
- the molar ratio of MgO to surfactant is from about 20:1 to 100:1 or from about 25:1 to 50:1.
- the molar ratio of MgO to Ci -5 carboxylic acid is from about 50:1 to about 5:1 or from 30:1 to10:1 and the molar ratio of MgO to dispersant, for example, an alkylated sulfonic acid, is from about 20:1 to 100:1 or from about 25:1 to 50:1.
- the high boiling hydrocarbon carrier is a material or mixture of materials well known in the art with a boiling point of 280 °C or higher, often much higher, for example, mineral oils, oligomers or polymers of alpha olefins, aromatic systems such as polycyclic aromatics and alkylated derivatives thereof, long chain alkanes including waxes and other similar natural or synthetic materials.
- part of the reasoning for choosing a high boiling carrier is that part of the process requires temperatures of 280 °C and higher.
- the optional organic solvent has a boiling point below 280 °C, typically 210 °C or lower, and it is generally desirable to remove it by distillation prior to microwave irradiation.
- the solvent can be used to make the initial reaction mixture more fluid and stirrable during a preliminary heating step, especially if very low amounts of carrier hydrocarbon are used.
- the solvent is chosen so that it does not interfere with the overall process.
- aliphatic or aromatic hydrocarbons with boiling points ranging from about 80 °C to about 240 °C, for example, boiling points ranging from about 80 °C to about 220 °C and mixtures thereof are conveniently used, including linear and cycloaliphatic compounds such as octanes, decanes etc, and aromatic hydrocarbons such as xylene, mesitylene, ethylbenzene, butyl benzenes, tetralin and the like. Lower boiling solvents are optional and are readily removed, if desired, by distillation once the process reactions are complete.
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Abstract
Microwave irradiation is used to prepare stable dispersions of small particle metal oxides, such as magnesium oxide and calcium oxide, from a composition prepared from a mixture comprising an oxide, hydroxide or carbonate of the metal, a carrier, a sulfonic or carboxylic acid dispersant, and typically a low MW carboxylic acid and water. Dispersions with an average particle size of one micron or less, often from 1-100 nm, are typically obtained.
Description
MICROWAVE PROCESS FOR PREPARING
STABLE METAL OXIDE DISPERSIONS
Stable dispersions of small particle metal oxides, such as magnesium oxide and calcium oxide, with an average particle size of one micron or less, often from 1-100 nm, are prepared by microwave irradiation of a composition prepared from a mixture comprising an oxide, hydroxide or carbonate of the metal, a carrier, a sulfonic or carboxylic acid dispersant, and typically a low MW carboxylic acid and water.
BACKGROUND OF THE INVENTION
Fine particle metal oxides have a variety of commercial uses. For example, overbased detergents, e.g., compositions comprising overbased alkaline metal or alkaline-earth metal compounds such as metal oxides and often complexed with an organic dispersant, are well known additives for lubricating oil compositions and petroleum fuels. In such cases, the metal oxide is most conveniently added and used as a dispersion in a carrier.
Petroleum fuels such as residual fuel oils contain large amounts of impurities which result in corrosive deposits in the equipment. For example, crude oil usually contains 1- 500 ppm of vanadium in the form of a porphyrin complex depending on the source. Because of its origin as a concentrate from the refining process, residual oil contains several times more vanadium than the crude from which it was derived. The combustion of these vanadium-containing fuels produces very corrosive deposits which can destroy a metal part, such as a gas turbine blade, in a matter of hours.
The presence of sodium in fuel can also have catastrophic consequences. For example, in maritime use the sodium level can be increased because of the introduction of sodium chloride through the air intake and contamination of the fuel by sea water. During combustion, the sodium can react with sulfur in the fuel to form a sulfate which is deposited in turbine parts.
Overbased detergents, perform a variety of functions including anti-corrosion, deposit control, acid scavenger functions For example, overbased magnesium compounds complexed with sulfonate and carboxylate dispersants, have long been used as anti- corrosion and acid neutralization additives for lubricating oils and greases, anti-corrosion and acidic neutralization additives during the combustion of fuels such as residual fuel, pulverized sulfur-containing coal, corrosion inhibitors in fuels containing vanadium etc. The addition of overbased magnesium detergents to, for example, boiler fuels or gas turbine fuels, is known to reduce corrosion, presumably by forming magnesium complexes with the vanadium or sodium.
Overbased metal detergents are also added to lubricating oils to prevent or remove deposits of oil-insoluble sludge, varnish, carbon and lead compounds which otherwise form on internal combustion engine parts and for combating severe rust conditions which may be encountered during shipping or storage of machinery or exposure to out-door weather. Detergent additives for automotive and diesel engine oils also chemically react with the highly acidic by-products of combustion that find their way into the lubricating oil system.
Obviously a useful dispersion of metal oxide must be stable during storage and the overbased metal must stay well dispersed in the lubricant or fuel. A variety of parameters will affect the stability and activity of these dispersions such as the dispersants and carriers employed, particle size of the solid components, and the relationship between metal and dispersant. The process by which the overbased metal compounds and complexes are prepared will greatly influence the actual physical make up and properties of the overbased metal dispersion, impacting particle size and distribution of the metal compound throughout the dispersion, the viscosity and stability of the dispersion, the amount of the metal within the dispersion etc.
Overbased metal additives, for example, overbased MgO dispersions are often added as a dispersion in a high boiling liquid hydrocarbon. Part of the rationale for supplying MgO dispersions in high boiling carriers, i.e., carriers with boiling points over 200 °C, often greater than 250 °C or 280 °C, and even much greater than 300 °C is due to the manner in which the dispersions are made. For example, overbased stable MgO dispersions
with fine particle sizes and good flowcharacteristics are typically produced, even when starting with MgO as a starting material, through thermal decomposition of Mg(OH)2 or Mg(OH)2 derived intermediates which require high temperature (300-350°C). Thus, the use of high boiling point solvents as carriers is dictated by practical processing considerations.
US Pat. 4,163,728, discloses magnesium-containing dispersions prepared by high temperature decomposition of magnesium salts of carboxylic acids to MgO in a dispersant-containing fluid. In the process, Mg(OH)2 , an organic carboxylic acid or sulfonic acid surfactant such as naphthenic acid, acetic acid and water are heated in a high boiling hydrocarbon to temperatures up to 350 °C, which is above the
decomposition point of magnesium acetate, 323 °C. It is believed that magnesium acetate is formed in situ and decomposes at the high temperatures used. Water is also removed at the elevated temperatures.
US Pat. 4,293,429, discloses a variation of US Pat. 4,163,728 which begins with MgO instead of Mg(OH)2 . In the process, the bulk MgO is converted to magnesium acetate which forms suspended MgO particles of less than 5 microns, and preferably less that 1 micron. Thus, the coarse MgO particles are converted into a dispersion of stabilized MgO microparticulates. Lower temperatures fail to provide the fine particle size MgO.
US 4,129,589, discloses a process for preparing an over-based oil-soluble magnesium salt of a sulfonic acid by contacting carbon dioxide gas with a mixture comprising an oil- soluble magnesium salt of a sulfonic acid, magnesium oxide, water, and a promoter system comprising a carboxylic acid of 1 to 5 carbons in an inert solvent for lowering the viscosity of said mixture to facilitate mixing. The products of US 4,129,589 had acceptably low viscosity but the magnesium content was typically 9-10% and no more than 14%.
US 6,197,075, discloses an overbased magnesium sulfonate, carboxylate or phenate product containing at least 14% and up to about 18% by weight of magnesium, useful as a deposit control additive for residual fuel oils and turbine fuels prepared by contacting a mixture of i) a sulfonic acid, phenol or carboxylic acid or salt thereof, ii) a magnesium oxide, iii) a co-promoter comprising a lower carboxylic acid, a lower alcohol,
a succinic anhydride and water, and iv) a solvent and/or oil, with an acidic gas such as carbon dioxide at 50 °F up to the reflux temperature of the mixture to overbase the reaction mixture.
The overbased metal compositions described above and elsewhere are best described as products by process as there is typically no simple chemical formula which adequately correlates to the essential material makeup and the physical properties of the product. Often, the molecular structures of the metal complexes are not fully known and are not a critical aspect of the invention. For example, two compositions containing compounds with the same chemical formula in the same amounts and differing only by the manner in which they were prepared can have very different physical properties.
While the use of high boiling solvents or carriers in the above processes can provide useful dispersions, there is the need for improved products and methods. For example, MgO dispersions with a higher magnesium content are desirable. However simple modification of known procedures to prepare overbased detergents with high metal content can lead to unforeseen drawbacks including unacceptably high viscosities and gelling. Also, attempts to concentrate the dispersion by distillation to get higher Mg content must be carried out at very high temperatures or reduced pressure.
Co-pending application US 13/167,127, incorporated herein by reference, describes a method of obtaining free flowing MgO dispersions with high Mg content in high boiling carriers using a mixture of solvents and defined quantities of lower carboxylic acid and water. Co-pending provisional application US 61/502,914, incorporated herein by reference, discloses a process for preparing similar MgO dispersions in lower boiling solvents by performing some of the processing steps under increased pressure.
Along with heat, light etc, microwave radiation is a source of energy that can be used to promote chemical reactions. In some cases, the products produced from a microwave induced reaction are different than those produced by thermal or UV initiated reactions; in some cases the products are the same but the chemical conversion is more efficient. Makhluf, et. al, "Microwave-Assisted Synthesis of Nanocrystalline MgO and Its Use as a Bacteriocide" Advanced Functional Materials 2005, 15, 1708-1715; Sugiyama, et. al, Matsuda, T. "Synthesis of Magnesium oxide catalyst in a Microwave plasma reactor" 9th
Int. Symp. Plasma Chem. 1989, 2, 820-824; and Nakano, et. al, "Surface Characterization of Metal Oxide fine Powders Prepared by Microwave Cold Plasma: AFM Observations of Silica Surface" 11th Int. Symp. Plasma Chem. 1993, 1 , 1422-1427 disclose the use of microwave radiation in the production of inorganic particles.
It has been discovered that microwave irradiation can be used to advantage in the preparation of stable, small particle size metal oxide dispersions, such as those used as overbased metal oxide lubricant and fuel additives. Stable dispersions of sub-micron particles are obtained, typically while avoiding the very high temperatures that are otherwise required.
SUMMARY OF THE INVENTION
The present invention provides a method for preparing stable dispersions of small particle size metal oxides, for example, overbased metal oxide dispersions, said method comprising subjecting a preliminary composition or preliminary dispersion formed from a mixture comprising a metal hydroxide, oxide or carbonate, a sulfonic or carboxylic acid dispersant, and an organic carrier, e.g., a high boiling hydrocarbon carrier to microwave irradiation resulting in a dispersion of metal oxide particles having an average particle size of one 1 micron or less, often having an average particle size of from 1-100 nm.
In one embodiment, the preliminary composition which is subjected to microwave irradiation is a preliminary dispersion formed by heating to a temperature of 85 °C, typically higher, e.g., from 100 to 220 °C, a mixture comprising a metal hydroxide, oxide or carbonate, a sulfonic or carboxylic acid dispersant, a high boiling hydrocarbon carrier, a low MW carboxylic acid, i.e., a C1-5 carboxylic acid and water, optionally in the presence of an organic solvent. Often, water and other volatiles are removed, e.g., by distillation, before subjecting the resulting preliminary dispersion to microwave irradiation.
No additional solubilizing or dispersing agents, promoters or reactants such as carbon dioxide, amines, alcohols etc are needed to obtain the desired metal oxide dispersions and metal content of up to 40 or 50 weight %, and in certain embodiments higher, based on the total weight of the dispersion can be prepared. For example, metal contents of 10%, 15%, 20%, 30%, 35%, 40% and higher can be prepared.
A specific chemical formula for the composition of the dispersion is not fully descriptive of the product, and the molecular structures of the metal oxide complexes of the invention are not fully known, however, the product obtained is a free flowing dispersion of predominately submicron metal oxide particles engulfed by and complexed to a sulfonate or carboxylate dispersant. Other metal compounds such as traces of metal hydroxide are also believed to be present.
The dispersions of the invention can be used as formed or may be further modified and are effective additives in fuels, lubricating oils, such as petroleum based fuels and lubricants, anti corrosive paints, and as part of any formulation containing similar materials. For example, the stable metal oxide dispersion of the invention is added to fuels and lubricants used in gas turbine, boiler, cracking and engine operations etc.
DESCRIPTION OF THE INVENTION
According to the invention, a preliminary composition, e.g., a preliminary dispersion is prepared from a mixture comprising
a) 5-80%, e.g., 5-50%, of a metal hydroxide, metal oxide or metal carbonate
b) 2-15% of a sulfonate or carboxylate dispersant
c) 10-70% of a high boiling hydrocarbon carrier selected from mineral oils, alkylated benzenes, oligomers or polymers of alpha olefins, polycyclic aromatics, alkylated derivatives of polycyclic aromatics and waxes,
d) 0-10% of a C1-5 carboxylic acid,
e) 0%-30% water
and
f) 0 - 60% of an organic solvent,
wherein the percentages are by weight based on the total weight of the mixture, and then subjected to microwave irradiation to yield a metal oxide dispersion with average particle size of less than 1 micron.
The microwave irradiation may be performed with or without external heating, however it is likely that even without additional heating the temperature of the reaction mixture will increase. There is no specific limitation on the type of reaction vessel used, however, if a sealed vessel is used, common provisions must be made to account for the build up in
pressure, whereas if the vessel is "open", either exposed to the atmosphere or under an inert atmosphere at ambient pressure, common provisions must be made to account for any byproducts, starting materials or solvents that may evaporate.
In one embodiment, the preliminary dispersion is prepared by subjecting the mixture of a) through f) to a preliminary heating step. In another embodiment, the mixture of a) through f) is subjected to a preliminary heating step and distillation to remove volatiles. The distillation may be a separate from the preliminary heating step, may occur during the preliminary heating step, or partial distillation may occur during preliminary heating followed by a second step to complete distillation, for example, a separate vacuum distillation step or distillation under higher temperatures or while using certain distillation equipment such as a thin film evaporator, distillation column etc may be used.
For example, a mixture comprising a), b), c) and any optional d), e) and f) above is heated, to temperatures of from about 85 °C to about 220 °C, for example from about
85 °C to about 180 °C, often from about 90 °C to about 150 °C, typically the mixture is heated at reflux, with stirring or other agitation for about 0.25 to 5 hours, generally 0.5 to
4 hours, for example 1 to 3 hours, during which time volatiles may be distilled and collected;
the mixture is then distilled, or further distilled, at a temperature of from about 125 °C to about 240 °C, for example from about 150 °C to about 220 °C, or from about 165 °C to about 240 °C, optionally under vacuum;
cooled and then subjected to microwave irradiation.
The time required for microwave irradiation is subject to various parameters including the intensity and wavelength of irradiation.
The metal of the hydroxide, oxide or carbonate is an alkaline metal or alkaline-earth metal, i.e., Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba or Ra, typically selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr and Ba. In many embodiments the metal is an alkaline-earth metal selected from Mg, Ca and Ba, for example, Mg.
Excellent results are achieved when the sulfonate or carboxylate dispersant is an alkylarylsulfonate or alkylaryl carboxylate dispersant, for example, an alky! benzene
sulfonate. In the process, there is less than a molar equivalent of the dispersant present relative to metal hydroxide, oxide or carbonate.
In most embodiments of the invention both water and a C1-5 carboxlic acid are added to the mixture from which the preliminary composition is formed. Less than a molar equivalent of the C1-5 carboxlic acid is added, relative to metal hydroxide, oxide or carbonate, often much less than a molar equivalent, but there can be significantly more than a molar equivalent of water added. Typically, when water and C1-5 carboxlic acid are added, the mixture is subjected to the preliminary heating step above and volatile distillates are removed, i.e., distilled, prior to microwave irradiation. Reaction, or complex formation, involving water, C1-5 carboxylic acetic acid, metal compound and / or dispersant may occur during this heating step and volatiles, including water, may be removed.
Even if a distillation is performed prior to microwave irradiation, it may still be necessary to remove water upon microwave irradiation as it is possible to form water during the this part of the process. Of course it is desirable to remove most or all of any added or generated water at some point as the final product dispersion will contain significantly less than 8% water, in many cases the final product dispersion will contain less than 2% water, for example, less than 1 % water.
The organic solvent f) is optional and in general is removed or greatly reduced by distillation before microwave irradiation. The organic solvent is described in more detail below, has a with a boiling point below 280 °C, generally has a with a boiling point below 220 °C, for example a boiling point ranging from about 80 °C to about 210 °C, and is not the same as the high boiling hydrocarbon carrier.
For example, a mixture comprising
a) 5-50% of a metal hydroxide, metal oxide or metal carbonate
b) 2-15% of a sulfonate or carboxylate dispersant
c) 10-70% of a high boiling hydrocarbon carrier selected from mineral oils, alkylated benzenes, oligomers or polymers of alpha olefins, polycyclic aromatics, alkylated derivatives of polycyclic aromatics and waxes,
d) 1-10% of a C1.5 carboxylic acid,
e) 8%-30% water
and
f) 0 - 60% of an organic solvent with a boiling point below 220 °C, for example a boiling point ranging from about 80 °C to about 210 °C, for example xylene or mesitylene, is stirred and heated under reflux for about 0.5 to about 4 hours, for example from about 0.5 to about 2 hours, for example about 1 hour, and then heated from about 165 °C to about 240 °C to distill off volatiles, resulting in a reaction mixture which is cooled to below 100 °C, for example cooled to approximately room temperature, and subjected to microwave irradiation in a commercial microwave ( e.g., 2.45 GHz) to a yield MgO oxide nanoparticle dispersion in excellent yield, with average particle size expected to be from about 1 to about 100 nm.
For example, a mixture comprising
a) 5-40%, typically 10-40%, for example 10-25, of a metal hydroxide, metal oxide or metal carbonate
b) 2-10%, for example 3-10%, for example 3-7% of a dispersant, for example an
alkyl benzene sulfonic acid
c) 10-70%, for example, 10-50%, for example 15-40%, of a high boiling hydrocarbon carrier,
d) 1-7%, for example, 1-4% or 2-5% of a C1-5 carboxylic acid,
e) 8%-30%, for example 10%-20%, for example, 12-18% water
and
f) 10— 60%, for example 20-60%, for example 30-50% of an organic solvent with a boiling point ranging from about 80 °C to about 210 °C, is stirred and heated under reflux for about 0.5 to about 2 hours, for example about 1 hour, and then heated from about 165 °C to about 220 °C to distill off volatiles;
cooled to approximately room temperature, and then subjected to microwave irradiation in a commercial microwave. The dispersion obtained may be used as is, or further purified, concentrated, diluted or otherwise modified.
Most or all of the added water is removed from the preliminary dispersion by distillation prior to microwave irradiation, however, the original reaction mixture from which the
preliminary dispersion is prepared typically contains at least 8%, often at least 10% by weight of water, based on the total weight of the mixture, and in many embodiments 12% or more. In certain embodiments, the amount of water is comparable by weight to the amount of metal hydroxide, oxide or carbonate, and in some particular embodiments, the weight of water is higher. In terms of molar equivalents relative to, e.g., metal oxide or metal carbonate, the reaction mixture contains from about a 5:1 to 1 :1 molar ratio of water to metal compound, for example, from about 3:1 to 1 :1. Ratios of from 2.5:1 to 1 :1 , or from 2:1 to 1 :1 are common, such as 1.5, 1.8, 2, 2.2 and 3 molar equivalents of water relative to metal compound can be employed. The process can also be used to prepare metal oxide dispersions starting with metal hydroxides, but in that case, less water is typically added due to the hydroxy groups present in the starting metal compound.
The C1-5 carboxylic acid can be any such acid, for example, acetic acid, propionic acid, butyric acid, pentanoic acid; excellent results have been obtained using acetic acid. A small amount of this acid relative to MgO is generally employed in the reaction, for example, the molar ratio of MgO to C1-5 carboxylic acid is from about 100:1 to 2:1 , for example, from about 50:1 to about 5:1 , or from about 30 to 1 to 10:1 , such as a molar ratio of MgO to C1-5 carboxylic acid of about 20:1.
The dispersant is a sulfonic acid or carboxylic acid. Mixtures of dispersants may be used including mixtures of sulfonic acids, mixtures of carboxylic acids or mixtures including both sulfonic and carboxylic acids. Excellent results have been obtained using sulfonic acid dispersants widely known by those skilled in the art as oil-soluble sulfonic acids.
For example, sulfonic acid dispersants be derived from natural petroleum fractions or various synthetically prepared sulfonated compounds. Typical oil-soluble sulfonic acids which may be used include: alkane sulfonic acids, aromatic sulfonic acids, alkaryl sulfonic acids, aralkyl sulfonic acids, petroleum sulfonic acids such as mahogany sulfonic acid, petroleum sulfonic acid, paraffin wax sulfonic acid, petroleum naphthene sulfonic acid, polyalkylated sulfonic acid, and other types of sulfonic acids which may be obtained by fuming sulfuric acid treatment of petroleum fractions. In one embodiment, an alkaryl sulfonic acid, i.e., an alkylbenzene sulfonic acid, is used as dispersant with excellent results.
Carboxylic acid dispersants which may be used are also well known in the art. The carboxylic add dispersants are not the same as the C1-5 carboxylic acid required for the invention, as the dispersants have more than 5 carbon atoms, typically much more than 5 carbon atoms. Some examples include, lauric, myristic, palmitic, stearic, isostearic, archidic, behenic and lignoceric acids; aromatic acids such as alkyl salicylic acids.
Mixtures of carboxylic acids include commercial grades containing a range of acids, including both saturated and unsaturated acids. Such mixtures may be obtained synthetically or may be derived from natural products, for example, tall, cotton, ground nut, coconut, linseed, palm kernel, olive, corn, palm, castor, soybean, sunflower, herring and sardine oils and tallow.
In many embodiments of the invention, the dispersant is a naturally occurring or synthetic sulfonic acid. Excellent results have been obtained using, for example, alkyated arylsulfonic acids, for example, alkylated benzenesulfonic acids. In general, the sulfonic acid dispersant will have a MW of 300 or higher, often 350 or higher, for example 400 or higher. Mixtures of sulfonic acids may be used, for example, alkylated benzene sulfonic acids may be mono-alkylated, di-alkylated or mixtures of mono- and di- alkylated compounds may be used and in some embodiments, benzene sulfonic acid may be alkylated by alkyl chains of varying lengths. In such cases, the MW is the number average molecular weight. For example, excellent results have been obtained using alkyated benzene sulfonic adds with an average MW of from about 350 to 1000.
In general, a molar ratio of MgO to dispersant of from about 10:1 to 200:1 is employed in the reaction, frequently the ratio is from about 20:1 to 200:1. In certain embodiments the molar ratio of MgO to surfactant is from about 20:1 to 100:1 or from about 25:1 to 50:1.
In many embodiments, the molar ratio of MgO to Ci-5 carboxylic acid, for example acetic acid, is from about 50:1 to about 5:1 or from 30:1 to10:1 and the molar ratio of MgO to dispersant, for example, an alkylated sulfonic acid, is from about 20:1 to 100:1 or from about 25:1 to 50:1.
The high boiling hydrocarbon carrier is a material or mixture of materials well known in the art with a boiling point of 280 °C or higher, often much higher, for example, mineral
oils, oligomers or polymers of alpha olefins, aromatic systems such as polycyclic aromatics and alkylated derivatives thereof, long chain alkanes including waxes and other similar natural or synthetic materials. Obviously, part of the reasoning for choosing a high boiling carrier is that part of the process requires temperatures of 280 °C and higher.
The optional organic solvent has a boiling point below 280 °C, typically 210 °C or lower, and it is generally desirable to remove it by distillation prior to microwave irradiation. The solvent can be used to make the initial reaction mixture more fluid and stirrable during a preliminary heating step, especially if very low amounts of carrier hydrocarbon are used. The solvent is chosen so that it does not interfere with the overall process. For example, well known aliphatic or aromatic hydrocarbons with boiling points ranging from about 80 °C to about 240 °C, for example, boiling points ranging from about 80 °C to about 220 °C and mixtures thereof are conveniently used, including linear and cycloaliphatic compounds such as octanes, decanes etc, and aromatic hydrocarbons such as xylene, mesitylene, ethylbenzene, butyl benzenes, tetralin and the like. Lower boiling solvents are optional and are readily removed, if desired, by distillation once the process reactions are complete.
The product of the process and the process itself represent embodiments of the invention.
EXAMPLE
In a 2000 mL 3-neck round bottom flask, was charged 298 grams of MgO (98%), 120 grams of an alkyl benzene sulfonic acid dispersant, 500 grams of high boiling hydrocarbon ALCHISOR DE, 1 ,000 grams of Xylene, 300 grams of water, and 62 grams of glacial acetic acid under ambient conditions. The mixture was stirred and heated to reflux for 1 hr. The mixture was further heated to 180 °C to remove all volatiles. The resulting product was cooled down to room temperature to provide a gray preliminary dispersion with a small amount of sediment. The preliminary dispersion was subjected to microwave irradiation in a commercial microwave (2.45 GHz) to yield MgO oxide nanoparticte dispersion with average particle size expected to be between 1-100 nm.
Claims
1. A process for preparing a stable, free flowing overbased metal oxide dispersion, wherein
a) 5-80% of a metal hydroxide, metal oxide or metal carbonate
b) 2-15% of a sulfonate or carboxylate dispersant
c) 10-70% of a high boiling hydrocarbon carrier selected from mineral oils, alkylated benzenes, oligomers or polymers of alpha olefins, polycyclic aromatics, alkylated derivatives of polycyclic aromatics and waxes,
d) 0-10% of a Ci_5 carboxylic acid,
e) 0%-30% water
and
f) 0 - 60% of an organic solvent having a boiling point of less than 280 °C,
wherein the percentages are by weight based on the total weight of the mixture, are combined to form a preliminary dispersion, which is subjected to microwave irradiation to yield after irradiation a metal oxide dispersion with average particle size of less than 1 micron.
2. The process according to claim 1 wherein the metal of the hydroxide, oxide or carbonate is selected from Li, Na, K, Cs, Mg, Ca, and Ba.
3. The process according to claim 2 wherein the metal of the hydroxide, oxide or carbonate is selected from Mg, Ca, and Ba.
4. The process according to claim 3 wherein the metal of the hydroxide, oxide or carbonate is Mg.
5. The process according to claim 1, 2, 3, 4 or 5 wherein the sulfonate or carboxylate dispersant is an alkylarylsulfonate or alkylaryl carboxylate dispersant.
6. The process according to claim 5 wherein
a) 5-50% of a metal hydroxide, metal oxide or metal carbonate
b) 2-15% of a sulfonate or carboxylate dispersant
1.3
c) 10-70% of a high boiling hydrocarbon carrier selected from mineral oils, alkylated benzenes, oligomers or polymers of alpha olefins, polycyclic aromatics, alkylated derivatives of polycyclic aromatics and waxes,
d) 0-10% of a Ci 5 carboxylic acid,
e) 0%-30% water
and
f) 0 - 60% of an organic solvent,
are combined and heated to temperatures of from about 85 °C to about 220 °C for from about 0.25 to about 5 hours,
and voiatiles are removed by distillation to form the preliminary dispersion which is then subjected to microwave irradiation.
7. The process according to claim 6 wherein
a) 5-40%, typically a metal hydroxide, metal oxide or metal carbonate
b) 3-7% of an alkyl benzene sulfonic acid dispersant,
c) 10-70% of a high boiling hydrocarbon carrier,
d) 1-7% of a Ci_5 carboxylic acid,
e) 8%-30% water
and
f) 10-60%, of an organic solvent with a boiling point of from about 80 °C to about 210 °C, are combined, heated and distilled to remove voiatiles to form the preliminary dispersion.
8. The process according to claim 7 wherein the metal hydroxide, metal oxide or metal carbonate is magnesium oxide or magnesium hydroxide, the C -5 carboxylic acid is acetic acid, and the organic solvent is xylene or mesitylene and the metal oxide dispersion formed is a magnesium oxide dispersion with an average particle size of less than 1 micron.
9. The process according to claim 8 wherein the metal oxide dispersion formed is a magnesium oxide dispersion with an average particle size of from about 1 nm to about
100 nm.
10. A magnesium oxide dispersion obtained by the process according to claim 1.
11. A lubricant or fuel composition comprising the magnesium oxide dispersion according to any of claims 1 to 10.
12. The composition according to claim 11 wherein the lubricant or fuel is petroleum based.
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US13/681,548 US20130178404A1 (en) | 2012-01-06 | 2012-11-20 | Microwave Process for Preparing Stable Metal Oxide Dispersions |
US13/681,548 | 2012-11-20 |
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US4129589A (en) | 1976-07-15 | 1978-12-12 | Surpass Chemicals Limited | Over-based magnesium salts of sulphonic acids |
US4163728A (en) | 1977-11-21 | 1979-08-07 | Petrolite Corporation | Preparation of magnesium-containing dispersions from magnesium carboxylates at low carboxylate stoichiometry |
US4293429A (en) | 1980-01-16 | 1981-10-06 | Petrolite Corporation | MgO Dispensions |
US6197075B1 (en) | 1998-04-02 | 2001-03-06 | Crompton Corporation | Overbased magnesium deposit control additive for residual fuel oils |
JP2011012290A (en) * | 2009-06-30 | 2011-01-20 | Tokyo Institute Of Technology | Method for producing metal fine particle from metal oxide or metal hydroxide by microwave emission, and production device therefor |
-
2012
- 2012-11-20 US US13/681,548 patent/US20130178404A1/en not_active Abandoned
- 2012-12-04 WO PCT/US2012/067699 patent/WO2013103459A1/en active Application Filing
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US4129589A (en) | 1976-07-15 | 1978-12-12 | Surpass Chemicals Limited | Over-based magnesium salts of sulphonic acids |
US4163728A (en) | 1977-11-21 | 1979-08-07 | Petrolite Corporation | Preparation of magnesium-containing dispersions from magnesium carboxylates at low carboxylate stoichiometry |
US4293429A (en) | 1980-01-16 | 1981-10-06 | Petrolite Corporation | MgO Dispensions |
US6197075B1 (en) | 1998-04-02 | 2001-03-06 | Crompton Corporation | Overbased magnesium deposit control additive for residual fuel oils |
JP2011012290A (en) * | 2009-06-30 | 2011-01-20 | Tokyo Institute Of Technology | Method for producing metal fine particle from metal oxide or metal hydroxide by microwave emission, and production device therefor |
Non-Patent Citations (4)
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DATABASE WPI Week 201108, Derwent World Patents Index; AN 2011-A90452, XP002695502 * |
MAKHLUF: "Microwave-Assisted Synthesis of Nanocrystalline MgO and Its Use as a Bacteriocide", ADVANCED FUNCTIONAL MATERIALS, vol. 15, 2005, pages 1708 - 1715 |
NAKANO: "Surface Characterization of Metal Oxide fine Powders Prepared by Microwave Cold Plasma: AFM Observations of Silica Surface", 11TH INT. SYMP. PLASMA CHEM., vol. 1, 1993, pages 1422 - 1427 |
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