KR19990079234A - Additives of emulsion fuel oil - Google Patents

Abstract

The present invention relates to additives used in the production of emulsion fuel oils with low environmental pollution by stabilizing hydrolysis and improving combustion efficiency in preparing emulsion fuel oils by adding water to heavy oil or waste oil. It is intended to maintain the overall evaporation capacity with less fuel by compensating for one flame temperature drop.

Description

Additives of emulsion fuel oil

The present invention relates to an additive used to prepare emulsion fuel oil by adding water to heavy oil or waste oil. The present invention suppresses the generation of sulfur oxides (hereinafter referred to as SOx) and nitrogen oxides (hereinafter referred to as NOx) in combustion exhaust gas and generates a sold out oil. It contributes to air pollution prevention measures by reducing water, and also provides additives that can maintain chlorine efficiency in spite of hydrolysis in the fuel, and at the same time, the material is inexpensive and easily available. By adopting the substance, it is intended for the real user to promote economic benefits in many ways.

The inventor of the present invention has developed an additive of emulsion fuel oil by patent No. 31360 (1990.1.24), which compensates for the performance deterioration such as thermal efficiency and output due to hydrolysis in heavy oil combustion, and suppresses SOx and NOx. It provided a means.

The present invention has been aimed at supplementing the reduction of combustion efficiency by using vaporization power due to the combustion of magnetic iron powder in the colloidal phase for the purpose of promoting combustion, and the industrial purpose has been achieved to some extent.

The effects of additives that can lead to combustion or complete combustion can significantly reduce the generation of sold-out, NOx, and SOx, compared to no additives. However, it has been found that there are limitations in responding to the recently tightened air pollution control regulations.

In addition, the intercalation of magnetic iron oxide, which is the main ingredient in the present invention, causes long-term storage of fluctuations, such as a decrease in pH of the product, resulting in a decrease in emulsion capacity, and a cumbersome manufacturing process. I found out that there was a lack of satisfaction for the real user in the low-cost medicine manufacturing process.

The present invention has been successful in developing the above-described object to overcome the above-mentioned defects and to study the additives that can respond to the new air pollution prevention regulations.

[Means for solving the problem]

The present invention improves on the fact that the material of the former magnetic iron oxide originated from ferric sulfate. In general, it is well known as a metal that effectively oxidizes during combustion. According to the present invention, an effective material represented by equivalent amounts of Cu, Co> Mn> Fe> Ni> Pb > K> Ba in order.

The addition of iron oxides or hydroxides to Japanese Laid-Open Patent Publications 1979 (昭 -53) -125410 or 1987 (16762) 167392 for Fe among these materials lowers the incidence rate such as promoting the reduction of NOx by catalytic action during combustion. It is known to be effective in

In 1979 (昭 53) -125410, the addition of water is known to reduce NOx. In Japanese Patent Publication 1993 (平 5) -79117, it is known that the oxidation of ultra fine powdered iron oxide (Fe ₂ O ₃ ) is large and the effect of promoting combustion of unburned carbon is excellent.

In particular, it has been suggested that the effect of suppressing the oxidation of iron oxide SO ₂ -SO _{3 in the} fine powder and the occurrence of thermal NOx is great.

According to the Japanese Patent Publication No. 1993 (平 5) -60517, the presence of iron hydroxide (Fe (OH) ₂ ) greatly suppresses the generation of SOx, NOx and air pollutants due to the presence of iron hydroxide (Fe (OH) ₂ ). As suggested about the effect of suppressing the low temperature corrosion of the boiler due to the high temperature corrosion of SOE, SO ₂ , SO ₃ generation, etc., the performance of the electric invention No. 31360 has a synergistic effect of this effect and has shown its practical utility.

In the smoke and these specifications, such reductions in emissions, SOx, NOx and abatement are recorded, but no mention is made of the amount of steam generated by the flame temperature associated with boiler efficiency. According to the inventor's experience, this reduction of evaporation amount has always been encountered in the combustion of emulsion fuel. In terms of NOx suppression measures, the higher the amount of water added, the better, but the Japanese Fuel Association's VOL 57 (1978) indicates that 40% of the amount of water has a practical value, but water additions of about 30% are usually carried out. As pointed out in the specification of Prior Patent No. 31360, the flame temperature drop of about 50 ° C due to water evaporation by the injected water always leads to a shortage of steam generation, which is a serious defect that has lost the value of the emulsion fuel combustion utility surface. will be.

In the present invention, in order to reduce the SOx NOx reduction in mixing magnetic iron oxide, Mg and Ca powders were mixed and hydroxyl ((CooH) ₂ 2HO) was interposed as an oxidation enhancer, but Ba (OH) was newly added as an alkaline earth metal. Overcoming these defects by intervening ₂ minutes and interposing hexamethylenedetramine ((CH ₂ ) ₆ N ₄ and tannic acid (C ₁₆ H ₅₂ O ₄₆ ), which is used as a synthetic resin and rubber vulcanization accelerator, To achieve the desired purpose

Ba is a representative alkaline earth metal, along with Ca and Mg, and is known as an excellent material in terms of its affinity for SO ₃ and its neutralizing power. Therefore, Ba acetate is a suitable reagent for analyzing SOx in exhaust gas in KS M 2105. Emphasis is placed on the prominent substance being used, and it was prayed to cope with SOx countermeasure by adding Ba (OH) ₂ minutes to the ultra fine powder in the additive.

As is well known, Ba (OH) ₂ reacts with SO ₃ in the combustion gas (BaO + SO ₃ → BaSO ₄ ) while producing BaO in combustion to reduce the effect of sold out, resulting in BaSO ₄ (contrast of XRay). Most of them escape into the stack together with the combustion gas, but some of them remain in the combustor system in the form of BaO or BaSO ₄ to play the role of improving the furnace and preventing corrosion. It is known.

That is, BaO has a high melting point (mp) of 1923 ° C, and BaSO ₄ has a temperature of 1580 ° C. These are all low-melting heavy oil materials centered on V ₂ O-Na ₂ SO ₄ ( ) It is known as a substance that acts on slag (around 600 ℃) to increase the overall melting point and make it porous (porous) to prevent the deposition of slag of the tube.

It is not possible to clarify the factors through the substance having such an effect, but the following synergistic effect is achieved to achieve the present invention.

In the present invention, hexamethylenedetramine and tannic acid are added to additives during various experiments for the purpose of promoting the foaming of emulsion fuels. This phenomenon has been experimentally identified. This means that as mentioned in the technical data of THE ROLFITE CO, a well-known additive maker in the United States, "If the flame color is changed from red yellow to yellow bright color, it means that the flame temperature rises by about 50 ℃." It is regarded that thermal compensation is wonderfully realized by maintaining the high combustion temperature due to the decrease in flame temperature due to water. This phenomenon, of course, is thought to be enhanced by the micro-mixture of Fe, Ba, Mg, etc., which are active ingredients, according to the principle of increasing the reaction speed by increasing the specific surface area of the material.

In particular, as described above, it was clearly observed that the use of Ba (OH) ₂ did not cause the slag material to adhere to the tube surface (good heat transfer). For reference, it is known that fuel loss is more than 1.5% when 1mm of slag material is used. Therefore, it is certain that the use of this additive contributes to fuel saving.

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The emulsion fuel additive of the present invention is obtained as a precipitate through the adsorption process of naphthenic acid, oleic acid, petroleum sulfonic acid, etc., which are well known microalkaline alkali metal oxides or iron oxides. Evenly dispersed in the dissolved water medium by the intervention of surfactants such as sodium dodecylbenzene sulfonate, eliminating precipitation, flocculation and sedimentation even after long-term preservation in an extremely stable state. An additive was produced. In addition, the additive of the present invention thoroughly forms a fine powder of micron units, the surface area thereof is increased, and the physical and chemical activity is high, thereby increasing the ionization tendency of the metal, thereby facilitating catalysis (oxidation) in an ionic state at a high temperature flame. To achieve complete combustion.

This not only suppresses the generation of SOx and NOx dusts, which are air pollutants, but also improves the brightness of the flames, thereby providing thermal compensation and superheater by heavy oil mixtures such as V, Na and S. Low temperature corrosion caused by high temperature corrosion and SO ₂ SO ₃ can be greatly suppressed

[Example]

Manufacture example

The material of the present invention is made of ferric sulfate (FeCl ₃ ), which is a raw material for producing magnetic iron oxide powder, which is proposed in the previous invention patent No. 31360, and developed to meet the demands of the times by improving the process procedure. It is.

Hereinafter, the preparation example is as follows.

Prepare 300 ml of 15% MgCl ₃ aqueous solution, 350 ml of 20% BaCl ₂ aqueous solution, and 350 ml of 25% NaOH aqueous solution, form a red-mixed solution, and adjust the pH to 10 ± 0.5.

Maintaining the liquid temperature at 80 ° C. A pulverized colloid mill (PUC-60 made in Germany), which has a grinding and grinding effect of shearing, is thoroughly treated for 30 minutes in a pulverizing process to increase the specific surface area. Thus, 10 parts of naphthenic acid, 10 parts of oreic acid is slightly heated to 85 ° C to maintain sufficient adsorption at low speed to form a mixed solution of Mg and Ba.

Separately, 120 ml of ferric chloride 40% solution and 20% sodium carbonate (Na ₂ Co ₃ ) solution were kept at a mixed pH of 9-10 and thoroughly ground for 30 minutes with an electric grinding colloid mill at 80 ° C. Instead, it was prepared for the deterioration of the product.

Thus, a mixture of 7 parts of kerosene and 9 parts of kerosene sulfonic acid was injected at 85 ° C. to allow a sufficient adsorption reaction at low speed. Both of these operations are gradually aggregated over time and the solution becomes transparent, so this is filtered and the inorganic salts are removed. ) Was added to 1000 ml of a solution in which 30 g of hexamethenedetramine and 8 g of tannic acid were dissolved, and 5 parts of polydeconyl sulfonate (5 parts) polyoxynonylphenool ether (HLB 10) was stirred at low speed for 30 minutes to prepare a uniform dispersion. To complete.

Example of operation

Since the additive prepared in the above production example is stirred and injected into the additive of 200-500 branch 1 of the fuel using an appropriate emulsion emulsifier, the C heavy oil combustion is performed and the amount of NOx, SOx, and sold out generated at the outlet of the boiler air heater. Was measured and SO ₃ was measured at the economizer outlet.

Used boiler 25T / H capacity Hwaseong Boiler Co., Ltd. Burner is steam jet, regular steam pressure is 7Kg / cm ² and fuel is 1.166 ℓ / H fuel oil.

The emulsion fuel oil used was 1515 L / H (about 30% UP), of which C was 1060 L of water, 445 L of water, and 7.5 L of additive.

This mixing ratio was able to maintain the usual steam pressure as it was before.

Therefore, at 1166 ℓ / H (formerly) of the use of heavy oil, the actual consumption can keep the same evaporation output with the use of 1060ℓ, resulting in fuel savings of about 106 ℓ / H (about 9%) and the following It has been greatly improved as shown in the table.

* NOx, SO _2, SO ₃ , ppm are measured, mg / Sm ³ sold out

Claims (1)

Add Ba and Mg materials as ancillary materials for intercalating iron oxide (FeO ₃ ) for the purpose of promoting emulsion combustion fuel.Then, they thoroughly carry out the fine grinding process and the naphthenic acid, The process of sedimentation of phosphoric acid and petroleum sulfonic acid by injection adsorption sediment is carried out to obtain the filtrate. The filtrate is added to a solution containing hexamethylenedetramine and tannic acid, and dodecylbenzenesulfonic acid soda and poly Additives by adsorbing oxynonylphenool ether sufficiently to improve the stability of electric main components uniformly.