JP2008514766A - Direct combustion type burner, additive for liquid or liquefied hydrocarbon fueled to open flame, and method for producing the same - Google Patents

Abstract

  The present invention relates to the field of fuel additives, and in particular to additives for hydrocarbons fueled to burners and flames to increase fuel efficiency and / or to reduce undesirable emissions such as pollutants. is there. The fuel additive of the present invention includes a phosphorus-containing parent solution. The phosphorus salt is at least partially dispersed and / or dissolved in water or other suitable solvent to form a phosphorus-containing parent solution that serves as a base for the fuel additive. The phosphorus-containing parent solution is added to or mixed with the dispersion fluid.

Description

  This patent application claims priority to US Provisional Patent Application No. 60 / 613,699, filed Sep. 28, 2004. The entire text of this provisional patent application is incorporated herein by reference.

  The present invention relates to the field of fuel additives, particularly for hydrocarbons fueled in burners and flames to increase fuel efficiency and / or to reduce undesirable emissions such as pollutants. It relates to the agent.

  Many hydrocarbon fuels have been used, each with its own advantages and disadvantages. Examples of such fuels are diesel, kerosene, heavy cuts, and bunker heavy oil. In order to increase the combustion efficiency of this type of fuel, chemical compounds have been used as a combustion aid. Many of these additives contained metallic elements such as magnesium, iron, copper, cerium, calcium, and barium. Each of these elements has advantages and disadvantages in certain applications. Disadvantages of certain iron compounds are limited solubility in fuels, toxicity, and expensive as additives. Also, interaction with sulfur and sulfur precipitates may be formed, which is undesirable.

  Also, in addition to the purpose of improving combustion efficiency, the reduction of heavy fuel soot emissions is a concern, particularly in direct fired applications. The industry has been unable to make substantial progress in the development of fuel additives to reduce soot and particulate emissions in these areas.

Combustion additives including combustion catalysts to reduce soot and particulate emissions from open flame burners and other directly burned applications would be advantageous. For diesel fuels and heavy fuels used in such applications, fuel additives that increase combustion efficiency and / or reduce pollutants will be particularly advantageous. It would also be advantageous to reduce soot, particulates, and nitrogen emissions from fuel applications. In addition to the reduction of NO _x, reduction or reduction of HCN emissions it has been highly desirable.

  It would be desirable to have an additive that burns cleanly without producing precipitates during the combustion process.

  The present invention includes fuel additives and methods of using the additives associated with hydrocarbon fuels.

The fuel additive of the present invention comprises a parent solution containing phosphorus, including [Y] _x H ₂ PO ₄ , [Y] _{x +} HPO ₄ , where [Y] is a cation. Yes. Y is two salt compounds and does not need to be the same cation. The cation portion of the salt component may be any cation, with potassium being the preferred cation. In this case, preferred components would be KH ₂ PO ₄ , K ₂ HPO ₄ . These salts are at least partially dispersed and / or dissolved in water or other suitable solvent to create a phosphorus-containing parent solution. Advantageously, this fuel additive embodiment is an ammonia-free solution. One preferred embodiment adds these ingredients in the presence of water to make a phosphorus-containing parent solution as an aqueous parent solution. Water acts as a solvent. Other preferred parent solution solvents include alcohol. Another preferred cation group would be an alkali metal or a Group 1A element. NH ₄ used as Y may form a fuel additive that enhances fuel performance, but it may be preferable to avoid ammonia and avoid ammonia at all.

The phosphorus-containing parent solution is added to or mixed with the dispersion fluid. A dispersion fluid is a fluid that can hold salt in the dispersion fluid at least in a partially dispersed state and that can be miscible with the hydrocarbon fuel or held in solution. In a preferred embodiment, most of the solvent is removed from the phosphorus-containing parent solution in the dispersion fluid by thermal means to create a fuel additive. This fuel additive can be added to contact the fuel in a direct combustion burner or open flame and enhance combustion when burned. Enhanced combustion means that fuel efficiency is increased when compared to fuel without added fuel additives, or the amount of pollutants in the exhaust gas resulting from combustion is reduced, or a combination of these effects. means. Typical pollutants can include NO _x , HCN, SO ₂ particulate matter, carbon monoxide, and other known pollutants resulting from combustion of hydrocarbon fuels. It is noted that various regions have focused on minimizing specific pollutants based on atmospheric characteristics. Contaminants targeted, such as NO _x and HCN, or it is convenient to weight loss combination of contaminants. Instead, increasing fuel efficiency reduces the total amount of contaminants and is economically advantageous.

Another preferred embodiment of the phosphorous-containing parent solution comprises adding [NH ₄ ] ₂ HPO ₄ to [Y] _x H ₂ PO ₄ , [Y] _{x +} HPO ₄ and water. Yet another embodiment is that the solution contains [Y] _x H ₂ PO ₄ , [Y] _{x +} HPO ₄ , [NH ₄ ] ₂ HPO ₄ , NH ₄ C ₂ H ₃ O ₂ and water. Including adding NH ₄ C ₂ H ₃ O ₂ , where the C ₂ H ₃ O ₂ ^— ion is an acetate group. When producing a fuel additive using an ammonium compound, the ammonium compound is defined as a compound containing NH _x groups, and the nitrogen in the solution is essentially all in the form of ammonium ions. There is only a negligible amount of free ammonia in the solution. In a preferred embodiment, the solution is at a pH between about 6.0 and 8.0.

Another preferred embodiment of the phosphorus-containing parent solution comprises adding [Y] _x PO ₄ to [Y] _x H ₂ PO ₄ and [Y] _{x +} HPO ₄ .

Although orthophosphoric acid has been described, it is also referred to as phosphoric acid, which includes pyrophosphoric acid, an orthophosphoric acid condensation analog. The difference is that PO ₄ ³⁻ becomes P ₂ O ₇ ²⁻ or other condensed phosphoric acid through the process of condensing orthophosphoric acid. Therefore, [Y] _x H ₂ PO ₄ and [Y] _{x +} HPO ₄ are precursors to pyrophosphate. Thus, the use of pyrophosphate and other condensed forms is included in the definition of the orthophosphoric acid form.

  The phosphorus-containing parent solution of one embodiment of the present invention can be used in any type of environment, either a hydrophilic or a hydrophobic environment. In the case of a hydrophobic environment, it may be necessary to select one or more carrier fluids in view of proper dispersion. Also included in preferred embodiments are dispersants used with carrier fluids to make fuel additives. For liquid hydrocarbon fuel applications, preferably, the at least one carrier fluid can be a fluid having at least some hydrophilic properties, which fluid is miscible with the fuel and together with the dispersant is a compatibilizer. Acts as

The fuel additive of the present invention enhances combustion such that more complete combustion is achieved and combustion is promoted to CO ₂ and H ₂ O when compared to fuel combustion without the fuel additive. Useful for. The result is a product of incomplete combustion, as well as a reduction in NO _x and SO ₂ and hence an increase in fuel efficiency.

Fuel additives are used so that a sufficient amount of fuel additive is added to the fuel to increase fuel efficiency or reduce pollutants. The terms “enhanced” and “enhanced combustion” refer to any of these effects. Examples of contaminants reduction is the reduction of the NO _x and HCN in the exhaust gas resulting from the direct combustion burner or open flame. Conveniently, these two effects are considered through the addition of the fuel additive of the present invention. A preferred embodiment includes adding between about 50 and 150 ppm phosphorus to the fuel through the addition of fuel additives. Increasing phosphorus is equally effective. It is noted that a very cost effective solution is produced with low weight percent phosphorus. Another preferred target is about 1 ppm to 150 ppm phosphorus. Practical test results were generated from a low concentration of phosphorus at only 0.25 ppm.

  The present invention relates to a method for enhancing the fuel performance of a hydrocarbon fuel in a combustion system, the step of supplying to the hydrocarbon fuel an amount of the above-mentioned fuel additive effective to enhance the fuel performance, and the hydrocarbon fuel. Including the step of combusting the fuel with a fuel additive. The combustion system can be any means known to those having ordinary skill in the industry for hydrocarbon combustion. The combustion system can include one or more direct combustion burners or open flames. In a preferred embodiment, the method is used with a liquid or liquefied hydrocarbon fuel. The result of adding an additive to a hydrocarbon fuel is an enhanced fuel containing a substantial amount of hydrocarbon fuel suitable for combustion and an amount of fuel additive capable of enhancing combustion. Preferably, the enhanced fuel contains an amount of phosphorus that can reduce emissions when combusting the enhanced fuel as compared to combustion of a hydrocarbon fuel that does not contain a fuel additive. More preferably, the enhanced fuel contains between about 1 and 150 ppm by weight phosphorus.

An alternative embodiment of the present invention is a method for enhancing the fuel performance of a hydrocarbon fuel in a combustion system, the step of adding a chemical additive composition to the hydrocarbon fuel in an amount effective to enhance fuel performance. Including methods. The chemical additive composition is made by (i) mixing the reactive NH ₂ group source with one of the following in an aqueous medium to make an intermediate solution:
(A) Raise the pH of the intermediate solution to more than about 12 to produce aqueous ammonia / alkali metal hydroxide, or (b) lower the pH of the intermediate solution to about 0 to make it acidic Phosphate source for making ammonium mixtures.
The next step is to combine the intermediate solution of step (ia) with the phosphate source in a ratio sufficient to create a highly exothermic reaction, or the intermediate solution of step (ib) and the hydroxylation. Including combining objects. This results in reactive NH ₂ groups being included in the solution when forming the chemically added composition. This chemically added composition is added to the hydrocarbon fuel.

  The parent solution or chemical additive composition of the present invention can be added to or include a combustion fuel. Again, it would be advantageous to include a dispersant that promotes dispersion in the hydrocarbon-based fuel. Typical fuels are kerosene, diesel fuel and residual fuel.

  A substantial amount of fuel suitable for combustion is combined with a phosphorus-containing parent solution or chemical additive composition in an amount sufficient to reduce emissions or increase efficiency when burning the enhanced fuel. Sometimes enhanced fuel is created. In some circumstances, the dispersion fluid is a large amount of target fluid, i.e. fluid containing the desired fuel.

The composition of phosphoric acid, alkali metal hydroxide, and reactive NH ₂ based source was investigated in US Pat. No. 5,540,788 for conversion surface. The disclosure of this patent is incorporated herein by reference. The present invention involves the use of a conversion surface composition as a fuel additive. In one embodiment, the fuel additive is a chemical additive composition for enhancing a hydrocarbon fuel, the chemical additive composition comprising the composition disclosed in US Pat. No. 5,540,788. . This embodiment is unique in terms of using a reactive NH ₂ source, which must be advantageous under certain circumstances. Although chemical compositions containing reactive NH ₂ groups have certain advantages, it may result in the presence of free ammonia. Various other embodiments of the fuel additive of the present invention avoid the production of free ammonia and the problems associated therewith.

The fuel additive of the present invention is believed to accomplish gas phase conversion of hydrocarbon fuels to achieve more complete combustion and produce CO ₂ and H ₂ O in the process. Preferably, the fuel additive is supplied as a dispersion in a dispersion fluid. Preferably, the manufacturing process includes making an aqueous parent solution that is emulsified and subsequently added to the base oil. Dispersion can be facilitated by the use of emulsifiers and dispersants. In a preferred embodiment, a dispersant having a total base number of 30 to 160 is used on an oil free basis. As a result of performing the test using the infrared technology and other test technologies, it was confirmed that the hydrocarbon fuel containing the fuel additive of the present invention is combusted and CO generated from the exhaust gas is reduced.

U.S. Pat. No. 5,540,788 (Defalco patent) teaches a method of creating an iron-phosphorus surface by forming a conversion surface on an iron substrate by feeding a phosphating compound into a lubricating fluid. ing. The present invention also includes the use of a Defalco composition as a fuel additive for introduction into a burner or open flame. The composition includes a phosphate source, an alkali metal hydroxide, and a reactive NH ₂ group source. In particular, the reactive NH ₂ Motogen as a result of advanced exothermic reaction described in Defaruko patent, to produce a reactive NH ₂ group. Tests suggest that similar compounds that act as reactive NH ₂ group sources in the above reactions do not produce reactive NH ₂ groups under different physical conditions. The reason is that these compounds follow different reaction pathways. This special chemistry comes from the highly exothermic reaction described in the Defalco patent. Also, the high pH physical conditions stem from the production of free ammonia.

  Both the novel compositions disclosed herein and the previously described Defalco compositions can be used to produce enhanced fuel performance.

  The present invention involves the use of fuel additives in direct combustion burners and open flames. This is particularly valuable for burners that use heavy oil, such as bunker fuel, including bunker C heavy oil. Use with a burner or flame appears to provide combustion benefits that allow for the reduction of particulates and other emissions. The method of the present invention is effective at the high temperatures produced as part of the combustion process because the fuel additive is included or present in the flame with the fuel. The fuel additive acts as a catalyst to enhance combustion.

An example of a preferred formulation of the present invention includes the following ratios: 1.597 moles KH ₂ PO ₄ , 0.693 moles K ₂ HPO ₄ , 0.315 moles [NH ₄ ] ₂ HPO ₄ and water. The pH of the solution can be controlled by manipulating the ratio of these components. By manipulating the ratio of the resulting H ₂ PO ₄ ⁻ , HPO ₄ ²⁻ ions, solutions can be made in the preferred pH range of about 6.0 to about 8.0.

In a preferred embodiment, KH ₂ PO ₄ , K ₂ HPO ₄ , [NH ₄ ] ₂ HPO ₄ , and water are added to a phosphorus-containing parent solution, which is added to a dispersion fluid, such as a refined oil dispersion fluid, and Mixed with dispersant. Exemplary dispersants include polyalkenyl succinimides such as Texaco TFA 4690C, Oronite ODA 78012, Ethyl Hitec 646, and the like. It must also be advantageous to include certain carrier fluids. Exemplary carrier fluids include polyoxypropylene monools, diols and polyols, polyoxybutylene monools, diols and polyols, particularly Bayer Actelar ND17. The phosphorus-containing parent solution is added at about 10% by weight of the refined oil dispersion fluid. This is heated to release a significant amount of solvent, in this case water. The mixture can be described as a colloid in this respect. When the resulting solution is mixed with fuel, an effective amount of phosphorus in the solution can be diluted. An example of a preferred embodiment is 0.3% by weight phosphorus in solution. Upon fuel addition, the phosphorus content can range from 5 to 100 ppb and is still effective. Preferably 1-250 ppm of phosphorus is used in the fuel. Larger amounts are also effective. More preferably, the phosphorus concentration is 1 to 150 ppm by weight in the fuel containing the fuel additive.

  An example of an alternative embodiment of a phosphorus-containing parent solution for use in fuel comprises mixing about 2.6 moles (M) of orthophosphate with alkali metal and ammonium cations, and the resulting aqueous parent solution Is pH 7 at ambient temperature. A modest amount of this aqueous parent solution is suspended in a mixture of refined oil dispersion fluid and dispersant and diluted so that most of the water in the aqueous parent solution is removed by heating to a phosphorous concentration of about 0.3% by weight. Is done. This mixture is further diluted and used as an additive to the fuel. The dilution is preferably performed with a similar refined oil dispersion fluid. Group II base oils are preferred. Other preferred dispersion fluids are light hydrocarbons, gasoline, polygas, kerosene, diesel, naphtha gas oil, group I, III, IV, V and VI base oils as defined by API, aromatic oils, polybutene, polyglycerol, and more Includes heavy oil, or a combination thereof. When added to the fuel, the aqueous parent solution produced in this manner functions to reduce pollutant molecule emissions under normal operating conditions. An example of an alternative embodiment includes using phosphoric acid, potassium hydroxide, ammonium hydroxide in water. Acetic acid may also be added. The amount of ingredients can be adjusted to reach the desired pH.

1. A phosphoric acid / acetic acid solution [H ₃ PO ₄ / HOAc solution] is prepared. In this operation, the H ₃ PO ₄ / HOAc solution is about 90 mol% H ₃ PO ₄ and 10 mol% HOAc.
2. Prepare deionized water for the reaction.
3.2,736.39 pounds of potassium hydroxide are added to the water.
4). To this aqueous solution is added 1,315.14 pounds of ammonium hydroxide (29%).
5. An H ₃ PO ₄ / HOAc solution is added to the resulting solution to react.
6). After the reaction, the pH is adjusted to about 7.0 using acetic acid. The product obtained in this reaction is useful as a chemical additive and enhances hydrocarbon fuel.

Laboratory tests using a fuel additive consisting of KH ₂ PO ₄ , K ₂ HPO ₄ , [NH ₄ ] ₂ HPO _{4 in} a refined oil dispersion fluid as a diesel fuel additive greatly improves fuel efficiency . With this formulation, it was evaluated that sodium can also be used as a cation. Group IA metals are also preferred cations. Factors related to cation selection include commercial cost and corrosion resistance.

The fuel additive according to Example 2 that used in combination with a low sulfur diesel fuel, when compared to diesel fuel without the addition of the fuel additive, reduced CO emissions in the exhaust gas 74%, by SO ₂ 34% decrease and 55% decrease in fine particles.

The above fuel additive that used in combination with natural gas, when compared to the combustion of natural gas without the addition of the fuel additive, the generation of carbon monoxide is reduced 87%, NO _x is reduced by 18%.

Ingredients Pound unit weight ratio phosphoric acid 2,583 0.25
Potassium hydroxide 2,736 0.26
Ammonium hydroxide 1,315 0.13
Acetic acid 672 0.06
Deionized water 3,105 0.30
Total phosphorus-containing parent solution 10,411 1.00

Ingredient Input Pound Unit Weight Ratio Star 4 Base Oil 8,544 0.79
Kerosene 1,282 0.12
ODA78012 205 0.02
Hitec 646 205 0.02
Actclear ND17 85 0.01
Phosphorus-containing parent solution (Example 5) 273 0.03
Total 10,748 1.00

  This is further diluted in the base oil to adjust the desired rich phosphorus content in the fuel additive. To make the fuel additive, the solvent is removed from the solution. In this case, the solvent is water and dehydration is performed by heating.

An alternative embodiment includes using [NH ₄ ] H ₂ PO ₄ , [NH ₄ ] ₂ HPO ₄ and water. In a preferred embodiment, the solvent is one that is defined by the solubility or dispersibility of the salt in the solvent and the volatility of the solvent. For example, the salt is preferably dispersed throughout the solvent, and the solvent can boil off the solvent from the solution and is preferably recovered for reuse without affecting the resulting product. It is volatile so that

The present invention has shown and described only a few of the forms of the invention. It will be apparent to those skilled in the art that various modifications can be made without departing from the scope of the present invention. For example, the introduction of salt into the fuel or dispersion fluid can be performed by high speed shear mixing without the creation of an intermediate solution and subsequent heat removal of the solvent. As for the salt, [Y] _x H ₂ PO ₄ , [Y] _{x +} HPO ₄ are [Y] _x [H ₂ PO ₄ ] _z , [Y] _{x +} [HPO ₄ ] _z (where, x And z are variable integers).

Claims (14)

A fuel additive comprising a salt mixture and a dispersion fluid, wherein the salt mixture comprises:
(A) [Y] _x H ₂ PO ₄ , and (b) [Y] _{x +} HPO ₄ , where [Y] is a cation, and the dispersion fluid at least partially dispersed the salt The fuel additive can be added in contact with the fuel in the direct combustion burner or open flame and burned to enhance combustion and be enhanced. Combustion is a fuel additive that can be measured by improving fuel efficiency or reducing the amount of pollutants in the exhaust gas resulting from combustion of fuel and fuel additive. The fuel additive according to claim 1, further comprising [NH ₄ ] ₂ HPO ₄ . The fuel additive according to claim 2, further comprising NH ₄ C ₂ H ₃ O ₂ , wherein C ₂ H ₃ O ₂ is an acetate group.   The fuel additive according to claim 1, wherein the pH of the solution is between about 6.0 and 8.0. A method for enhancing the fuel performance of a hydrocarbon fuel in a combustion system including a direct combustion burner or an open flame, wherein an amount of the fuel additive effective to enhance the fuel performance relative to the direct combustion burner or the open flame And burning the hydrocarbon fuel with the fuel additive, the fuel additive comprising:
(A) [Y] _x H ₂ PO ₄ , and (b) [Y] _{x +} HPO ₄ , where [Y] is a cation, and the dispersion fluid at least partially dispersed the salt The fuel additive can be added in contact with the fuel in the direct combustion burner or open flame and burned to enhance combustion and be enhanced. Combustion is a method that can be measured by improving fuel efficiency or reducing the amount of pollutants in the exhaust gas resulting from combustion of fuel and fuel additives. The method of claim 5, wherein the fuel additive further comprises [NH ₄ ] ₂ HPO ₄ . Fuel _additive, a method of increasing the _{NH 4 C 2 H 3 O 2} ( _wherein, C ₂ H 3 _{O 2} is acetate group) fuel performance of claim 5 further comprising a.   The method for enhancing fuel performance according to claim 5, wherein the hydrocarbon fuel is a liquid hydrocarbon fuel. An enhanced fuel comprising: (a) a substantial amount of hydrocarbon fuel suitable for combustion; and (b) an amount of fuel additive according to claim 1 capable of enhancing combustion.   The enhanced fuel of claim 9, wherein an amount of phosphorus between about 1 and 150 ppm by weight is present in the hydrocarbon fuel.   10. The boost of claim 9, wherein the amount of fuel additive is an amount capable of reducing emissions when burning the enhanced fuel as compared to combustion of a hydrocarbon fuel containing no fuel additive. Fuel. A method of creating an enhanced hydrocarbon fuel for use in a combustion system comprising:
(A) adding an effective amount of a chemical additive composition to a hydrocarbon fuel to enhance fuel performance, the chemical additive composition comprising a phosphate source, an alkali metal hydroxide A reaction product obtained by mixing a product, ammonium hydroxide, and water.   13. The method of claim 12, wherein the chemically added composition makes an enhanced hydrocarbon fuel further comprising acetic acid. A method of creating a fuel additive for enhancing combustion of hydrocarbon fuel, comprising:
(A) [Y] _x H ₂ PO ₄ and [Y] _{x +} HPO ₄ (where [Y] is a cation) are mixed in a solvent, and the salt is at least partially dispersed in the solvent; Creating a parent solution containing phosphorus;
(B) mixing the phosphorus-containing parent solution with the dispersion fluid such that the phosphorus-containing parent solution is generally dispersed in the dispersion fluid;
(C) In order to create a fuel additive that can be added to a direct combustion burner or open flame in the presence of a hydrocarbon fuel and enhance combustion when burned, Removing a substantial portion of the solvent from the mixture.