RU2471858C2 - Method of increasing rate and completeness of fuel oxidation in combustion systems - Google Patents

Abstract

FIELD: chemistry.SUBSTANCE: method of intensifying fuel oxidation in combustion systems involves increasing the rate of oxidation, raising oxidation temperature and/or increasing the rate of increase of oxidation temperature. The method involves adding a catalytic additive to an oxidant and/or fuel before or during the fuel oxidation process, where the catalytic additive is a solid substance, its solution or suspension, or a liquid substance or its emulsion, in form of a separate catalytic substance or a catalytic mixture of substances. The catalytic substance or at least one of the substances in the catalytic mixture contains at least one functional carbonyl group and has in the infrared spectrum at least one intense absorption band in the region from 1550 to 1850 cm. Said catalytic substance or at least one substance in the catalytic mixture is selected from: monocarboxylic acids and anhydrides thereof; dicarboxylic acids and anhydrides thereof; carboxylic acid salts; dicarboxylic acid salts; carboxylic acid amides; dicarboxylic acid amides; carboxylic acid anilides; dicarboxylic acid anilides; carboxylic acid esters; dicarboxylic acid monoesters or diesters; carboxylic acid imides; dicarboxylic acid imides; carbonic acid diamide; acyclic and cyclic carbonic acid esters; urethanes; aminocarboxylic acids whose molecules contain amino groups (NHgroups) and carboxyl groups (COOH group); peptides and proteins whose molecules are built from a-amino acid residues linked by peptide (amide) bonds C(O)NH. The catalytic additive is added in amount of 0.0000001-01 wt %. The fuel used is solid, gaseous or liquid fuel selected from AI-92 petrol, diesel or masout.EFFECT: faster fuel oxidation, high oxidation temperature, higher rate of increase of oxidation temperature, higher enthalpy of combustion products, more complete fuel combustion, fewer solid deposits on engine parts, reduced harmful emissions with exhaust gases, reduced fuel combustion.5 cl, 3 tbl, 2 dwg, 9 ex

Description

The invention relates to oxidation technologies and can be used in solid, liquid and gaseous fuel combustion systems used in a wide range of industries (firing, smelting, pyrometallurgy, etc.), utilities (waste incineration, boiler, etc. ), energy (various types of internal combustion engines, thermal power plants, etc.), etc. for getting work and / or getting energy.

Oxidation, in the narrow sense of the word, is the combination of a substance with oxygen. In a broader sense, any chemical reaction, the essence of which is the removal of electrons from atoms or ions. The most important oxidizing agents include oxygen, ozone, hydrogen peroxide, chlorine, fluorine, potassium permanganate and others. The oxidation process is one of the most common in nature and technology. Such, for example, combustion of all types of fuel, corrosion of metals.

Combustion can occur in open flame systems (e.g. coal, gas and oil boilers, as well as furnaces) and closed flame (e.g. gasoline, diesel and gas turbine internal combustion engines).

Currently, a large arsenal of methods is known to intensify the process of fuel oxidation. For this, physical, chemical, and constructive methods of influencing the kinetics of the process are used to accelerate the burnup or decomposition of fuel particles.

It is known that metal-containing fuel additives catalyze the burning of carbon and thus reduce emissions in the form of solid particles either by inhibiting the agglomeration of solid particles (alkali metals), accelerate the oxidation of carbon at maximum combustion temperatures by increasing the concentration of hydroxyl radicals (alkaline earth metals), or by increasing the rate of catalytic oxidation by lowering the light-off temperature of solid particles (transition metals).

The prior art method of improving combustion and slag according to the patent of the Russian Federation No. 2304610 (publ. 08/20/2007), which includes introducing a catalytic additive into the fuel combustion system, the additive being introduced into the fuel before burning.

The known method has universality in fuel - solid, liquid and gaseous and in the state of aggregation of the catalytic additive, but has its drawbacks. The additive is a multicomponent mixture of a manganese-containing organometallic compound, an alkali metal compound and a magnesium-containing compound, which can be separately introduced into the process by themselves, but the presence of each of them is mandatory. In addition, the substances used as additives have their own narrowly targeted effects: a mixed metal catalyst - reducing the emission of solid carbon particles due to the catalytic burning of carbon; magnesium-containing compound - improving the properties of slag formed during the combustion of fuel. There is reasonable reason to believe that the additives have an insufficient effect on the combustion process, as the introduction of additional additives that improve combustion, provided that they do not adversely affect the amount and formation of slag, which characterizes the method as not sufficiently effective. In addition, the additive is introduced exclusively into the fuel before the start of the combustion process and does not ensure the completeness of its combustion (oxidation), which causes operational problems.

A known method of catalyzing the combustion of fuel according to the patent of the Russian Federation No. 2386078 (publ. 04/10/2010), comprising introducing additives into the fuel combustion system, the fuel and the additive being introduced simultaneously or separately.

The method allows to reduce the pollution created by emissions from the combustion chamber, and provides a more efficient and cleaner combustion compared to known solutions. The method allows to improve the thermal efficiency of the fuel combustion system by maintaining the flame temperature of the combustion system and reducing excess air levels, as well as reducing the amount of soot that is deposited on the internal surfaces of the fuel combustion system.

The catalytic additive contains one or more inorganic salts or one or more compounds containing a metal, but if only one compound is used, the additive must necessarily contain a salt of platinum or rhodium, which are very expensive metals. In addition, only platinum allows when implementing the method in internal combustion engines to increase the combustion rate, as a result of which the flame is maintained and the power is increased. Therefore, not all additive substances have a multidirectional effect.

Additive substances, decomposing into elemental form in the oxidation zone, create traditional combustion elements that catalyze reactions with oxygen and with molecules and radicals formed as intermediaries in the combustion process. An increase in the concentration of oxygen atoms and the formation of free radicals increases the burning rate and, accordingly, the efficiency of the process during the residence time of the additive in the oxidation zone.

The disadvantages of this method include the restriction on the state of aggregation of the additive — aerosol, the need for preliminary preparation and ensuring its stability, the need to create an aerosol delivery system that requires sophisticated hardware design for supplying an aerosol under pressure.

With all its advantages, the known method does not provide complete combustion of fuel, because unburned carbon takes place and is deposited in the fuel combustion system. The presence of unburned carbon is an indication of combustion inefficiency.

There is a method of improving the operation of combustion plants according to patent No. 2366690 (published on September 10, 2009), adopted as a prototype, comprising introducing additives into the fuel combustion system, the additive being introduced into the fuel, into the furnace, or into the combustion plant after the furnace.

The method is universal in fuel and in the aggregate state of the additive, but it uses multicomponent catalytic additives (an alloy comprising at least two metals, each alloy component has a narrow direction of action), preferably, multilevel entry into both the fuel and the furnace is carried out at predetermined entry points, the selection of which affects the achievement of the functional result of the method. There is a need for additional introduction of a combustion catalyst. In the case of using the method with respect to liquid fuel, in order to dissolve the alloy in the fuel, it is treated with an organic compound using sophisticated equipment during processing. The importance of determining the combustion conditions makes the known method very dependent on the permanently changing (when using the method in practice) properties of the fuel used, the composition of the air / fuel mixture and other factors. The mismatch between the calculated data and the conditions in the fuel oxidation system will lead to irreproducibility of its results, including not providing the required completeness of fuel combustion.

The objective of the present invention is to provide an effective way to increase the rate and completeness of oxidation of fuel, universal in fuel (solid, liquid or gaseous), which will result in an increase in the enthalpy of the combustion products (upon receipt of work), density of the radiant flux (upon receipt of energy), oxidation rate, temperature and rate of temperature rise during the period of fuel oxidation due to the use of a catalytic additive, universal in place, the moment it is added to the fuel oxidation system and atnomu state, while simplifying the method and its hardware design across the entire spectrum of applications.

In addition, the applicant believes that the catalytic additive used according to the present invention contributes to a more complete combustion of the fuel in the oxidation volume, and not on the surfaces of the specified volume. The products of fuel underburning are also subjected to additional oxidation, which ultimately increases the completeness of their combustion and, accordingly, the operational advantages depending on it, in particular, the absence of solid deposits and, accordingly, the need for cleaning during operation of devices and communications, as well as minimization environmental issues.

Moreover, the implementation of the possibility of increasing the oxidation rate, temperature and the rate of temperature rise during the oxidation period due to the introduction of additives, according to this technical solution, allows you to conduct the target process at an acceptably high technological speed with the maximum possible reduction of the oxidizing agent.

All known methods, in contrast to the claimed, are characterized by insufficient efficiency of branched chain oxidation reactions, especially low-temperature fuels.

The problem is solved by the proposed method for increasing the speed and completeness of fuel oxidation in combustion systems, including the use of a catalytic additive introduced into the oxidizing agent and / or fuel before or during the oxidation of the fuel, which is a solid substance, its solution or suspension, or liquid substance or its emulsion, in the form of an individual catalytic substance or a catalytic mixture of substances. In this case, the catalytic substance or at least one of the substances of the catalytic mixture is selected from the series: monocarboxylic acids and their anhydrides; dicarboxylic acids and their anhydrides; carboxylic acid salts; salts of dicarboxylic acids; carboxylic acid amides; amides of dicarboxylic acids; carboxylic acid anilides; dicarboxylic acid anilides; carboxylic acid esters; dicarboxylic acid monoesters and diesters; carboxylic acid imides; imides of dicarboxylic acids; carbonic diamide; carbonic esters acyclic and cyclic; urethanes; aminocarboxylic acids, the molecules of which contain amino groups (NH ₂ groups) and carboxyl groups (COOH groups); peptides and proteins whose molecules are constructed from residues of α-amino acids interconnected by peptide (amide) bonds of C (O) NH, the additive being introduced in an amount of from 0.0000001 to 0.1 wt.%, and solid fuel is used or liquid or gaseous fuel or a mixture thereof.

A comparative analysis shows that the inventive method differs from the closest analogue by the multifunctionality of the added additive due to the multifunctionality of the additive substances (in the prototype, multifunctionality is achieved by creating a special alloy in which each metal performs certain functions, requires the introduction of combustion modifiers and special additional additives), without the need using numerical hydrodynamic models or measurements to detect problem areas for chemicals, another mechanism of action of the additive on the oxidation process - it is a spin catalyst (in the prototype, the chemical interaction of the additive with fuel and oxidizing agent), another initial structure of the additive, which does not undergo any special effects before using it (in the prototype, an alloy of metals is used , which must be made, requiring in some cases even the application of an additional coating on its particles for dissolution in the fuel).

The introduced individual catalytic substances or a catalytic mixture of substances increase the enthalpy of the combustion products (upon receipt of work), the density of the radiant flux (upon receipt of energy), the oxidation rate, temperature, and the rate of temperature rise during the period of fuel oxidation by increasing the rate of recombination of free radicals.

When considering the conversion of thermal energy into mechanical energy, as well as the efficiency of thermal processes, enthalpy is an extremely important thermodynamic property. Enthalpy is the energy content of a system, including internal energy and work done on the system. The enthalpy of the gaseous products of combustion N (kJ / kg) is equal to the product of the mass of the products of combustion M by their heat capacity C and the combustion temperature T _g , i.e. H = SMT _g .

The energy transfer from the combustion products is mainly carried out by radiant heat transfer. Radiation heat exchange is carried out by means of electromagnetic waves. Thermal radiation is the process of propagation in space of the internal energy of a radiating body through electromagnetic waves. The causative agents of these waves are material particles that make up the substance. The practical calculations of gas radiation are based on the Stefan-Boltzmann law. As a result, the density of integral radiation from the surface of the gas layer is determined by the equation:

where ε _g is the degree of blackness of the gas layer, depending on the temperature, pressure and thickness of the gas layer, with ₀ = 5.67 W (m ² · K ⁴ ) is the emissivity of a completely black body. For H ₂ O and CO _{2, the} values of ε _g are given in the form of nomograms convenient for practical calculations. The degree of blackness of gas mixtures is defined as the sum of the degrees of blackness of the individual components. The density of the radiant flux transmitted from the gas to the surrounding walls (shell) is calculated by the equation:

- эффективная степень черноты оболочки.where ε _g is the degree of blackness of the gas at a gas temperature T _g ; And _g is the absorption capacity of the gas at a shell temperature T _article ;

- the effective degree of blackness of the shell.

The applicant theoretically substantiated that greater efficiency of the processes based on fuel oxidation can be achieved if it is possible to provide a high oxidation rate, temperature and temperature rise rate due to the introduction of the additive, compared with the same oxidation conditions, but without the introduction of the additive.

The applicant also theoretically substantiated that it is possible to find a substance or mixture of substances that would increase both the enthalpy of gaseous products of combustion and the density of the radiant flux by increasing the rate of oxidation and, accordingly, increasing the temperature of combustion.

The practical effect of adding a catalytic substance or a catalytic mixture of substances to increase the rate and completeness of fuel oxidation is manifested in a significant increase in both the enthalpy of gaseous products of combustion and the density of the radiant flux transferred from the gas to its surrounding walls. Due to this, a greater amount of mechanical work can be performed and / or a greater amount of thermal energy transferred with a fixed amount of fuel supplied, or the amount of fuel can be reduced in order to obtain a given amount of work and energy. In any case, there is a significant increase in the efficiency of this process.

The term “catalytic” was used by the applicant because the substances introduced to achieve the technical result exhibit the properties of a “spin catalyst”, i.e. induces transitions between triplet and singlet states in electrons on the outer electron shells of free radicals. The formulation “spin catalysis” and “spin catalyst” is adopted in spin chemistry, a field of science in which the laws of the behavior of spins and magnetic moments of electrons and nuclei are studied. Spin chemistry is based on a universal and fundamental principle, which states that any chemical reaction is allowed only if the full spins of the reactants and products coincide. In the absence of spin identity, the reaction is forbidden.

The applicant believes that by influencing the spin dynamics of free radicals during the oxidation of fuel components using a “catalytic” substance, the enthalpy and density of the radiant flux of the gas obtained as a result of this process can be substantially changed.

Combustion is the process of combining a substance with oxygen, accompanied by the release of energy. To start the combustion process, the combustible substance must first be heated to the ignition temperature. The commenced combustion process can continue provided that as a result of the combustion of the substance sufficient heat is released to maintain its ignition temperature. During combustion, the molecules of the combustible substance are split, consisting mainly of carbon C and hydrogen H, as well as the oxidizer (oxygen O ₂ ), whose fragments (free radicals having an unpaired electron on the outer electron shell) then join (recombine) with the formation of combustion products, mainly H ₂ O and CO ₂ . The energy released during combustion, in the first moment after the reaction is concentrated in the resulting fragments of molecules or radicals. These are activated, i.e. possessing excess energy, the radicals react again. As a result of such successive reactions, a chain process arises.

In combustion reactions, not only molecular, but also spin dynamics is important, which plays a double role in elementary chemical acts. On the one hand, it actively affects the mechanism and kinetics of the reaction. On the other hand, spin dynamics react very sensitively to the molecular dynamics of an elementary chemical event. It is known from spin chemistry that two fundamental factors control chemical reactions - energy and spin. Moreover, the prohibition of chemical reactions on the back is insurmountable. If in a chemical reaction the colliding electrons on the outer electron shells of free radicals have antiparallel spins (↑ ↓ are the projections of the spins on the quantization axis), i.e. the total spin is zero (S = 0), while in the singlet state, the formation of a chemical bond occurs. If interacting electrons have parallel spins (↑↑, ↓↓, →-05) i.e. the total spin is equal to unity (S = 1), being in the triplet state, the molecule can form only in the triplet, excited state. Since such states usually lie high in energy, in the vast majority of cases, chemical reactions in a triplet pair are impossible.

According to the Wigner rule, the statistical weight of the meetings of two free radicals in the singlet state is 1/4, and the statistical weight of the meetings in the triplet state is 3/4. In the vast majority of cases, the ground state of the products of the chemical reaction is singlet, and therefore it should be expected that only a quarter of the occurrences of the recombining radicals can give the reaction product. Such processes, as a rule, proceeds non-activation, i.e. the activation energy of the reaction is close to zero. The resulting molecule is in the ground electronic state. The reaction proceeds quickly and efficiently if the molecule has the ability to transfer the energy released during the formation of the bond to other particles or redistribute it between many vibrational modes.

If we use a “spin catalyst”, which facilitates the conversion of an electron pair on the outer electron shells of converging radicals from a triplet spin state to a singlet state, this ratio (3/4 to 1/4) can be changed in the direction of increasing convergence in the singlet state. The action of the “spin catalyst” is not associated with a decrease in the activation energy of the interaction. The magnetic interactions of converging free radicals with the “spin catalyst” make a negligible contribution to the interaction energy, but they change the spin state of the electrons on the outer electron shells and remove the spin prohibition on the recombination of radicals. Thus, the “spin catalyst” controls the interaction, inducing transitions between the triplet and singlet states in the electrons on the outer electron shells of the converging free radicals, which are characterized by different energy abilities. By increasing the probability of free radical convergence in the singlet state, the number of recombinations with the formation of final combustion products with the release of energy per unit time will increase, which will lead to an increase in the combustion temperature.

An increase in the combustion temperature will entail an increase in the enthalpy of gaseous products of combustion Н = СМТ _g (kJ / kg) and a significant increase in the density of integral radiation from the surface of the gas layer, since according to the Stefan-Boltzmann law in the formula (T _g / 100) ⁴ .

All methods that allow to intensify the process of fuel oxidation and using physical (increasing pressure during combustion and the temperature of the supplied fuel and oxidizer, the effect of electric and magnetic fields), chemical (introducing an additional oxidizing agent or decomposition and combustion catalysts) and structural (fine crushing and spraying, intensification mixing) methods of influencing the kinetics of the process, are ultimately reduced to increasing the likelihood of a fuel connecting with an oxidizing agent. The proposed method for increasing the speed and completeness of fuel oxidation in combustion systems allows the oxidation process to be intensified using not technical methods that have already largely exhausted themselves, but rather affect the spin dynamics of free radicals during oxidation by introducing very small amounts of substances that act as “spin catalysts” into the oxidation zone.

Thanks to this method of conducting the process, not only an increase in temperature and rate of temperature rise is achieved, but also a decrease in the mechanical and chemical underburning of the fuel, which results in a decrease in the amount of carbon deposits in the combustion zones with a low temperature, as well as a decrease in unoxidized components (CO and CH) in the products oxidation.

Table 1 shows the data obtained experimentally using a calorimeter, showing the increase in the rate of rise of the water temperature in the calorimeter 1 minute after burning the fuel, depending on the use of a specific substance or mixture of substances as an additive compared to standard oxidation conditions. Since the calorimetric bomb is filled with an oxidizing agent (oxygen) under high pressure, other factors, with the exception of the described method, do not affect the increase in the burning rate. The g / tf reduction shown in the title of column 3 of table 1 is the unit for measuring the concentration in the bomb - grams per tonne of standard fuel.

Table 1. Substance class Substances Concentration in a bomb, g / tf Change in water temperature in a calorimeter 1 minute after fuel combustion, ° С Liquid fuel (dean) Solid fuel (coal) Gaseous fuel (methane) clean with the addition clean with the addition clean with the addition Carboxylic Acid Salts sodium acetate 2.5-3.0 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2 ammonium acetate 2.0-3.0 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2 Dicarboxylic Acid Salts ammonium oxalate 2.5-3.5 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2 potassium oxalate 3.5-4.0 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2 Amides of carboxylic acids acetamide 5.0-6.0 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2 benzamide 4.0-5.5 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2 Amides of Dicarboxylic Acids oxamide 5.0-6.0 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2 succinamide 3.0-4.0 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2 Carboxylic Acid Anilides acetanilide 1.0-1.5 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2 formanilide 2.0-2.5 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2 Dicarboxylic Acid Anilides oxanilide 1.5-2.5 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2 succinanilide 2.0-3.0 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2 Carboxylic Acid Esters ethyl acetate 0.5-1.0 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2 butyl butyrate 0.7-1.2 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2 Monoesters and Diesters of Dicarboxylic Acids octyl phthalate 0.6-0.7 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2 dibutyl phthalate 0.6-0.8 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2 Carboxylic Acid Imides acetic acid imide 0.9-1.0 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2 propionic acid imide 0.85-1.0 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2 Dicarboxylic Acid Imides adipic acid imide 0.7-0.8 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2 succinimide 0.75-0.9 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2

Total Carbonic Amide carbonic diamide (urea) 2.0-2.5 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2 Carbonic acid esters (organic carbonates) acyclic and cyclic dibutyl carbonate 0.08-0.12 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2 propylene carbonate 0.09-0.14 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2 Urethanes ethyl carbamate 1.0-2.0 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2 propyl carbamate 0.5-0.6 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2 Aminocarboxylic acids glycine 2.5-3.5 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2 lysine 0.9-1.5 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2 Peptides and Proteins carnosine 3.0-4.0 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2 protamine 2.5-3.5 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2 Mixtures of substances urea 0.2-0.3 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2 acetic acid 0.15-0.25 ethyl acetate 0.5-0.6 urea 0.2-0.30 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2 oxalic acid 0.25-0.35 benzamide 0.3-0.4 succinimide 0.25-0.35 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2 succinic anhydride 0.3-0.4 formanilide 0.55-0.65 ethyl acetate 0.3-0.4 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2 oxanilide 0.2-0.3 ammonium acetate 0.25-0.35 octyl phthalate 0.5-0.55 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2 glycine 0.6-0.65 potassium oxalate 0.4-0.5 succinanilide 0.25-0.35 0.2-0.3 0.5-0.7 0.12-0.15 0.35-0.42 0.3-0.5 0.9-1.2 urea 0.2-0.3 carnosine 0.15-0.25

Due to the introduction of additives, according to the present technical solution, it is possible to carry out the target process at the maximum possible reduction of the oxidizing agent, which entails a decrease in the amount of heat carried away from the combustion zone with exhaust gases, and also allows an additional increase in the combustion temperature.

The catalytic additive of the present invention, which increases the rate and completeness of fuel oxidation, when used in practice in any particular field of application, determines the improvement of the performance of devices that implement the inventive method, and optimizes the functional results during their operation.

The additive according to the invention is effective when used in the following range of applications, which is not limiting of the invention when it is put into practice.

Application of the proposed method for the operation of internal combustion engines of both piston engines operating on Otto, Diesel or Trinkler cycles, and gas turbine units allows to increase the efficiency of these engines. On reciprocating internal combustion engines, through the use of a catalytic additive, the combustion rate and the combustion temperature of the fuel increase, correspondingly increasing the enthalpy of the combustion products, which leads to an increase in the maximum combustion pressure of the cycle and the maximum degree of pressure increase, which entails an increase in the average indicator pressure and accordingly increases the indicator engine efficiency over the entire load range. In gas turbine plants, the application of this method also entails an increase in the speed and temperature of combustion of the fuel, respectively increasing the enthalpy of the combustion products and the pressure in the combustion chamber, thereby increasing the efficiency of the installation. Increasing the completeness of fuel oxidation in internal combustion engines, the proposed method provides a reduction in carbon formation on the internal cavities of the combustion chambers and improves the environmental performance of engines by reducing under-oxidized compounds (CO, CH and ash) in the exhaust gases.

Using the proposed method in technological processes associated with the firing of materials (limestone, cement clinker, building materials (brick, ceramics, expanded clay)), by increasing the combustion temperature and the density of the radiant flux, these processes can be conducted at a higher speed or, without changing the speed of the technology reduce fuel consumption.

This method can be applied in all pyrometallurgy processes, a set of metallurgical processes occurring at high temperatures. When firing (oxidizing, sulfatizing, reducing, calcining, etc.), smelting (blast furnace, open-hearth, oxygen-converter, etc.), converting ferrous and non-ferrous metals, refining and agglomeration, the proposed method due to the possibility of obtaining higher temperatures and more complete oxidation allows you to conduct processes at maximum technological speed and / or to reduce the specific consumption of fuel and / or oxidizer.

Upon receipt of thermal energy in the power system, the proposed method, increasing the density of the radiant flux, the enthalpy of combustion products and the completeness of oxidation of the fuel, increases the efficiency of boilers operating both on solid (layered, chamber and fluidized bed combustion), and on liquid and gaseous fuels. Increasing the completeness of oxidation of fuel in boiler plants, the proposed method provides a reduction in carbon formation on heat transfer surfaces and improves the environmental performance of boilers by reducing unoxidized compounds (CO, CH and ash) in the exhaust gases.

In all the above areas of application, the proposed method allows the use of lower-quality fuel (with increased ash content and water cut, lower combustion temperature, etc.), because due to the increase in the speed and completeness of oxidation, the problems arising during fuel combustion are eliminated. All known methods, in contrast to the claimed, are characterized by insufficient efficiency of the occurrence of branched chain oxidation reactions, especially low-calorie fuels.

Due to the decrease in atmospheric air intake, and, accordingly, the nitrogen contained in it, as well as due to the effect of the catalyst on the spin dynamics during decomposition and oxidation during fuel combustion, a decrease in the emission of nitrogen oxides is observed. This is an undoubted advantage of the described method, since an increase in the combustion temperature by other methods leads to an increase in emissions of nitrogen oxides.

Examples of the implementation of the invention are illustrated by the following practical results.

Example 1. During research on a motor stand using all the necessary equipment, more than 120 indicator diagrams were recorded on various operating modes of the T-520 engine using AI-92 standard gasoline, and then, on the same operating modes, the engine was tested on gasoline with the introduction of a catalytic additive (in particular, ammonium acetate) according to the claimed method in an amount of 1 g per 1000 l of gasoline.

The most significant results were obtained when the engine was running at n = 1250 min ^-1 and a torque value of 0.35 M _cr.max . Typical indicator charts obtained at this engine operating mode are shown in FIG. 1 (at an ignition timing of 5 ° p.p. (crankshaft rotation)), and in FIG. 2 (at an ignition timing equal to 15 ° p.c.v.), the results of processing indicator charts are presented in table 2.

Table 2. Parameter Units rev. Ignition timing, ° p.c. 5 fifteen AI-92 AI-92 + additive AI-92 AI-92 + additive The average indicator pressure, p _i MPa 0.296 0.314 0.399 0.407 Maximum cycle pressure, p _z MPa 1.15 1.46 1.93 2.17 The position of the point z relative to TDC, φ _z ° p.c. 32,0 23.9 15,2 11.0 Maximum pressure rise rate, dp / dφ _max MPa / ° p.c. 0,026 0,048 0,097 0,120

An analysis of the results shows that using the additive, the increase in the maximum combustion pressure of the cycle ranged from 12.5 to 27% (at different ignition timing).

In this case, the point of maximum pressure of the cycle in all cases shifts closer to TDC (top dead center).

It can be noted that the change in the course of the pressure rise curve when working with and without the additive in all cases begins from the moment the combustion of the air-fuel mixture develops (from the point of separation of the combustion curve from the compression curve). On the expansion curve, the lines of the indicator diagram during combustion of the air-fuel mixture with and without additives are almost identical, i.e. the additive used does not affect the expansion process.

It should be noted that in this case, the completeness of the indicator diagram increases markedly (the area under the curve of variation of the internal cylinder pressure increases), which indicates an improvement in the combustion process (in particular, its speed and completeness and, in general, an increase in cycle efficiency). This increase in the efficiency of the combustion process is due to the action of the additive in the flame propagation phase over the volume of the combustion chamber (the so-called second phase of combustion). In this phase, usually 70-80% of the heat introduced into the fuel cycle is released. The temperature of the working fluid at the end of this phase rises to 2200-2300K, and the pressure reaches a maximum.

The maximum degree of pressure increase also increases significantly (by 24-85%), which indicates a slight increase in the rigidity of the combustion process, without which it is impossible to improve the characteristics of the process itself.

These conclusions correlate well with the data on the change in the average indicator pressure p _i : with the introduction of the additive, the growth is 2-6%. Since the average indicator pressure determines the value of the indicator efficiency, an increase in p _i indicates a noticeable change in the fuel combustion process as a result of the introduction of additives, as a result of which the indicator engine efficiency increases.

Thus, we can conclude that the introduction of additives in the fuel has a noticeable effect on improving the course of the active phase of the combustion process and, as a whole, leads to an increase in the engine indicator indicators.

Example 2. The tests were carried out on a VAZ-11113 OKA car on running drums in a driving cycle. The test results are shown in table 3.

Table 3. Emissions of toxic components, g / km tests Fuel consumption, according to test results, l / 100 km Hydrocarbons M _CH Carbon Monoxide M _CO Nitrogen oxides M _NO Cross-country toxicity measurement results When working on standard gasoline AI-92 0.012 1.015 0.024 5,6 drums When operating on AI-92 gasoline with an additive (in particular acetamide) 2 g per 1000 l of gasoline according to the invention 0.009 0.7 0,020 5.1 EURO-2 international standards 0.2 2,3 0.15 -

When tested on running drums in a driving cycle, the decrease in toxic components when using a catalytic additive was: for hydrocarbons CH - 25%, for carbon monoxide CO - 31%, for nitrogen oxides NO - 17%. Thus, we can confidently conclude that with the introduction of additives, the completeness of fuel combustion significantly increased.

Example 3. The tests were carried out at the bush No. 1 of the Nizhne-Luginetskoye oil field at diesel power plants of DES - 315 kW.

The controlled parameters were: average load (kW), fuel consumption (l), the amount of electricity generated (kW · h). The technical condition of diesel power plants was also monitored.

Prior to testing, the average fuel consumption at an average load P _cp = 230 kW was 60.754 l / h. The specific fuel consumption for the generation of electric energy for the period from June 1, 2008 to July 23, 2008 was 0.297 l / kW · h.

In the period from July 24, 2008 to August 16, 2008, diesel fuel was used with an added additive (in particular, oxamide) according to the invention in an amount of 4.5 g per 1000 liters of diesel fuel. The average fuel consumption for this period at an average load of P _cf = 230 kW was 56,406 l / h. The specific fuel consumption for the generation of electric energy for the specified period amounted to 0.247 l / kW · h.

The use of fuel additives allowed to reduce the hourly fuel consumption by 7.16% and the specific fuel consumption for the generation of 1 kWh of electricity by 16.85%. Control examinations did not reveal deviations in the operation of diesel power plants from normal operating modes.

Thus, by increasing the completeness of fuel combustion, the introduction of an additive predetermined the improvement of the operating characteristics of power plants and optimized the functional results during their operation.

Example 4. The tests were carried out on a steel hot water boiler KVm - 1.86 KB, equipped with a mechanical firebox with a screwing bar type TShPm - 2.0 of boiler room No. 6 of the municipal unitary enterprise of Biysk "Heat energy". Solid fuel was burned in a boiler equipped with an automatic system that allows controlling the temperature of the exhaust gases, the vacuum before the exhaust fan, the pressure of the blower fan, the pressure of the water leaving the boiler, and the temperature of the water entering and leaving the boiler. In the course of the tests, instrumental measurements of the combustion temperature of coal were carried out using the Luch partial radiation pyrometer. Samples of entrainment from the trap and ash from the boiler were analyzed for the content of unburned coal in the ablation and quantitative determination of the burning of coal in the ash.

The additive solution (in particular, urea 3.0 g + acetic acid 4.0 g per 1 ton of fuel) was injected directly into the air duct behind the blower fan using an Etatron DS Type BV 1-3 peristaltic dosing pump, the air temperature in the air duct was 7 ° C. The amount of the supplied aqueous solution of the additive is 1000 ml per hour.

Within two hours, control measurements of the parameters of the boiler were carried out. During this period, the average water temperature at the inlet to the boiler was 43.075 ° C, and at the exit from the boiler 60.57 ° C (ΔT ₂ = 17.495 ° C), the water flow through the boiler was Q ₁ = 164.238 m ³ . The average combustion temperature of coal on the surface was T _pir = 1210 ° C.

Then the flow of the additive solution was turned on. Over the next two hours, the average water temperature at the inlet to the boiler was 43.1 ° C, and at the exit from the boiler 62.87 ° C (ΔT ₂ = 19.77 ° C), the water flow through the boiler was Q ₂ = 166.014 m ³ . The average combustion temperature of coal on the surface was T _pir = 330 ° C.

The heat energy generation during the period of control measurements was E ₁ = ΔT ₁ × Q ₁ × С _p = 17.495 ° С × (164.238 × 10 ³ ) kg × (4.19 × 10 ³ ) J / (° С × kg) = 12.039 GJ = 2.87 Gcal or 1.437 Gcal / hour.

The heat energy generation during the additive supply period was E ₂ = ΔT ₂ × Q ₂ × С _p = 19.77 ° С × (166.014 × 10 ³ ) kg × (4.19 × 10 ³ ) J / (° С × kg) = 13.752 GJ = 3.282 Gcal or 1.641 Gcal / hour.

Coal consumption remained unchanged since on the control panel the boiler load period of 5 minutes was set.

Laboratory analysis of the samples showed that the content of unburned coal in fly ash was 68% under normal conditions and 48.5% when working with the additive, and the mineral content in ash was 87% under normal conditions and 91% when working with the additive.

As a result of tests, it was found that the boiler efficiency increased by 14.2%, thermal energy production increased, the content of unburned coal in fly ash decreased by 39.3%, the burnup of coal loading improved, the temperature of coal burning on the surface increased by 120 ° С.

Example 5. The tests were carried out in JSC "Guryevsky Metallurgical Plant", Guryevsk, Kemerovo region, steel production site, open-hearth furnace No. 1, on fuel oil TKM-16 according to TU 38401-58-74-2005.

All current process parameters were controlled by instruments. Fuel oil consumption was measured by a YOKOGAMA flowmeter of the ROTAMAS series (Japan), which determines the mass and volumetric fuel consumption, current and total. The torch temperature in the furnace was monitored using a Mikron-M90L pyrometer designed to measure the temperature of combustion products containing CO ₂ . The quantity and chemical composition of the smelted steel were controlled by OTC laboratory assistants.

Before starting the test, a fuel sample was taken from the supply tank. According to the analysis, the flash point in the open crucible was t _sun = 141 ° C. After introducing 340 g of the additive (in particular, oxanilide) into the supply tank with 170 tons of fuel oil (in particular, oxanilide) in the form of a solution, a sample was taken for analysis, which showed a decrease in the flash point in the open crucible t _sun = 129 ° C due to the manifestation of the catalytic properties of the additive. As a result of the introduction of the additive, tar-paraffin deposits dispersed from the bottom of the tank. The improvement of the rheological properties of fuel oil was manifested in a significant (~ 20%) decrease in viscosity.

Prior to testing, the furnace worked with standard nozzles ⌀ 9.0 mm installed on it.

During the test, the open-hearth furnace was switched to operation with fuel with an additive and nozzles ⌀ 7.5 mm were installed. By the end of the test day, nozzles ⌀ 6.1 mm were installed and the nozzles were tuned for optimal operation, resulting in an improvement in the operation of the open-hearth furnace, which resulted in an intensification of the flame burning in the center of the furnace. This made it possible to optimize the heat transfer in the furnace bath and reduce the heat load on the arch of the furnace and nozzle. The temperature of the exhaust gases and smoke in the hog also decreased.

The torch temperature in the middle window of the furnace was 1800 ° C for filling and 2000 ° C for melting and lapping. This made it possible to intensify the operation of the open-hearth furnace without increasing the thermal load on the structural elements. At the same time, fuel oil consumption was reduced from 2200 l / h to 2150 l / h for filling and from 2350 l / h to 2200 l / h for melting and finishing. The results of data processing showed that, according to averaged indicators, the melting time in experimental melts was reduced by 30 minutes, and the average fuel oil consumption for melts decreased by 9.4%. During the testing period, the quality and quantity of steel smelted corresponded to the nominal operating conditions of open-hearth furnace No. 1.

The use of a catalytic additive allows to intensify the melting process and reduce specific fuel consumption per unit of output. At the same time, the thermal load on the arch and nozzles of the open-hearth furnace is reduced. By optimizing the combustion process, the emission of CO, CH and ash into the surrounding atmosphere is reduced.

Example 6. The tests were carried out at a metallurgical plant in the sintering furnace mill for calcining limestone with the introduction of additives (in particular, 0.2 g of dibutyl carbonate per 1000 nm ³ (gas volume under normal conditions) of methane in the secondary air supplied for combustion. 200 l capacity and additive solution Preliminary measurements were made on the composition of the exhaust gases After 12 hours of operation of the peristaltic pump supplying the additives, the exhaust gases and torch temperatures were measured on the peripheral mountains Due to an increase in the temperature of the flame in the furnace compared to the initial one, which was 1050-1150 ° C, the gas supply was reduced by more than 300 ° C by 40 nm ³ / h. A day after the start of the test after measurements of the combustion parameters were reduced gas supply at another 20 nm ³ / h. The gas consumption of the working kiln was 490 nm ³ / h instead of 550 nm ³ / h at the beginning of the tests. The reactivity of the obtained lime was in accordance with the standards, the phenomenon of "burnout" was not observed.

Example 7. Improving fuel efficiency and improving the quality of the agglomerate when using a catalytic additive during agglomeration was determined on a belt sintering machine. The additive (in particular, 1.5 g of ethyl carbamate + 0.7 g of dibutyl phthalate per 1 ton of coke) was fed into the pelletizing drum during secondary mixing of the charge materials. In the production of fluxed agglomerate with increased oxidation of iron, the oxygen content (O ₂ ) in the furnace gases and under the charge layer, the temperature of the combustion products, and the flow rate of air and natural gas were measured as controlled parameters. The charge conditions, fuel consumption (C - 4.1%) and charge moisture were constant for these experiments. The height of the combustion zone was determined by the change in the content of CO ₂ in the layer. The amount of excess heat in the alomerized layer can be judged by the increase in the FeO content in the cake. As a result of the tests, the following results were achieved: a 12% reduction in the consumption of solid fuel (coke breeze), an increase in the speed of sintering, alignment of the FeO content with the height of the cake, i.e., a more homogeneous sinter with constant mechanical strength of the cake. The additive (in particular, 0.2 g of propylene carbonate per 1000 nm ^{3 of} gaseous fuel) was also fed into the air supplied to the burner for burning gas in the incendiary furnace of the sintering furnace. Due to a significant increase in the combustion temperature in the first and second sections of the hearth, gas consumption was reduced by an average of 25%. Also, according to the results of measurements, a significant decrease in CO and NO _X in the furnace gases was revealed.

Example 8. The increase in the efficiency of using the oxidizing agent and the optimization of the oxygen-converter process when using a catalytic additive in the conversion of cast iron was determined at a metallurgical plant in the converter shop. The tests were conducted on a 250-ton top-purged oxygen converter. The additive (in particular, acetanilide) in the form of an aqueous solution was introduced into the oxygen supplied to the converter using a metering pump immediately before the lance. As a result of an increase in the oxidation rate of carbon, silicon, manganese, and phosphorus contained in pig iron, the temperature of the steel in the converter increased by 100 ° С, as compared to conventional melts. This made it possible to increase the share of steel scrap during loading by 46.4 kg / t of steel. An increase in the СО ₂ content in the exhaust gases was also 1.5–2 times higher than the СО ₂ values for standard purge modes, which indicates an increase in the degree of CO afterburning in the converter.

Example 9. The use of the catalytic additives, according to the invention, to fuel oils and heating oils can significantly increase the completeness and intensity of combustion of fuels. The concomitant cleanliness of heat transfer surfaces contributes to an increase in the heat transfer coefficient, as well as lower operating costs. Significantly improves the environmental parameters of the exhaust gases.

Tests in oil-fired boiler rooms show that the average reduction in fuel oil consumption when using an additive is 8-12%, depending on the mode of operation of the boiler, in addition, it becomes possible to use low-quality fuel oils and with increased water cut regardless of the type and quality of the boiler equipment used . Specific boiler houses on which tests were carried out and equipment used: boiler house of Altayvitamins CJSC Biysk, steam boilers DE 10/14 with GM-7 burners; boiler house LLC Teplo, village of Aktash, Altai Republic, steam boilers of the DKVR-4/13 brand; boiler house LLC "Sphere", Barnaul, steam boilers "LOOS UNIVERSAL U-MB" (Germany), operating pressure up to 16 bar, with high-pressure burners; boiler room MUP "Teploservice" of the Sloboda Kirov region, steam boilers DKVR-6.5 with burners "Weishaupt" (Germany).

All of the above examples should not be construed as limiting the invention to the field of practical applications. The above examples in the production environment show the optimization of the target process through the use of a catalytic additive that increases the rate and completeness of oxidation of the fuel, which determines the improvement of the performance of the devices when it is introduced into the process.

Manifesting in the implementation of the claimed invention, a technical result, confirmed, according to the description, by theoretical evidence and practical information, allows us to solve the problem of creating an effective way to increase the speed and completeness of oxidation of fuel in combustion systems.

Claims (5)

1. The method of intensification of fuel oxidation in combustion systems, and the intensification of fuel oxidation includes increasing the oxidation rate, increasing the oxidation temperature and / or increasing the rate of rise of the oxidation temperature, including: introducing a catalytic additive in the oxidizer and / or fuel before or during the oxidation of the fuel, where the catalytic additive is a solid, its solution or suspension, or a liquid substance or its emulsion in the form of an individual catalytic substance or catal mixtures of substances, and in this case:
the given catalytic substance or at least one of the substances of the catalytic mixture contains at least one functional carbonyl group and has in the IR spectrum at least one intense absorption band in the range from 1550 to 1850 cm ^-1 , and the specified catalytic substance or at least one of the substances of the catalytic mixture is selected from the following series: monocarboxylic acids and their anhydrides; dicarboxylic acids and their anhydrides; carboxylic acid salts; salts of dicarboxylic acids; carboxylic acid amides; amides of dicarboxylic acids; carboxylic acid anilides; dicarboxylic acid anilides; carboxylic acid esters; dicarboxylic acid monoesters and diesters; carboxylic acid imides; imides of dicarboxylic acids; carbonic diamide; carbonic esters acyclic and cyclic; urethanes; aminocarboxylic acids, the molecules of which contain amino groups (NH ₂ groups) and carboxyl groups (COOH groups); peptides and proteins whose molecules are constructed from residues of a-amino acids, interconnected by peptide (amide) bonds of C (O) NH;
the specified catalytic additive is introduced in an amount of from 0.0000001 to 0.1 wt.%;
and solid, liquid or gaseous fuel, or a mixture thereof, is used as fuel. 2. The method according to claim 1, characterized in that the catalytic additive is introduced in an amount of from 0.0000001 to 0.00009 wt.%. 3. The method according to claim 1 or 2, characterized in that the fuel burned is a solid fuel. 4. The method according to claim 1 or 2, characterized in that the combusted fuel is a gaseous fuel. 5. The method according to claim 1 or 2, characterized in that the combustible fuel is a liquid fuel selected from standard gasoline AI-92, diesel fuel and fuel oil.

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