JP2005520927A - Catalytic metal additive concentrates and methods for making and using the same - Google Patents

Abstract

A metal-based combustion catalyst for an internal combustion engine or other combustion device is improved.
(A) A catalyst metal addition concentrate comprising a fuel-soluble platinum and / or cerium component which is stable at a temperature of 100 ° C. or higher and is uniformly dispersed in an organic carrier in an amount capable of normally maintaining a solid. (B) A high-temperature stable platinum and / or cerium fuel additive addition unit encapsulated with a solid polymer as a leaching control component, and a method for producing and using the unit.

Description

  The present invention improves the supply of metal combustion catalysts to internal combustion engines and other combustion devices and effectively provides a slow and reliable supply of metal additives including platinum-containing catalyst components (or compositions) to the fuel. The present invention relates to a novel method for enabling the creation of an additive supply means having the ability to Furthermore, the present invention provides additive release materials and methods designed to be applicable with various delivery mechanisms.

  A number of approaches have been taken to supply fuel additives to combustors such as internal combustion engines. Some additive supply means require the use of a mixture of a low volatility or high viscosity solvent carrier and a highly concentrated catalyst. Since platinum and other catalytic metal components are poorly soluble in heavy solvents, they are not freely soluble or fully dissolved in a form that can be applied by some mechanism used to achieve slow release to fuel. Not stable.

  Patent Document 1 discloses a method for continuously metering a liquid additive in a fuel supply line. Because this liquid delivery device is complex and has other drawbacks, improvements to solid, soluble additive material based devices were necessary.

  In another system, Davis discloses a soluble member in US Pat. He provides fuel filter components that contain fuel additives in a waxy substrate. In a preferred form, the fuel additive includes a microbicide that may be present in the combustion device and the fuel and dissolves more in the fuel than in the water. Microbicides have a high melting point and properly release microbicides without disturbing exhaust gas emissions and without excessive release of fuel additives that adversely affect the engine and fuel components Encapsulated in a waxy substrate with combustion properties. The fuel additive may also include cetane improvers, antioxidants, stabilizers, combustion improvers, and emission reduction agents. The waxy substrate is made from paraffin, which is said to be a hydrocarbon mixture with clean combustion properties. The insert is received in the hollow cylinder of the fuel filter can. It slowly releases the fuel additive on the vertically supported and dissolved wax substrate.

  Patent Document 3 describes a fuel filter containing a fuel additive that can be released into fuel. The fuel release rate is said to be adjusted to a substantially constant rate in order to maintain a uniform level of fuel additive in the fuel. Fuel from the filter chamber travels through the diffusion orifice and contacts the additive tablet with the outer coating. The fuel diffuses through the coating, contacts the fuel additive component, and dissolves in the fuel to provide a fuel component comprising the dissolved additive. The fuel component is back-diffused from the cladding into the interior and mixed with the fuel. The fuel additive may be liquid or solid, and two or more fuel additives may be combined or combined with a suitable polymer. They can be solid or semi-solid materials such as tablets so that the release of additives into the fuel can be controlled. The fuel additive can further include a wide range of binders, complexing agents and mold release agents. When the additive is provided in liquid form, it is preferably combined with a suitable agent to form a solid or semi-solid form. The term fuel additive includes antioxidants, antiwear agents, cetane improvers, corrosion inhibitors, emulsifiers, detergents, dispersants, flow improvers, lubricants, and metal deactivators. In other embodiments, the fuel additive can be embedded within a solid matrix. The matrix can be hydrocarbon soluble or hydrocarbon insoluble. If the matrix material is hydrocarbon insoluble, the fuel must be matrix permeable and contactable with the fuel additive. It has been disclosed that there are particular advantages to embedding liquid additives in a solid matrix. This is said to provide a means of controlling the rate of additive release into the fuel.

  In Patent Document 4, Refebre describes an oil filter containing an oil-soluble thermoplastic additive material. The thermoplastic material includes an oil oxidation and acid generation resistant additive and is placed in a casing between the particulate filter material and the felt pad. The thermoplastic material may be rice granular pellets or high molecular weight polypropylene in the form of spaghetti strands. The additive consists of about 10-17 wt% thermoplastic material / additive combination, and the additive is released when the thermoplastic material melts above ambient oil temperature. High molecular weight polypropylene is superior in use as a thermoplastic material compared to polyester, polycarbonate, polyallomer, polyethylene, and polysulfone, and it is described that ethylene propylene polypropylene is particularly desirable.

  In Patent Document 5, Paul et al. Describe an oil filter including an oil-soluble solid polymer body in which an oil additive is compounded. Polymers with desirable properties include ethylene-propylene copolymers with molecular weights in the range of 200,000-300,000; ethylene-ethyl acrylate polymers with molecular weights in the range of 200,000-300,000; molecular weights of about 500,000 Note that it can be used practically in the system, such as, for example, an oxidized polypropylene having a molecular weight of; An example of a polymer that has been described as being highly satisfactory is polyisobutylene having a molecular weight in the range of about 60,000-135,000. Similarly, in U.S. Patent No. 6,099,056, Neyland describes an oil filter having a polymer insert that carries an oil additive. The additive is encapsulated so that the polymer slowly dissolves in the oil.

  In Patent Document 7, an apparatus for directly adding a solid additive such as ferrocene to a fuel for an internal combustion engine is described. The solid additive is contained in a replaceable cartridge that is placed in a portion that fills the neck of the fuel tank. Fuel filling the neck dissolves the additive in the fuel.

  The literature describes the preparation of platinum and / or cerium-based fuel additive units that can be used to release platinum and / or cerium combustion catalysts in fuel in a very small amount by dissolution or diffusion. Is not listed.

  Accordingly, there is a need for a solid addition form of platinum and / or cerium and / or iron-based combustion catalysts, a method for producing the resulting additive components, and a practical system for adding fuels using the same.

USP 4,662,327 USP 5,507,942 USP 6,238,554 USP 5,591,330 USP 4,075,098 USP 3,336,223 USP 5,456,217

  The subject of the present invention is, for example, turbines, boilers, combustion furnaces, process heaters, heat recovery units, diesel engines, etc. that contain carbon and use fuels such as fossil fuels, distillates, residues and gaseous fuel It is to provide a novel method that meets the above needs with a solid addition form of metal-based combustion catalyst for combustion fuels.

  The present invention, in one aspect, provides a material that is effective in supplying a unit for adding small amounts of platinum and / or cerium combustion catalysts into the fuel by dissolution or diffusion. In this aspect, the present invention provides a catalytic metal additive concentrate (referred to herein as CMAC), usually in a solid, semi-solid or sticky form.

  The present invention also provides an addition unit for providing a catalytic metal fuel additive in the fuel simply and effectively so as to be effective at moderately low concentrations. The addition unit is a fuel filter, fuel / water separator or other device made to contact diesel fuel when it is sent to the engine or stored in a fuel tank or other part of the fuel system. For use, it can be provided in any suitable shape, for example, cylindrical, cuboid, spherical, or similar.

  In one means of the present invention for providing an addition unit for adding small amounts of platinum and / or cerium combustion catalysts into the fuel by dissolution or diffusion, a catalytic metal additive concentrate (referred to herein as CMAC) is provided. Prepare and encapsulate with solid polymer. Variations on this means utilize CMAC in various physical states including solid, semi-solid or highly sticky forms. Encapsulation can be achieved by embedding or dispersing CMAC in a suitable polymer. Suitable polymers are structurally complete at the temperatures encountered, but release effective concentrations of catalyst in the fuel under conditions in contact with the fuel. If desired, the CMAC can be dispersed in one polymer and the resulting composition can be embedded in the same or different polymer.

  In some cases, the CMAC can be embedded in the polymer by mixing with the polymer powder, melting the polymer while mixing with the CMAC, and solidifying the mixed polymer and CMAC into the desired shape. The solubility characteristics of the polymer in the fuel are selected to define or limit the emission rate of the additive. The additive unit according to the present invention can supply the additive to the fuel in a practically low ppm range.

  The preferred physical form for the CMAC material of the present invention is usually the solid form. Alternatively, the addition unit can be a semi-solid (sticky and not flowing out of its own weight) CMAC that can remain in contact with the flowing fuel as well. CMAC may also be sticky and easy to flow out and deform completely at ambient temperature. If desired, the rate of additive application to the fuel is adjusted by a relatively high viscosity CMAC to maintain very limited contact with the fuel stream, for example using a bypass region.

Also provided are methods for making these products and their use in additional additive systems that cause dissolution of the catalyst addition units.
A number of preferred embodiments of the invention are described below. Here, an equivalent composition is assumed.

  According to the present invention, in an internal combustion engine or other combustion apparatus, the fuel additive addition unit can supply the catalytic metal fuel additive in the fuel simply and effectively so as to be effective even at a low concentration.

  The present invention is for combustion, such as turbines, boilers, combustion furnaces, process heaters, heat recovery units, diesel engines, etc., using carbon and fuels such as fossil fuels, distillates, residues and gaseous fuels. It relates to a novel process that meets the above needs with a solid addition form of a metal-based combustion catalyst for fuel.

  In one aspect, a catalytic metal additive concentrate (referred to herein as CMAC) is provided to form a unit for adding small amounts of platinum and / or cerium by dissolution or diffusion into the fuel. These additive units can easily and effectively provide catalytic metal fuel additives in the fuel so that they are effective even at suitable low concentrations.

  Preferably, the addition unit for adding a small amount of platinum and / or cerium combustion catalyst according to the invention by dissolution or diffusion into the fuel can be produced by encapsulating CMAC with a suitable polymer. CMAC can be in a variety of physical states including solid, semi-solid or highly sticky forms. Encapsulation can be achieved by embedding or dispersing CMAC in a suitable polymer. Suitable polymers are structurally complete at the temperatures encountered, but release effective concentrations of catalyst in the fuel under conditions in contact with the fuel. In some cases, it is useful to simply wrap the CMAC with a polymer film. If desired, the CMAC can be dispersed in one polymer and the resulting composition can be embedded in the same or different polymers.

  In some cases, the CMAC can be embedded in the polymer by mixing with the polymer powder, melting the polymer while mixing with the CMAC, and solidifying the mixed polymer and CMAC into the desired shape. The solubility characteristics of the polymer in the fuel are selected to define or limit the emission rate of the additive. The additive unit according to the present invention can supply the additive to the fuel in a practically low ppm range.

  The preferred physical form for the CMAC material of the present invention is usually the solid form. Alternatively, the addition unit can be a semi-solid (tacky and does not flow out on its own weight) CMAC so that it can remain in contact with the flowing fuel as well. CMAC may also be sticky and easy to flow out and deform completely at ambient temperature. If desired, the rate of additive application to the fuel is adjusted by a relatively high viscosity CMAC to maintain very limited contact with the fuel stream, for example by a bypass region.

  The addition unit supplies the catalytic metal fuel additive in the fuel so that it is effective even at suitable low concentrations. The addition unit is a fuel filter, fuel / water separator or other device made to contact diesel fuel when it is sent to the engine or stored in a fuel tank or other part of the fuel system. For use, it can be provided in any suitable shape, for example, cylindrical, cuboid, spherical, saddle shaped or similar.

  CMAC is usually prepared in solid form and encapsulated with a solid polymer as one means of producing an addition unit for adding small amounts of platinum and / or cerium into the fuel by dissolution or diffusion. As used herein, the term “usually solid” defines that one cubic inch of material substantially retains its shape under its own weight at 20 ° C. for at least 60 minutes, with preferred materials being solid at temperatures of 50 ° C. and above. It means that. Encapsulation is achieved by embedding or dispersing CMAC in a suitable polymer. Suitable polymers are structurally complete at the temperatures encountered, but release effective concentrations of catalyst in the fuel under conditions in contact with the fuel. If desired, the CMAC can be dispersed in one polymer and the resulting composition can be embedded in the same or different polymers.

  In some cases, CMAC can be embedded in the polymer by mixing with the polymer powder to melt the polymer and solidify the mixture into the desired shape. The solubility characteristics of the polymer in the fuel are selected to define or limit the emission rate of the additive. The additive unit according to the present invention can supply the additive to the fuel in a practically low ppm range.

  Alternatively, the addition unit can be a semi-solid (tacky and does not flow out on its own weight) CMAC so that it can remain in contact with the flowing fuel as well. Here, the additive fuel addition rate is adjusted by a relatively high viscosity CMAC to maintain very limited contact with the fuel stream, for example by a bypass region.

  Commonly encountered solvents such as toluene, light mineral oil and kerosene usually have boiling points that are too low for added units containing solid CMAC. Furthermore, they have viscosities that are too low for added units containing semi-solid CMAC. Importantly, they are metal solubility that is too low for good application of solid or semi-solid CMAC. These conventional solvents inhibit the favorable formation of high additive concentrations when they exhibit solubility limits, especially very low with the appropriate platinum compounds. Some of these conventional solvents only have the ability to dissolve only a few tens of percent of the active metal-containing component. This is also true for toluene, which is a particularly good solvent. Simply adding a solid platinum compound to a solid or semi-solid CMAC is unstable and prevents the fuel bone catalyst (FBC) from being carried to the combustor and downstream components at a uniform concentration, resulting in the presence of metal in the fuel ( In particular, fluctuations in the Pt) concentration will result in irregular performance of the additive.

  In addition to these problems, the decomposition temperature of the most soluble form of platinum is too low to use some of the most preferred polymers in the production of solid CMAC. In this regard, platinum COD (also referred to herein as “COD-Pt-diphenyl”), ie, 1,5-cyclooctadiene platinum diphenyl described in Patent Document 8, Patent Document 9, and Patent Document 10, is about Decomposes at 200 ° F. The disclosures of these patents are hereby incorporated by reference. Thus, the dispersion of COD-Pt-diphenyl in a preferred polymer having a melting point of 150-200 ° C. (around 350 ° F.) causes decomposition of the Pt complex and eventually produces metallic platinum. This also results in a very uneven introduction of platinum into the system.

  Not all fuel-soluble platinum materials decompose under these conditions, but the use of them still leaves severe implementation problems. Platinum acetylacetonate has a decomposition temperature above 200 ° C., however, it is difficult to dissolve in any solvent, only about 0.5% even in toluene, and higher aromatic solvents include More difficult to dissolve. It is hardly soluble in aliphatics such as mineral oil. Other suitable platinum compounds exhibit similar problems.

  In one aspect, the present invention provides a stable dispersion of a platinum compound in a cerium (or other catalyst compound such as iron standard) soap solution at a prespecified catalyst ratio (eg, a suitable Pt / Ce ratio). The fuel additive solids are prepared by mixing the dispersion with the fuel soluble polymer under conditions effective to homogenize the dispersion within the polymer and forming the polymer into a pre-specified shape. A method of manufacturing an additive form is provided.

  A stable dispersion of a platinum compound having a pre-specified Pt / Ce ratio in this cerium soap (or other catalyst) solution is obtained by adding the specified platinum compound as a solid or other form to the cerium soap solution and ball milling. Alternatively, it can be produced by grinding in a suitable particle mill and atomizing the solid into small particles that can form a stable dispersion. The soap present in the cerium soap solution disperses the solid platinum compound and prevents agglomeration and the resulting loss of stability. If necessary, additional dispersants can be added. There are many known of these, but one of the most preferred is oleic acid. Others include amphoteric compounds such as oleylimidazoline and the like. If there is a sufficient amount of oleate in the catalyst metal concentrate, such addition is not necessary.

  This procedure results in a stable or semi-stable dispersion without the addition of further steps. However, solvent evaporation reaches at least two additional endpoints: one is to further concentrate the additive package and the other is to bring the viscosity of the resulting solution to a level at which complete dispersion stability is achieved. Is to increase. This also removes the low-boiling solvent that is a source of trouble. Solvent evaporation in combination with a suitable process can result in a usable form of a final additive concentrate containing up to about 50% cerium and 1% platinum (both on a metal basis) in the liquid. . These are very high concentration types of catalytic metals.

  This stable dispersion is also formed by adding the platinum compound as a solution, usually in a light medium such as toluene, in soap, and evaporating the light medium along with the light components in a solvent evaporation process. This results in the precipitation of small particles of solid platinum compound dispersed in the cerium soap solution. These can then be milled or made independent of the required stability.

  In another aspect, the present invention dissolves the platinum and / or cerium component in a low boiling solvent containing an amount of the high boiling solvent sufficient to maintain the fluidity of the component in the absence of the low boiling solvent. Prepare a solution, evaporate the low boiling solvent to prepare a sticky catalytic metal addition concentrate, and mix the fuel soluble polymer and the sticky catalyst solution under conditions effective to homogenize the dispersion within the polymer. And a method of producing a solid additive form of the fuel additive by forming the polymer into a specified shape.

  In this case, mineral oil and other high boiling point aliphatics in which ordinary platinum compounds do not dissolve so much are preferred. The use of more soluble solvent systems is actually detrimental because they promote crystal growth and dissociation of the solid dispersed phase, causing disintegration of the dispersion. The inorganic form of platinum can also be used, but the resulting cake or liquid will release a finer stream of platinum compound than the dissolved form. This is acceptable if the particle size is small enough to prevent settling elsewhere in the system, filter clogging and injection failure. That is, very small, highly pulverized and dispersed platinum oxide particles or similar compounds are conceivable.

  The polymer used to mix the platinum with other catalyst dispersions or the above solution is a polymer that dissolves in the fuel to a sufficient extent to release the additive into the fuel, as in the above cited patent. It is. Olefin-based polymers such as polyethylene, polypropylene, and copolymers of ethylene and propylene can be used with good effect. In embodiments where the solvent is used to dissolve the catalyst component to mix with the polymer in molten form, both the catalyst component and the solvent have the property of surviving in a suitable form. The catalyst is described below. The hydrocarbon type solvent is preferably one that has a high boiling point from the beginning or is free of low boiling point components by evaporation. The preferred boiling point of the solvent is 100 ° C or higher, and preferably 150 ° C or higher. Specific examples are shown below.

The polymer and CMAC can be blended in a suitable proportion to provide the desired release rate when in contact with the fuel under operating conditions. Typically, the CMAC: polymer ratio should be about 3: 1 to about 1: 100, typically about 1: 1 to about 1:10. The metal concentration in the blend is desirably in the range of about 10-600 mg metal per gram of blend, more narrowly about 300-500 mg metal per gram of blend. As an example of a blend suitability test, 1 cm ³ of the blend is placed in 1 liter of fuel and the metal concentration in the fuel is measured. A preferred blend of polymer and CMAC material equilibrates at a level within the desired addition rate given below.

  The blend of polymer and CMAC material is typically shaped and molded by heating, for example at an elevated temperature of about 150 ° C. to about 300 ° C. Preferred polymers melt or soften at temperatures in this range. Typically, the polymer and CMAC mixture is shaped by a suitable molding or other shaping technique, such as compression molding, injection molding, extrusion, and the like. If desired, in some applications, the blend of polymer and CMAC material can be wrapped with a suitable polymer film that allows the fuel to permeate and reach the fuel at a controlled rate. Typical films are ABS, polyalkenes, polyalcohols such as polyvinyl alcohol, polyesters such as polyvinyl acetate, and other polymers that have or can produce similar fuel permeability. Preferred polymers include those to which dipping, coextrusion or simple lamination techniques can be applied.

  When required in a particular process or combustor, a suitable fuel can be treated with a CMAC made in accordance with the present invention. It is a diesel fuel, for example No. Distilled spill fuels including two diesel fuels, gasoline, jet fuels such as Jet A, etc., and “monoalkyl ester based oxygenated fuels”, ie fatty acid esters, preferably triglycerides such as soybean oil, canola oil and / or Alternatively, it can be one or a blend of fuels selected from the group consisting of biologically derived fuels, such as fuels consisting of methyl esters of fatty acids derived from tallow. Other hydrocarbons including liquids and gases, such as natural gas, or fuels derived from gases and / or emulsions can also be used.

  The level of cerium and / or iron catalyst can be added to the fuel at a fairly uniform level that reduces the concentration in the fuel to 0.05 ppm and the level of platinum is as low as 0.0005 ppm.

  The process of the present invention preferably uses a fuel soluble, multi-metallic catalyst comprising fuel soluble platinum and cerium or iron. Cerium or iron typically has a concentration in the fuel of 0.5-25 ppm and a platinum concentration of 0.0005-2 ppm, preferably a cerium and / or iron concentration of 5-10 ppm, such as 7.5 ppm, and platinum Is added in an amount sufficient to achieve a concentration of 0.05-0.5 ppm, for example 0.15 ppm. A preferred ratio of cerium and / or iron: platinum is 75: 1-10: 1. A narrower range is 60: 1-25: 1.

  Fuels treated with the CMAC of the present invention include detergents (eg, 50-300 ppm), lubricants (eg, 25-about 500 ppm), other additives, and suitable fuel-soluble catalytic metal components, such as 0.1-2 ppm. Fuel soluble platinum group metal components such as platinum COD or platinum acetylacetonate and / or 2-20 ppm fuel soluble cerium or iron components such as cerium, cerium octoate, ferrocene, iron oleate, iron octoate and the like Analogs can be included.

  The combination of platinum and iron or cerium is effective at reducing carbon and soot deposits and emissions, even at low concentrations in the fuel, as well as high concentrations of cerium, iron or other metals without platinum. Metal concentrations of several ppm in the combination are as effective as 30-100 ppm of iron and / or cerium used alone. The metal concentration in the fuel achieved using the CMAC formulation of the present invention is sufficient in conventional levels of cerium to cause device fouling due to the high ash burden associated with the high metal concentration in the fuel. Or the problems often encountered when using iron can be avoided.

  Preferred binary and ternary platinum and other catalytic metal combinations coexist with standard additive components for distillate and residual fuels such as pour point reducing agents, antioxidants, corrosion inhibitors, etc. Can be made.

Specific cerium compounds include cerium III acetylacetonate, cerium III naphthenate, and other soaps such as cerium octoate, cerium oleate and stearate, neodecanoic acid, and octanoic acid (2-ethylhexanoic acid). Can be mentioned. Many of the cerium compounds are trivalent compounds such as: Ce (COCR) ₃ where R = hydrocarbon, preferably C ₂ -C ₂₂ and aliphatic, alicyclic, aryl and alkyl Contains aryl. Cerium is preferably at a concentration of (1-15 ppm cerium w / v fuel). This type of compound containing fatty acids is known as soap. Preferably, cerium is supplied as a cerium hydroxy oleate propionate complex (cerium diluted to 40 w% with light mineral oil). A preferred level is below this range, for example, 8 ppm or less.

Specific iron compounds include iron soaps such as ferrocene, iron (III) and iron (II) acetylacetonate, octanoate and stearate (usually commercially available as Fe (III) compounds), iron penta Examples include carbonyl Fe (CO) ₅ , iron naphthenate, and iron torate.

  1,5-cyclooctadiene platinum diphenyl (also referred to as platinum COD, also referred to as “COD-Pt-diphenyl”, described in Patent Document 11, Patent Document 12, Patent Document 13, for example, of some white metal components ) Can be used as a platinum source. Other platinum group catalyst components include commercially available or easily synthesized platinum group metal acetylacetonates, platinum group metal dibenzylidene acetonates, and aliphatic soaps such as tetramine platinum metal complexes, such as tetramine platinum oleate.

  Combustion of fuels treated in accordance with the present invention may have the oil phase emulsified with 1-30% water based on the weight of distilled fuel, residual fuel, aircraft kerosene or the like. In a preferred form, the emulsion is of a pronounced water-in-oil type and preferably contains surfactants, lubricants and / or corrosion inhibitors in addition to the other components described above. A discussion of suitable emulsion forms and additives can be found in US Pat. Additives introduced into the fuel according to the present invention can improve combustion efficiency and reduce particles as an enhanced emission control for diesel engines without the use of oxidation catalysts or particle filters. Also, good carbon combustion in an open flame combustion source reduces carbon deposition on the heat exchanger surface and lowers the soot oxidation temperature in the downstream heat recovery device.

  The present invention will be better understood after reading the above description with reference to the following non-limiting examples. Here, all parts and percentages are based on weight unless otherwise specified.

  This example describes the production of solid CMAC according to the present invention comprising a cerium catalyst component. 200 g of cerium hydroxy oleate propionate complex (cerium diluted to 40 w% with light mineral oil) was mixed with 40 g of heavy mineral oil and charged into a 500 ml vacuum distillation apparatus. The temperature was adjusted by immersing the flask in an oil bath. The oil bath temperature was slowly increased by applying a vacuum with a water ejector device. After about 1 hour, the temperature reached 125 ° C. and the distillation was stopped, and the flask was reweighed, indicating that 50.46 g of solvent had flowed into the receiver from the treated weight. The resulting concentrate was calculated to have a cerium metal concentration of 42 wt%. When the beaker containing the resulting material was heated on a hot plate, the boiling point was 175 ° C. or higher, which was suitable for the process temperature resulting in the type of polymer used in the present invention that slowly releases the fuel additive substrate.

  The solid CMAC produced in Example 1 above was mixed with an ethylene-propylene polymer (melting point 150 ° C.) to a uniform blend at a weight ratio of 50:50 and heated to 175 ° C. in a compression molding machine. The slow release fuel additive insert was formed in a cylindrical form so that it could be inserted into a suitable container for entry into the fuel passage chamber.

  This example describes the production of solid CMAC according to the present invention comprising a catalyst component in which both platinum and cerium are in a weight ratio of cerium: platinum = 50: 1. To 200 g of cerium hydroxy oleate propionate complex (cerium diluted to 40 w% with light mineral oil), 3.2 g of platinum acetylacetonate was added and the material was ball milled overnight to produce platinum acetylacetonate in cerium concentrate. A semi-stable dispersion of was produced. The resulting mixture was mixed with 40 g of heavy mineral oil and charged into a 500 ml vacuum distillation apparatus. The flask was immersed in an oil bath, and the temperature was adjusted and a water ejector was evacuated to slowly raise the oil bath temperature. Processing was completed as in Example 1.

  This example describes the production of solid CMAC according to the present invention comprising a catalyst component in which both platinum and cerium are in a weight ratio of cerium: platinum = 50: 1. In this case, 310 g of 40% cerium concentrate was loaded into a 1 liter ball mill along with magnetic balls. Then 5.0 g of platinum acetylacetonate was added to the mill and the mill was sealed. The mixture was ball milled overnight to produce a semi-stable dispersion of platinum acetylacetonate in cerium concentrate. The resulting mixture slowly precipitated (in 1 or 2 hours) a small amount of solid platinum compound at the bottom of the container. A total of 288.7 g was recovered from the ball mill and transferred to a 500 ml round bottom flask. To this, 3.0 g oleic acid and 68 g heavy mineral oil were added and mixed into the cerium + platinum mixture in the flask. This was vacuum distilled and cooled under a water ejector vacuum to a final temperature of 130 ° C. as in the previous example. Analysis revealed that 76.0 g of light solvent was removed by distillation, leaving 283.7 g of a sticky product containing 0.80% platinum and 40.1% cerium. The final product obtained was found to be completely dissolved in the hydrocarbon solvent. This product was suitable for blending with polymer powder at 175 ° C. to form an additive wafer that provides fuel soluble forms of platinum and cerium under controlled conditions.

  This example repeats the procedure of Example 4, but adds oleic acid as a dispersant instead of heavy mineral oil. The process is essentially the same otherwise.

  This example describes the preparation of another CMAC according to the present invention containing a cerium catalyst component. 200 g of 40% cerium concentrate was mixed with 60 g of heavy mineral oil and charged into a 500 ml vacuum distillation apparatus. The temperature was adjusted by immersing the flask in an oil bath. A vacuum was applied with a water ejector and the oil bath temperature was slowly raised. After 90 minutes, the temperature reached 160 ° C. and the distillation was stopped and the flask was reweighed and it was found that 54.84 g of solvent had flowed into the receiver from the treated weight. The resulting concentrate was calculated to have a cerium metal concentration of 39 wt%. The results of this method were suitable for processing with a high melting point polymer at 175 ° C. and had a lower viscosity than Example 1, making it easier to process with polymer powder.

  This example describes the production of solid CMAC according to the present invention comprising a catalyst component in which both platinum and cerium are in a weight ratio of cerium: platinum = 50: 1. In this case, a platinum compound solution in a suitable solvent is added to the distillation apparatus (as in Example 4) to the mixture of cerium catalyst material and solvent. In this case, in particular, a 4.7% solution of 80 g of platinum plus 3100-SC, COD-Pt-diphenyl in toluene was added. The final process temperature was kept below 100 ° C. to avoid decomposition to platinum metal in the matrix.

  This example describes the production of semi-solid CMAC according to the present invention containing a cerium catalyst component, as in Example 7, but using platinum acetylacetonate instead of COD-Pt-diphenyl and the temperature Maintained below 250 ° C.

  This example repeats the procedure of Example 7, but in this case the platinum: cerium ratio was 1:15, and a proportional increase in the amount of platinum compound in the composition was obtained.

  This example describes the preparation of another CMAC according to the present invention containing a cerium catalyst component. 200 g of 40% cerium concentrate was mixed with 100 g of heavy mineral oil and charged into a 500 ml vacuum distillation apparatus. The temperature was adjusted by immersing the flask in an oil bath. A vacuum was applied with a water ejector and the oil bath temperature was slowly raised. After 90 minutes, the temperature reached 160 ° C. and the distillation was stopped and the flask was reweighed and it was found that 55 g of solvent had flowed into the receiver from the treated weight. The resulting concentrate was calculated to have a cerium metal concentration of 32 wt%. The results of this method were suitable for processing with a high melting point polymer at 175 ° C. and had a lower viscosity than Example 1, making it easier to process with polymer powder.

  The above description is intended to enable the skilled artisan to practice the invention. It is not intended to detail possible modifications and variations that would become apparent to a skilled artisan upon reading this description. However, such modifications and variations are intended to be included within the scope of the present invention as defined in the foregoing description and the appended claims. The claims are meant to encompass elements and any arrangement or sequence of steps that meet the intended purpose of the invention, unless expressly stated to the contrary.

USP 4,891,050 USP 5,034,020 USP 5,266,093 USP 4,891,050 USP 5,034,020 USP 5,266,093 USP 5,743,922

  The present invention is for combustion, such as turbines, boilers, combustion furnaces, process heaters, heat recovery units, diesel engines, etc., using carbon and fuels such as fossil fuels, distillates, residues and gaseous fuels. It is useful for adding to a fuel before combustion as a solid addition form of a metal-based combustion catalyst for fuel.

Claims (16)

  (A) a catalyst metal addition concentrate comprising a fuel-soluble platinum and / or cerium component which is stable at a temperature of 100 ° C. or more and is uniformly dispersed in an organic carrier in an amount capable of maintaining a solid in a normal state (b) A high temperature stable platinum and / or cerium fuel additive addition unit encapsulated with a solid polymer as a leaching control component.   The high temperature stable platinum and / or cerium fuel additive addition unit according to claim 1, wherein the catalytic metal addition concentrate is embedded in the polymer.   3. The high temperature stable platinum and / or cerium fuel additive addition unit according to claim 1 or 2, wherein the catalyst metal addition concentrate is uniformly dispersed in the polymer.   4. A high temperature stable platinum and / or cerium fuel additive addition unit according to any one of claims 1, 2 or 3, wherein the catalyst metal addition concentrate comprises platinum acetylacetonate.   The high-temperature stable platinum and / or cerium fuel additive addition unit according to any one of claims 1, 2, 3 or 4, wherein the catalyst metal addition concentrate comprises cerium soap.   Preparation of a stable dispersion of platinum component in a cerium soap solution at a pre-specified Pt / Ce ratio, and concentration of sticky catalytic metal consisting of fuel-soluble platinum and / or cerium component stable at a temperature of 100 ° C. A method for producing a solid form of fuel additive in which an object is enclosed with a leaching control polymer.   The method of claim 6 wherein the sticky catalytic metal addition concentrate is encapsulated by embedding in a leaching control polymer.   In addition, a dispersion of platinum component and cerium soap is mixed with a leaching control polymer under conditions effective to make the dispersion in the polymer uniform, and the resulting polymer mixture is formed into pre-specified shape addition units. The method of claim 6 including the steps of:   The method of claim 7 further comprising the step of embedding the additive unit in a leaching control polymer.   Prepare a solution in which platinum and / or cerium components are dissolved in a low-boiling solvent containing a sufficient amount of high-boiling solvent to maintain the fluidity of the components in the absence of the low-boiling solvent, and evaporate the low-boiling solvent. To prepare a sticky catalytic metal-added concentrate comprising a fuel-soluble platinum and / or cerium component that is stable at a temperature of 100 ° C. or higher, and from a fuel-soluble platinum and / or cerium component that is stable at a temperature of 100 ° C. or higher. A method for producing a solid form of fuel additive by encapsulating a sticky catalytic metal additive concentrate with a leaching control polymer.   A solid addition form of the catalyst according to any one of claims 1-10 is obtained, and the solid addition form of the catalyst is brought into contact with the fuel to partially dissolve the polymer and introduce the catalyst into the fuel before combustion. A method of using the fuel additive solid addition form.   A method of forming a catalytic metal addition concentrate comprising forming a mixture of catalytic metal soap and solvent and then removing the low boiling solvent.   13. The method of claim 12, wherein the high boiling point solvent is added before removing the low boiling point solvent.   The method of claim 12, wherein the catalytic metal soap comprises cerium soap.   The method of claim 14, wherein the catalytic metal further comprises platinum acetylacetonate.   The method of claim 14, wherein the catalytic metal further comprises COD-Pt-diphenyl.