KR100428749B1 - New soot-controlling catalytic fuel-additive compositions - Google Patents

Abstract

The present invention relates to a liquid crude combustion catalyst composition for suppressing combustion dust containing high concentration of ferrocene and enhanced low temperature phase stability, and more particularly, to reduce combustion dust including unburned carbon generated when burning heavy fuel oil. In the crude combustion catalyst composition used for the purpose of dissolving ferrocene used as a core oxidation catalyst at a high concentration, a specific aromatic solvent is selected as a basic solvent so that the dissolved ferrocene can be maintained in a stable solution even at low temperatures. The present invention relates to a new liquid phase combustion catalyst composition which greatly improves the complete dissolution stabilization and combustion dust suppression function of the composition by simultaneously solubilizing and stabilizing.

Description

Liquid crude combustion catalyst composition for suppressing combustion dust {New soot-controlling catalytic fuel-additive compositions}

The present invention relates to a liquid crude combustion catalyst composition for suppressing combustion dust containing high concentration of ferrocene and enhanced low temperature phase stability, and more particularly, to reduce combustion dust including unburned carbon generated when burning heavy fuel oil. In the crude combustion catalyst composition used for the purpose of dissolving ferrocene used as a core oxidation catalyst at a high concentration, a specific aromatic solvent is selected as a basic solvent so that the dissolved ferrocene can be maintained in a stable solution even at low temperatures. The present invention relates to a new liquid phase combustion catalyst composition in which the solubilization and stabilization of the composition are simultaneously improved, thereby greatly improving the complete dissolution stabilization and combustion dust suppression function.

Fuel oil has different combustion characteristics according to the type of fuel oil and the raw material of the fuel oil. Accordingly, the efficiency and the type and amount of combustion products in the combustion process are very different. Since the combustion characteristics of such fuel oils vary greatly from one combustion apparatus to another, combustion efficiency is generally evaluated by dividing into combustion in an internal combustion engine and combustion in a burner for a boiler.

Heavy fuel oils containing high boiling point organic compounds have very poor combustion characteristics, resulting in large amounts of unburned carbon or soot in the combustion process. Soot is one of the main components of soot and is one of the serious considerations when dealing with environmental pollution from combustion processes. Unburned carbon is an important component of incomplete combustion of materials with poor combustion characteristics in fuel oils such as polycyclic or cyclic compounds. It is either extinguished in the visible flame zone or secondary burned and extinguished in the external circulation zone, but part of it is mixed with the combustion gas and discharged.

The supporting additive added to reduce soot has a slight effect on reducing nitrogen oxides (NOx) because the temperature range in which nitrogen oxides are locally produced can be minimized by maintaining a uniform temperature distribution in the combustion field.

In addition, in the case of the crude catalyst for reducing soot, the amount of soot including unburned carbon is not directly proportional to the amount of the catalyst, but the overall tendency has a very high correlation similar to the proportional relationship. The amount of soot that can be reduced depends on the oil spray phase of the fuel oil, the properties and structure of the soot particles, and the amount of unburned carbon and is closely related to the efficiency of the entire combustion process, such as a boiler. In addition, since the addition ratio of the crude catalyst composition product is very low, such as 1/1000 or less based on the weight of the fuel oil, increasing the catalyst content in the crude catalyst composition product exhibits a distinct effect in most cases.

Commonly used supporting compositions for boiler fuel oils include secondary combustion catalysts, surface tension modifiers, sludge formation inhibitors, sludge dispersants, oxygen transfer agents, physical modifiers, corrosion inhibitors, flow promoters, dispersant agents, and particulate microexplosives. More than 10 different functional compounds can be mixed. Their physicochemical properties, including their dissolution properties, are very diverse and can often cause serious problems of phase stability, which must be overcome in particular when designing high concentrations of particularly poorly soluble materials.

Unburned carbon can be burned close to complete combustion in the secondary oxidation process by adding various types of oxidation catalysts to the fuel added to the fuel oil. In order to realize the secondary combustion by the catalytic oxidation, it is possible to use a catalyst including various transition metals, but in practice, due to the problem of secondary pollution by heavy metals in the form of oxides, it is relatively low in environmental risk and low in value. Catalysts based on inexpensive iron dominate. At this time, in order to improve the mixing properties and phase stability of the iron and fuel oil, an organic iron compound having good affinity and compatibility with the fuel oil is utilized, a ferrocene compound (ferrocene) is a typical case.

Ferrocene or ferrocene derivatives are organometallic compounds containing iron, and are widely used in various fields such as biotechnology, catalytic engineering, combustion engineering, military explosives, etc. It is a representative organo iron compound designed to maintain the structure and high affinity of organic molecules. That is, ferrocene is also used as an essential material for gene-related research and development, and is also used as a polymerization catalyst for polyolefins with other metallocene-based catalysts, and physically and / or with rubbers such as butyl rubber. It is chemically formulated and used as a raw material for the molding of propellants and explosives.

When utilizing ferrocene functionality in catalytic or combustion engineering, especially when added to a combustion combustion composition, it is necessary to maintain a stable state in the climatic environment in which the ferrocene-containing composition is exposed as a final product. It is an important technical aspect in terms of stable operation and maintenance of product performance.

Ferrocene is poor as an organometallic catalyst, such as used for preventing knocking in gasoline for internal combustion engines, or for catalytic combustion with the main purpose of removing soot generated during combustion of diesel oil or diesel fuel. It can be utilized as an important component of the crude combustion catalyst composition product used in mixing with various fuel oils showing combustion characteristics.

When ferrocene is utilized as a component of crude combustion catalyst composition products, it is applied to products in the form of mixtures with polar, nonpolar, or ionic organics, rarely inorganic or other organometallic compounds.

Organic materials mixed with ferrocene may include various aliphatic and aromatic materials, and the phase stability of ferrocene in the mixed composition is highly dependent on the physicochemical properties of the mixture dissolving ferrocene.

Until now, ferrocene is not classified as a general aromatic compound, and has been mainly dissolved in an aliphatic solvent due to the nature of most alkylated side branched ferrocene derivatives. However, although ferrocene is not classified as a conventional aromatic compound, similar characteristics of aromatics can be found by calculating the molecular orbital function of ferrocene. In other words, ferrocene has a molecular orbital electronic structure similar to pi (π) bonds, and is hardly soluble in acids, alkalis, and water, and a single simple organic solvent (alcohol, ether, etc.) or rarely, Since there is a characteristic that is limited to a low concentration in the same petroleum, it was a common method to be dissolved in a low concentration as described above and incorporated in the product.

That is, it is preferable to maintain the concentration or content of the ferrocene in a few% or more in order to maximize the functionality of the ferrocene in the practical aspect, or to reduce the logistics cost of the composition product containing ferrocene.

However, ferrocene is generally known to be poorly soluble in a single organic solvent, little solubility data is known, and especially when the temperature is lowered and supersaturated, it tends to grow from solution to needle needles. It has a low phase stability and easily precipitates as crystals.

Due to the above crystal growth and precipitation, and the possibility of high temperature deterioration of the product, there is a difficulty that the product containing ferrocene must be kept within a certain temperature condition range. In particular, in the case of the liquid composition, the phase instability due to the precipitation of ferrocene is very serious, and may cause various process obstacles in the application process of the composition.

For example, ferrocene-containing composition products mixed with diesel or heavy oils can cause plugging in the fuel supply system during the winter months, which can cause serious impediments in the continuous operation of combustion processes such as internal combustion engines and boilers. . Indeed, even in diesel fuels without ferrocene added in winter, special phase stabilizers may be added to prevent or mitigate the precipitation of acicular crystals in the wax components in fuel oils.

As mentioned above, the phase stability at low temperatures of liquid composition products must be a very strict product user specification, which is no exception to liquid composition products containing ferrocene, especially the requirements for phase stability at low temperatures. Silver becomes more serious when trying to increase the ferrocene concentration (or content) in the composition in order to enhance the function of ferrocene.

That is, the lower alcohol and polyisobutylene in the kerosene, polypropylene glycol or butylated hydroxy toluene and ferrocene (ferrocene) skeleton in kerosene as proposed by the inventor of the present invention 10-0227965 A fuel oil reforming aid composition prepared by adding an organoiron compound having a has been developed.

According to the above method, 70% by weight or more of kerosene, which is a kind of petroleum, is used as a basic solvent, and polybutene in oligomer form and a small amount of butylated hydroxy toluene are added, and an organic iron compound having a ferrocene skeleton is included. It is. However, the composition according to the invention maintains a stable liquid phase at room temperature conditions of 10 ℃ or more, but there is a problem that the added ferrocene is precipitated at a low temperature around 0 ℃ or less. Therefore, in order to continuously add the composition product to the combustion process in a low temperature environment, such as winter, the content of ferrocene had to be maintained at 0.5% by weight or less. That is, since the content of ferrocene is extremely low, the problem that the function of the secondary catalytic combustion of ferrocene is significantly reduced remains a problem to be solved.

Accordingly, the inventors of the present invention use an aromatic solvent or an aromatic mixed solvent of a specific composition as a solvent for dissolving the ferrocene, or when an aliphatic functional additive is to be included in the composition, an aromatic having a specific structure having an affinity with an aliphatic compound. The use of the compounds together has been found to be able to dissolve the ferrocene in a high concentration and to stabilize the liquid phase at low temperatures to complete the present invention.

Accordingly, the present invention uses an excess of specific aromatic solvents or mixed solvents as primary base solvents to easily solubilize ferrocene having physicochemical properties similar to aromatic compounds and to maintain a particularly stable liquid phase at low temperatures. It is an object of the present invention to provide a liquid crude combustion catalyst composition which may contain ferrocene and also, when applied to heavy fuel oil, greatly improves combustion dust suppression performance through a secondary combustion mechanism.

Figure 1 shows a simplified process of the laser optical combustion test by the light extinction method using a laminar diffusion flame.

Figure 2 shows a simplified structure of the laminar diffusion flame production burner of heavy fuel oil.

Figure 3 shows a simplified process of the laser optical combustion test by the light extinction method using a turbulent mixed flame.

Figure 4 simply shows the structure of the turbulent mixed flame production burner of heavy fuel oil.

FIG. 5 is a graph showing the relative amount of carbon deposits in the precision carbonization test by the induction system deposition method based on fuel without adding the combustion combustion catalyst composition.

The present invention relates to a combustion dust suppression combustion combustion catalyst composition containing ferrocene, comprising: 60 to 90% by weight of an aromatic solvent as a basic solvent and 1.0 to 12.0% by weight of ferrocene as a crude combustion catalyst. It is characterized by a crude combustion catalyst composition.

The present invention will be described in more detail as follows.

The present invention can dissolve a high concentration of ferrocene used as a core oxidation catalyst in the supporting catalyst composition for the purpose of reducing combustion dust including unburned carbon generated when burning heavy fuel oil, at a low temperature of the dissolved ferrocene It relates to a method for producing a liquid crude combustion catalyst composition capable of enhancing the combustion dust suppression function by improving the phase stability of the liquid phase combustion catalyst composition prepared accordingly.

The crude combustion catalyst composition according to the present invention is characterized in that a large amount of a specific aromatic solvent is used as a primary base solvent in order to solubilize ferrocene used as an oxidation catalyst at a high concentration.

Compared with the aliphatic compounds, the aromatic compounds are chemically stabilized in the molecule, and the combustion characteristics are generally inferior to those of the aliphatic compounds because of the relatively low flammable hydrogen content. However, if the aromatic solvent under consideration can be stabilized by dissolving ferrocene at a high concentration, it can be utilized as a basic medium of the crude addition composition of heavy fuel oil.

That is, since the combustion characteristics of the heavy oil, which is a combustion target, are very poor, if the supporting function of these added materials is superior, even if the aromatic solvent has a weaker combustion characteristic than the aliphatic solvent, it may be offset and overcome in the entire combustion process of the heavy oil, which is the combustion target. In particular, the complete combustion of aromatic polycyclic compounds (POM's) in the secondary combustion process may be promoted by the addition of ferrocene.

Substantially, the formation and combustion of the aromatic polycyclic bodies are affected by the type of aromatic compound to be added as a supporting composition, which may act in an adverse direction against the complete oxidation of the target unburned carbon and the improvement of energy efficiency. have. However, more effective than these side effects can be obtained by the addition of a secondary combustion catalyst, it is possible to prove the specification and efficacy of the effective supporting composition through a complex but experimental verification process.

The present invention proposes a method for preparing an effective catalyst composition as a crude combustion composition of heavy fuel oil by applying specific sophisticated experimental methods that can identify the combustion process governed by such conflicting effects.

That is, by selecting the basic solvent among aromatic solvents, the solubilization and phase stabilization are facilitated by physicochemical interaction similar to the aromatic compound represented by ferrocene.

Although an aromatic compound butylated hydroxy toluene was also used in the crude combustion catalyst composition containing ferrocene, the compound was added in a small amount for the purpose of suppressing the sludge generation by the oxidation process.

The aromatic compounds used in small amounts as described above could not contribute at all to the high concentration of ferrocene, and since the used aromatic compounds themselves do not exist as a liquid but as a solid at a temperature near the room temperature, they are used as a basic solvent. Not only could it not be utilized, but only a small amount was added because of the adverse effects of overdose, given the physicochemical properties of the compound.

On the other hand, in the present invention, solubility and stabilization of ferrocene can be minimized by adding an excessive amount of an aromatic solvent having the property of minimizing adverse effects on the combustion characteristics and maintaining a stable liquid state in the use environment temperature range of the composition product.

That is, while the composition range of the butylated hydroxy toluene, the aromatic compound proposed in the prior art, is limited to a maximum of 15% by weight as an additive, in the present invention, a strictly selected aromatic compound is 60 to 90 as a delivery medium for various additives. Excessive weight percent of the ferrocene can be used to dissolve the ferrocene stably and at low concentrations, i.e. the combustion characteristics change as the base solvent is changed from kerosene, an aliphatic mixed solvent, to a specific aromatic or mixed solvent. It is a feature of the present invention to present catalyst compositions in which the detailed type and composition of the additive material is adjusted according to the solvent, and the crude combustion performance is improved as a whole.

At this time, when the amount of the aromatic solvent is less than 60% by weight, it is difficult in terms of high solubilization and stabilization of ferrocene. When the amount of the aromatic solvent is higher than 90% by weight, it is not preferable in terms of the acceptability of functional additives and overexpression of combustion characteristics of the basic solvent itself. Was observed.

Aromatic compounds have good compatibility and commercial solubility with each other, but also have limited marginal solubility with aliphatic compounds. However, among aromatic compounds, it is very common to have a freezing point near or above room temperature.

Therefore, if the ferrocene-containing mixture is to maintain a stable phase in a wide temperature range including low temperature by using an aromatic compound as a base solvent, the problem of freezing or precipitation as described above must be experimentally confirmed, and a composition region in which freezing and precipitation can occur. The composition should be designed to avoid this.

Of course, the liquid-liquid equilibrium and the solid-liquid equilibrium should be considered independently of each other, so that a stable phase space region should be secured. It is possible to design base compositions or mixtures containing ferrocene optimized in terms of hyper-liquid phase equilibrium.

In addition, solvent products that can be used as a base solvent of the crude combustion catalyst composition product are more preferably selected from organic solvents that are mass-produced in petrochemical or coal chemical processes due to economical properties. In other words, it is appropriate to utilize solvent products which can be easily produced in large quantities or by-produced in large quantities in the production process of other chemicals in order to increase the economics and price competitiveness of the product.

Representative aromatic compounds from petrochemical or coal chemical processes, or mixtures thereof, which are discharged from the process, are BTX-based aromatic compounds and their mixed fractions (BTX oil), mixed xylene oil, methyl naphthalene fraction ( methyl naphthalene oil), anthracene oil and C9 aromatics (including C9 + fractions). However, since the methyl naphthalene fraction and anthracene fraction are relatively high in freezing point and are easily solidified, they are not easy to be used as a basic solvent of a composition that maintains a stable state in a liquid state at low temperature compared to other aromatic mixed oils or single compounds constituting them.

Therefore, in terms of practical use, it is preferable to utilize a mixed fraction of low molecular weight aromatic compounds except for the methyl naphthalene fraction and the anthracene fraction as described above directly or by processing.

In addition, when the crude combustion catalyst composition product containing ferrocene is a mixture which should include an aliphatic compound as a functional additive, compatibility and phase stability can be significantly improved by using an alkylated aromatic compound such as alkylbenzene together. Alkylated aromatic compounds may include alkyl groups in the form of linear chains or branched chains, and compounds in which the alkyl groups are partially derivatized with other functional groups may be used.

Among the candidate materials of the various usable alkylated aromatic compounds satisfying the above conditions, linear alkylbenzene and branched alkylbenzene or a mixture thereof may be utilized. The more preferable effect can be acquired when using the thing with one or more alkyl groups of 24 or less carbon atoms.

The materials are mass produced during the preparation of surfactants, are readily available, are very chemically stable, and have the property of mixing well with both aliphatic and aromatic compounds near room temperature. The alkyl chains present in the material can weaken the tendency of crystal formation due to the intermolecular overlap of aromatic compounds in the molecular structure, which can be further stabilized in terms of solid-liquid phase transition or precipitation separation even at low temperatures.

For the purpose of lowering the freezing point as described above, when a mixed solvent obtained by mixing aromatic compounds having different molecular structures is used as a basic solvent, the mixed composition is considered in consideration of both aspects of the solubility of ferrocene in the mixture and the precipitation temperature of ferrocene at the same time. Should be optimized

The low freezing base solvent mixture is determined by preparing mixture samples of differing compositions of the candidate solvent components. A circulating operation of cooling and heating the candidate mixture sample having each composition may exclude hysteresis effects with increasing temperature and cooling rate, and freezing points may be determined to determine the basic solvent composition that freezes below the target temperature. In practice, the samples are left at the desired limit temperature for a long time to check the composition area that does not freeze and repeat this to determine the optimum mixed composition. Phase instability due to liquid-liquid layer separation at room temperature can leave the samples prepared with each composition and then visually check for the presence of layer separation. If included, it can be confirmed experimentally by observing optical turbidity or scattering by shaking vigorously or stirring.

For example, benzene has very good solubility in ferrocene at room temperature, but the freezing point of benzene is high, and a stable liquid composition cannot be maintained at low temperatures. Therefore, even at the expense of some dissolving power, it is preferable to add a cosolvent and then use it as a base solvent of ferrocene to maintain a stable liquid phase at low temperature. In some cases, the intermolecular screening effect of the polymer chain may be used to prevent freezing of the base solvent or to prevent precipitation of waxy oligomers.

Solubility can be measured quantitatively by measuring the absorbance at the characteristic peak wavelength appearing in the spectrum after the absorption spectrum in the ultraviolet-visible region. In the case of ferrocene, it is dissolved in an organic solvent and the characteristic peak wavelengths of ferrocene are 326 nm and 442. The solubility can be determined by measuring the absorbance at nm.

In general, since the relationship between absorbance and concentration can be obtained linearly in the first proportion in the case of a low concentration region, it is preferable to obtain and use a calibration curve for absorbance for solutions having a concentration range of 0.1 to 0.5% by weight of ferrocene. . In order to measure the solubility at low temperatures where problems such as crystallization occur, an excess of ferrocene solute is added to a solvent and then left at constant temperature for a long time at a desired low temperature to cause precipitation and precipitation. Take only the supernatant, dilute the supernatant to a constant multiple of low concentrations, measure absorbance, and use the calibration curve and dilution scale to obtain accurate low temperature solubility data.

The combustion performance characteristics of the combustion combustion catalyst composition designed by the above method can be quantified and compared by various experimental methods. In recent years, the development of laser optical measurement technology for the high temperature flow field where combustion takes place can produce very sophisticated combustion experiment data within a short time. Because of the large quantities available, the experimental data obtained can be analyzed statistically to quantify the precise change in combustion characteristics and the performance of the coagulant.

Combustion process diagnosis using laser optics includes extinction, light scattering, Raman spectroscopy, laser induced fluorescence, exciplex fluorescence and laser incandescent laser induced incandescence, and degenerated four-wave mixing.

By applying the above laser optical technology to the combustion flow field, it is possible to precisely track the combustion process and to quantitatively compare and observe minute changes in the combustion process. The light extinction method, which is part of the method using the laser optical technology, will be described in more detail as follows.

Photodecay is effective in tracking the production and disappearance of unburned carbon or soot present in the combustion reaction field. Since the suit is optically close to the black body, it fully absorbs the incident light. Thus, within the range of Rayleigh scattering limits, it is possible to quantify the generation and disappearance of soot in a relatively simple manner, and to obtain an integrated volume fraction of soot that is accurately integrated along the light path. have.

The irradiated laser light may use a helium-neon laser light source, and signal noise, such as heat and heat generated from combustion, modulates incident light at a specific frequency, and photodiode Of the optical signals coming from the optical sensor, such as only the signal modulated at a specific frequency can be detected and removed. In practice, only such precise signals can be captured using a lock-in amplifier that removes noise at other frequencies using the orthogonality of the trigonometric function.

In most burners, the flame has an axisymmetric structure, so a one-dimensional scan through the central axis of the flame produces soot in the visible flame and external circulation region. The burner can be tracked, and the burner can be designed to utilize a flame to investigate combustion characteristics in the form of a symmetrical laminardiffusion flame or a turbulent mixed flame.

Heat is transmitted by conduction, convection, and radiation mechanisms, and the higher the temperature, the greater the importance of heat transfer by radiation. The soot is effective as a radiant heat transfer medium when the radiant heat transfer mechanism is of great importance such as large boilers.

As described above, the soot is closest to the ideal blackbody in terms of its ability to radiate radiant heat, so in some cases, a certain amount of soot is generated to transmit radiant heat and rapidly extinguish to such an extent that it rarely exists outside the visible flame region. In view of heat transfer, or larger, it is preferable. In particular, given the furnace structure and temperature distribution in large industrial boilers, it is ideal to have a certain amount of soot in the burner's flame and then disappear rapidly.

Another method of analyzing the soot inhibition effect of a crude catalyst composition added to fuel oil is to perform a precise carbonization test to observe the carbon deposition shape and to quantify and compare the amount of carbon deposition.

The method can actually be carried out by an Induction System Deposit (ISD) method, which finely injects fuel oil onto a high temperature metal surface with precise temperature control to forcibly carbonize it for a long time under flow conditions. This can be very useful for ascertaining the cumulative effect of waste carbon caused by carbonization in a high temperature environment outside of a flame influence area such as a spray nozzle.

In particular, heavy fuel oil is burned through energy generating process equipment, such as large capacity boilers, where it generates combustion dust containing a large amount of unburned carbon.

The crude combustion catalyst composition according to the present invention has a specific aromatic compound or mixture capable of maintaining a stable liquid phase at a low temperature and dissolving ferrocene at a high concentration as a basic solvent, and is added to heavy fuel oil to maximize the supporting characteristics including secondary combustion. The additive compound and its composition range were determined in detail.

The crude combustion catalyst composition according to the present invention facilitates the first atomization process by smoothly spraying at the first flame nozzle, and finely explodes the atomized particles into ultrafine particles in the combustion process and delivers oxygen through oxygenated molecules. Thus, the resulting aromatic polycyclic medium is quickly converted to a very fine soot, which leads to heat dissipation through the blackbody radiation heat transfer mechanism.

On the other hand, ferrocene, which has begun to decompose in the first half nozzle, is incorporated into the fine soot to act as a transition metal catalyst for the extinction oxidation of the soot in the middle and second half of the visible flame region. The specifications of the supporting composition were set to prevent the deposition of carbon residues at the abrasive injection nozzles by aromatic solvents. The mixed heavy oils do not produce sludge by the oxygen components in the air and the sulfur components in the heavy oils during the pre-combustion storage process. The additives with anti-oxidation function can be used in storage environment. The selected aromatic organic solvents are used to maintain the high concentration of ferrocene, the combustion engine catalyst, to provide a superior combustion performance for heavy fuel oils that surpasses the adverse reactions in the combustion process by aromatic organic solvents. It could be confirmed using an optical facility.

By the above-described method, it was possible to derive the specifications of the high performance support catalyst composition by designing the specification of the liquid support catalyst composition containing ferrocene at a high concentration and maintaining the phase stability at low temperature, and analyzing the performance of the composition precisely.

The present invention as described above will be described in more detail with reference to Examples, but the scope of the present invention is not limited by the following Examples.

Example 1

71.4 wt% of C9 aromatics (Techsol-100, LG Chem) generated from petrochemical process were used as the basic solvent, and 10.7 wt% of acetone and 3.6 wt% of linear alkylbenzene (LAB) were used as cosolvents. A crude combustion catalyst composition was prepared in which 4.0% by weight of isobutylene (LPB680, Daelim Industry, LPB680), 3.1% by weight of butylated hydroxy toluene, 3.5% by weight of isopropanol, and 3.7% by weight of ferrocene were prepared.

The crude combustion catalyst composition prepared as described above maintained a stable liquid phase without precipitation of precipitates even when left for 24 hours at a constant temperature maintaining condition of -15 ° C.

When maintaining the ratio of the additives except ferrocene as above, it was confirmed that the ferrocene can be dissolved while maintaining the phase stability up to 9.8% by weight based on the total weight.

Example 2

1.8 wt% polyisobutylene and butylated hydride were prepared using 42.6 wt% of benzene produced in the petrochemical process as a base solvent and 31.2 wt% of toluene and 7.8 wt% of linear alkylbenzene (LAB). A crude combustion catalyst composition was prepared containing 2.5% by weight of oxy toluene, 3.9% by weight of acetone, 2.7% by weight of isopropanol and 7.5% by weight of ferrocene.

Since pure benzene freezes at 5.5 ° C., it is essential to add co-solvents that can prevent freezing and increase the dissolving power of the additives. According to the present invention, when the weight ratio of benzene: toluene: alkyl benzene is 5: 4: 1 ~ 6: 3: 1, it was determined that a stable liquid phase can be maintained. In this embodiment, toluene and alkylbenzene are used as cosolvents. : Toluene: alkylbenzene was set to 5.4: 4: 1 by weight ratio.

The crude combustion catalyst composition prepared as described above maintained a stable liquid phase without precipitation of precipitates even when left for 24 hours at a constant temperature maintaining condition of -15 ° C.

When maintaining the composition ratio of the additives other than ferrocene as above, it was confirmed that the ferrocene is dissolved while maintaining the phase stability up to 12% by weight based on the total weight.

Example 3

71.6% by weight of mixed xylene oil (Daelim Corporation) produced in the petrochemical process was used as a base solvent, and 10.7% by weight of acetone and 3.6% by weight of linear alkylbenzene (LAB) were used as cosolvents. 2.1% by weight of hydroxy toluene, 2.7% by weight of poly (isobutylene succinimide) (manufactured by BASF), 2.4% by weight of polyisobutylene (product of Daelim Industry), 3.4% by weight of isopropanol and 3.5% by weight of ferrocene A crude combustion catalyst composition for heavy oil containing a main component was prepared.

The crude combustion catalyst composition prepared as described above maintained a stable liquid phase without precipitation precipitated even if left at least 24 hours under constant temperature maintaining conditions of -15 ° C.

The composition ratio of the additives except ferrocene was maintained as above, and the amount of ferrocene was increased to dissolve the ferrocene at a high concentration up to 8.0 wt% of the total weight, and the phase stability was confirmed.

Example 4

A crude combustion catalyst composition for heavy oil having the same structure as in Example 3 but including pure meta-xylene instead of mixed xylene fraction was prepared.

The crude combustion catalyst composition prepared as described above was confirmed to have phase stability of the composition within a range of up to 4.3% by weight of ferrocene solubility when left at -15 ° C for 24 hours or more.

Comparative Example 1

The existing crude combustion catalyst composition (Korean Patent Registration No. 10-0227965, fuel oil reforming assistant composition 1 of Example 5) containing kerosene as a base solvent and 1% ferrocene was prepared and used.

Comparative Example 2

As a reference fuel oil composition containing no crude combustion catalyst composition, a C9 aromatic fraction (Techsol-100, LG Chem) and a bunker-C oil were used in Experimental Example 4 using a solvent in a 1: 1 weight ratio.

Reference Example 1

The crude combustion catalyst composition and bunker-C oil were applied to Experimental Example 4 using a C9 aromatic fraction (Techsol-100, LG Chem) as a reference solvent that was not previously contained.

Experimental Example 1

A fuel oil obtained by mixing 1/3000 homogeneous mixtures of fuel oils by weight in bunker-C heavy oil diluted 1: 1 by weight ratio with kerosene was prepared. The extinction method was measured and compared by applying the extinction method while axially scanning the visible flame regions of, and the results are shown in Table 1 below.

division Volume fraction of the soot in the flame axis integrated along the light path (mm) Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Ferrocene content (% by weight) 3.7 7.5 8.0 4.3 1.0 Laminar diffusion oxide Value 2.487x10 ^-5 2.923 x 10 ^-5 2.890 x 10 ^-5 2.477 x 10 ^-5 2.676 x 10 ^-5 Final value 6.27 x 10 ^-7 4.57 x 10 ^-7 4.43 x 10 ^-7 5.73 x 10 ^-7 15.21 x 10 ^-7 Turbulent Mixed Flame Value 1.589 x 10 ^-6 1.641 x 10 ^-6 1.602 x 10 ^-6 1.573 x 10 ^-6 2.331 x 10 ^-6 Final value 5.67 x 10 ^-7 4.84 x 10 ^-7 5.33 x 10 ^-7 5.41 x 10 ^-7 11.72 x 10 ^-7

As shown in Table 1 above, as a result of comparing the effects on the generation and disappearance of the soot according to the content of ferrocene, the emission of the soot tended to be inversely proportional to the content of ferrocene for the same type of fuel oil. . This tendency was further aggravated by the increase in the content of heavy oil in the fuel oil samples used.

Depending on the base solvent and cosolvent, and the composition and composition of the final composition, the maximum and maximum values of the soot content vary sensitively, but the final soot content emitted from the outermost part of the visible flame is determined by the ferrocene catalyst It was found to be sensitive to content.

Experimental Example 2

Experimental Example 1 using the existing crude combustion catalyst composition prepared according to Comparative Example 1 containing kerosene as a basic solvent and containing 1% ferrocene and the new crude combustion catalyst composition prepared according to Examples 1 to 4 of the present invention. Comparison of soot generation and extinction behavior for laminar diffusion flames and turbulent mixed flames by light extinction method, but the crude combustion catalyst prepared according to Examples 1 to 4 in bunker-C fuel oil diluted 1: 1 with kerosene by weight The results of experiments on the laminar diffusion flame and the turbulent mixed flame with the composition and the crude combustion catalyst composition of Comparative Example 1 added in a weight ratio of 1/1000, 1/3000, and 1/5000 and replacing the burners are shown in Table 2 below. .

Amount of composition Unburned Carbon Amount ^* (Unit: mm) Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Laminar diffusion oxide 0 40.18 x 10 ^-7 40.18 x 10 ^-7 40.18 x 10 ^-7 40.18 x 10 ^-7 40.18 x 10 ^-7 1/1000 3.85 x 10 ^-7 4.50x10 ^-7 4.41 x 10 ^-7 3.37 x 10 ^-7 9.42 x 10 ^-7 1/3000 6.27 x 10 ^-7 4.57 x 10 ^-7 4.43 x 10 ^-7 5.73 x 10 ^-7 15.21 x 10 ^-7 1/5000 6.84 x 10 ^-7 4.85 x 10 ^-7 4.47 x 10 ^-7 6.72 x 10 ^-7 23.41 x 10 ^-7 Turbulent Mixed Flame 1/3000 5.67 x 10 ^-7 4.84 x 10 ^-7 5.33 x 10 ^-7 5.41 x 10 ^-7 11.72 x 10 ^{-7 * The} final volume fraction of unburned carbon integrated in the optical path in the thornfire

As shown in Table 2, the discharge concentration of the soot was sensitively changed depending on the amount of the supporting catalyst composition, and the soot discharge concentration of the high concentration catalyst composition according to the present invention was significantly lower than half of that of Comparative Example 1 at the same amount. It was confirmed.

Experimental Example 3

Experimental Example Using the existing crude combustion catalyst composition product prepared according to Comparative Example 1 containing kerosene as the basic solvent and containing 1% ferrocene and the new crude combustion catalyst composition prepared according to Examples 1 to 4 of the present invention. Compare the generation and extinction behavior of soot to turbulent mixed flames by light extinction method of 1, but compared to the crude combustion catalyst composition prepared according to Examples 1 to 4 in fuel oils prepared by varying the amounts of kerosene and bunker-C oil. The results of experiments by adding 1/3000 of the crude combustion catalyst composition of Example 1 by weight ratio are shown in Table 3 below.

Bunker-C additive amount (% by weight) Unburned Carbon Amount ^* (Unit: mm) Example 1 Example 2 Example 3 Example 4 Comparative Example 1 30 4.08 x 10 ^-7 3.73 x 10 ^-7 4.21 x 10 ^-7 4.23 x 10 ^-7 6.31 x 10 ^-7 50 5.67 x 10 ^-7 4.84 x 10 ^-7 5.33 x 10 ^-7 5.41 x 10 ^-7 11.72 x 10 ^-7 70 8.93 x 10 ^-7 5.62 x 10 ^-7 9.44 x 10 ^-7 9.51 x 10 ^-7 63.35 x 10 ^{-7 * The} final volume fraction of unburned carbon integrated in the optical path in the thornfire

As shown in Table 3, in turbulent mixed flames injected at a ratio of 1/3000, the effect of reducing the generation of soot as shown in Table 2 is due to an increase in the content of bunker-C heavy oil in the fuel oil used in the combustion test. It was observed to become clearer accordingly.

In other words, when the bunker-C heavy oil is 70% by weight or more, the difference in soot suppression performance is more markedly less than 10% compared to Comparative Example 1 in Example 2, and Comparative Examples in Examples 1 and 3 As compared with the case 1, it was confirmed that the soot discharge is suppressed to less than 15%.

Therefore, it was found that the worse the combustion characteristics of the fuel oil, the more prominent the catalytic combustion effect according to the present invention becomes.

Experimental Example 4

The crude oil and bunker-C oil price weight ratios of the crude combustion catalyst composition prepared according to Examples 1 and 2 were added to the fuel oil mixed with the kerosene and bunker-C oil price weight ratio 1: 1, and the crude oil and bunker-C oil price weight ratio of the existing crude combustion catalyst composition of Comparative Example 1 Samples added to fuel oil mixed with 1: 1 and kerosene and bunker-C oil containing no combustion-combustion catalyst composition and fuel oil mixed at a weight ratio of 1: 1 were used for induction system deposition (ISD). The precision carbonization test was carried out, but the surface temperature of the aluminum test rod was maintained at 300 ° C., the mixed fuel was quantitatively supplied at a flow rate of 1.0 ml per minute, and the flow rate of air supplied to the spray nozzle was 50 standard liter per minute (SLM). Was maintained. Each sample was sprayed and carbonized for 2 hours to observe the surface state of the test rod and to measure the adhesion amount.

The test results analyzing the content of each crude combustion catalyst composition and the propensity to inhibit the net adhesion amount are shown in Table 4 and the accompanying drawings of FIG. 5.

Addition ratio type 1/3000 1/5000 Theoretical value (mg) Correction value (mg) Relative value (-) Theoretical value (mg) Correction value (mg) Relative value (-) Example 1 50 48 0.533 59 57 0.633 Example 2 49 47 0.522 59 57 0.633 Comparative Example 1 56 54 0.600 56 54 0.600 Comparative Example 2 ^* 92 90 One 92 90 One Reference Example 2 - - 2 - - ^* C9 aromatic fraction (Techsol-100, LG Chem) and bunker-C oil is a result of applying to Experimental Example 4 using a base solvent mixed in a 1: 1 weight ratio.

As shown in Table 4, when the crude combustion catalyst composition is added at a ratio of 1/5000, it is confirmed that the carbon residue adhesion amount is increased compared to Comparative Example 1, which indicates that the main solvent used in the crude combustion catalyst composition In the case of the comparative example 1, it is because it is an aliphatic compound with good combustibility, whereas the example 1 and Example 2 are aromatic compounds with poor combustibility. That is, at the addition ratio of 1/5000, since the concentration of the crude combustion catalyst composition participating in the combustion process becomes very low, the secondary combustion function and the carbon deposition inhibiting function are weakened, and it is confirmed that the inverse function of the incomplete combustion of the aromatic solvent appears.

However, it can be seen that all cases tested exhibited the inhibitory effect of carbon residues compared to Comparative Example 2 without the addition of the combustion combustion catalyst composition.

In addition, when the input amount of the crude combustion catalyst composition is increased at a ratio of 1/3000, it can be seen that the carbon debris suppression performance is excellent in Examples 1 and 2 compared to Comparative Example 1. This is because when the crude combustion catalyst composition is applied at a ratio of 1/3000 which is actually applied, the effect of the high concentration of ferrocene and carbon deposition inhibitor containing the incomplete combustion tendency of the supplied aromatic solvent is sufficiently overcome to control the deposition of excellent carbon residue. The result shows that performance is achieved.

In addition, since the actual combustion catalyst composition is generally mixed with heavy fuel oil in the range of 1/1000 to 1/3000, better carbon deposition is achieved when using the combustion engine catalyst composition prepared according to the present invention as described above. Suppression performance can be exhibited.

As described above, by utilizing the technical means newly proposed by the present invention, it is possible to solubilize ferrocene, an organometallic compound which is added to the supporting catalyst composition and performs effectively, at high concentration, and especially in a low temperature environment such as winter season. By maintaining this, it is possible to exclude sources of obstacles such as path clogging that may occur in the combustion process, and to improve the mixability of the fuel oil and the crude combustion catalyst composition so as to exhibit stable product performance.

That is, not only can ferrocene be dissolved at a high concentration, but also has a wide range of phase stability zones, thereby stabilizing various functional additives of the crude combustion catalyst composition especially used in the combustion process of heavy oil, and The crude combustion catalyst composition can effectively reduce combustion dust generated when malignant heavy fuel oil is burned by efficiently secondary oxidation of unburned carbon.

In addition, according to the present invention, when applied to heavy fuel oil, the fluidity that can be injected into a large-scale combustion process is excellent, and the smoke reduction performance is excellent, and the effect of preparing a liquid catalyst composition for use in a low temperature environment including winter season is effective. have.

Claims (10)

In the combustion combustion catalyst composition for inhibiting combustion dust containing ferrocene, the combustion dust suppression agent comprising 60 to 90% by weight of an aromatic solvent as the basic solvent and 1.0 to 12.0% by weight of ferrocene as the crude combustion catalyst. Liquid crude combustion catalyst composition. The liquid crude combustion catalyst composition according to claim 1, wherein the basic solvent is a C9 aromatic fraction of a petrochemical process or an aromatic hydrocarbon mixed solvent prepared from the same. The liquid crude combustion catalyst composition according to claim 1, wherein the basic solvent is a mixed xylene fraction containing ethyl benzene and meta-xylene. The liquid crude combustion catalyst composition for inhibiting combustion dust according to claim 1, wherein the basic solvent comprises meta-xylene. The liquid crude combustion catalyst composition according to claim 1, wherein the basic solvent comprises benzene and at the same time comprises toluene and alkylbenzene. 6. The liquid crude combustion catalyst composition according to claim 5, wherein the basic solvent contains 10-25 wt% of alkylbenzene and 45-85 wt% of toluene. 7. The liquid crude combustion catalyst composition according to any one of claims 1 to 6, wherein the crude catalyst composition comprises an aliphatic solvent and an aromatic solvent together as a solvent component. The method of claim 7, wherein the supporting catalyst composition is a lower alcohol having 4 or less carbon atoms, polyisobutylene having a weight average molecular weight of 1000 or less, butylated hydroxy toluene, alkyl having at least one alkyl group having 24 or less carbon atoms. Liquid crude combustion catalyst composition for suppressing combustion dust, characterized in that it comprises benzene. The method of claim 8, wherein the supporting catalyst composition comprises 60 to 80% by weight of mixed xylene fraction, 2 to 10% by weight of alkylbenzene having at least one alkyl group of 24 or less carbon atoms, weight average molecular weight 1000 2 to 10 wt% of the following polyisobutylene, 1 to 7 wt% of isopropanol, 3 to 15 wt% of acetone, 1 to 5 wt% of butylated hydroxy toluene, A liquid crude combustion catalyst composition for suppressing combustion dust, comprising 0.5 to 5% by weight of poly (isobutylene succinimide) having a weight average molecular weight of 1200 or less and 1 to 12% by weight of ferrocene. According to claim 8, wherein the supporting catalyst composition is 35 to 50% by weight of benzene, 25 to 40% by weight of toluene, 3 to 15% by weight of alkylbenzene having at least one alkyl group of 24 or less carbon atoms, weight average molecular weight of 1000 or less 0.5 to 5% by weight of polyisobutylene, 0.5 to 5% by weight of isopropanol, 1 to 5% by weight of butylated hydroxy toluene, 1 to 5% by weight of acetone, and 1 to 12% by weight of ferrocene. Liquid crude combustion catalyst composition for suppressing combustion dust.