KR20010045991A - Fuel oil composition including waste edible oil - Google Patents

Abstract

PURPOSE: Provided is an environmental fuel oil composition using waste cooking oil and combustion accelerating auxiliary agents, which can be used for household heating and industrial boiler. CONSTITUTION: The fuel oil composition comprises 30-90pts.wt. of the filtered and refined waste cooking oil, 1-60pts.wt. of naphtha, gasoline, or thinner, and 0.01-10pts.wt. of low alcohol solution dissolving molybdenum compounds or caustic soda or a mixture thereof. The waste cooking oil is at least one selected from the group consisting of soya-bean oil, castor oil, cottonseed oil, coconut oil, paulownia seed oil, and fish oil.

Description

FUEL OIL COMPOSITION INCLUDING WASTE EDIBLE OIL}

The present invention relates to a fuel oil composition using waste cooking oil. More specifically, the present invention relates to a fuel oil composition which can be used as heating oil and various boiler oils by greatly reducing generation of air pollutants by adding waste cooking oil as a main component and adding a supporting component to promote combustion.

It is widely known to recycle waste oils of various edible oils such as soybean oil, corn oil, castor oil, cottonseed oil, palm oil, paulownia oil, fish oil and use them as clean fuel oil. The combustion apparatus of waste oil including waste cooking oil has a disadvantage in that a separate combustion apparatus is installed as a technique of additionally installing a blower, a carburetor, or the like in an existing combustion apparatus or a burner to burn waste oil. Examples of such a waste oil combustion apparatus are disclosed in Utility Model Publications 79-1823, 88-1676, 90-1373, 92-550 and the like.

The reaction of the spent cooking oil with methanol or ethanol under an acid or alkali catalyst yields an ester called biolight oil (or biodiesel oil), which is already known in US Pat. Nos. 4,164,506 and 4,608,202. However, this is the best way to obtain diesel (or diesel) alternatives for diesel engines, but it adds a separate transesterification process to remove by-products glycerol and fatty acids and also generates other wastes. There is a disadvantage that the manufacturing cost is expensive. Therefore, the activation of biodiesel oil requires economic support from the government and public organizations, and its use is still limited except in developed countries.

In addition, a technique for adding a combustion accelerator composed of alkali (for example, caustic soda or potassium hydroxide), magnetic iron, amine compounds, magnesium compounds, etc. to waste oil (Korean Patent Publication No. 89-2403, 89-2829, 93-4159, etc.) ) Is effective in removing sulfur oxides, but the effect of promoting combustion is not so great. Waste cooking oil is not much higher in sulfur content than diesel or kerosene distilled from crude oil. And emulsion oils made from waste oil and surfactants mixed with bunker C oil (or heavy oil) and water are well known techniques. This technology does not prevent the generation of pollutants above the environmental regulations due to the use of heavy oil, even if the use of heavy oil reduces the generation of suitable technologies or air pollutants.

It is an object of the present invention to manufacture and recycle fuel oil using waste cooking oil used as waste soap or laundry soap and animal feed, and to use it at home as a heating and industrial fuel oil at a lower cost than conventional fuel oil (kerosene or diesel). In order to reduce costs and to reduce the emissions of soot, organic compounds, nitrogen oxides, sulfur oxides and carbon monoxide than conventional fuel oils to provide an environmentally friendly fuel oil composition.

In order to achieve the above object, the present invention, (A) 30 to 90 parts by weight of filtered and refined waste oil, (B) 1 to 60 parts by weight of naphtha (petrol or thinner), (C) molybdenum compound and / or caustic soda It provides a fuel oil composition consisting of 0.01 to 10 parts by weight of a lower alcohol mixed solution containing.

In general, in the manufacture of fuel oil, waste animal and vegetable oils are usually liquid, but have high viscosity, poor ignition, and large amounts of air pollutants. Thus, the inventors have devised various methods to solve this problem. I solved the problems. That is, the present inventors have comprehensively solved problems such as high viscosity, low volatility, and low combustion of waste cooking oil itself, cost problems of the existing technologies, use of a separate device, and generation of air pollution. I tried to To this end, various combustion-promoting auxiliaries are added to the waste cooking oil, which has high flammability, flammability and combustion power, low viscosity, excellent flowability, and can be manufactured inexpensively with a simple mixer. Efforts have been made to achieve techniques for producing fuel oil compositions that are less than heating oil (kerosene or diesel). In addition, the fuel oil contains more than 60 parts by weight of waste cooking oil so that waste oil, which has been disposed or incinerated or recycled only as fertilizer, feed, and soap, can be used as an economic energy source.

The filtered and refined waste oil as component (A) may be suspended matter, food waste, at room temperature or below 60 ^o C using various filtration materials such as cotton wool, glass wool, quartz wool, filter paper or filter cloth. Simple removal of carbides and the like is used, and the filtration device may use a pressurization or pumping method to increase the filtration rate. In addition, waste cooking oil includes both vegetable oils obtained from soybeans, pizza horses, sesame seeds, cotton yarns, palms, etc., and waste animal and vegetable oils used and discarded with various animal oils such as various kinds of tallow, pork, and fish oils. However, the lower the viscosity of the heating oil as much as possible, the more advantageous and the freezing point near the room temperature or above 0 ^o C is not suitable as a fuel oil component of the present technology. Waste oil of more than 80 parts by weight has a problem of ignition in combustors such as oil boilers, and the average molecular weight of fuel is relatively large compared to heating oil (kerosene or diesel) even when forced combustion (about 3 times of diesel). There is a disadvantage in that the amount of carbon monoxide generated due to incomplete combustion increases. Therefore, the smaller the amount of waste cooking oil, the less air pollutants are generated during combustion. Various waste oils for automobile industry such as waste lubricating oil, such as waste cooking oil, which are difficult to burn because of high molecular weight, can also be applied to the present technology after filtration. The component (A) may be 30 to 89 parts by weight based on 100 parts by weight of the total composition, preferably 50 to 80 parts by weight, more preferably 60 to 75 parts by weight.

Naphtha which is the said (B) component means the light or heavy naphtha and the atmospheric distillate of crude oil. Since light naphtha is used as gasoline, which is an automobile fuel, gasoline can be used directly, and various industrial solvents (or thinners) with low toxicity as petroleum solvents can also be used. Moreover, the mixture which mixed naphtha and various organic solvents can also be used. Naphtha is a mixture of 5 to 9 carbon atoms. Its small molecular weight makes it highly volatile, helping to complex waste oils with high molecular weight and reducing air pollutants. It is preferred if naphtha and petroleum solvents are available at low cost, and the use of solvents based on naphtha is also economically desirable. However, when compared to naphtha, the thinner is mixed with oxygen-containing compounds, which helps to burn, but may increase the generation of air pollutants such as carbon monoxide and aldehydes. In the present invention, the naphtha is used 1 to 60 parts by weight, preferably 10 to 50 parts by weight based on 100 parts by weight of the total composition.

The lower alcohol mixed solution containing the molybdenum compound and / or caustic soda as the component (C) refers to a mixture prepared by selecting one or more of various molybdenum compounds and caustic soda (or sodium hydroxide). This mixture promotes the combustion of a mixture of waste cooking oil and naphtha, reduces the air pollutants such as sulfur oxides, nitrogen oxides, carbon monoxide and aldehydes, and performs a function of improving fuel efficiency by performing a complete combustion. The molybdenum compound may be used by selecting one or more selected from ammonium molybdate, sodium molybdate and phosphmomolybdic acid. Caustic soda can be easily purchased and used on the market, usually produced by the electrolytic method, and it is well known to reduce sulfur oxides and promote combustion by reacting with sulfur oxides when burning fuel oil, but there is a problem of causing corrosion due to alkali. . In addition, metal hydroxides such as potassium hydroxide, calcium hydroxide, and magnesium hydroxide, which have functions similar to those of caustic soda, may be used in combination with or replaced with caustic soda. Lower alcohol refers to methanol having 1 carbon to butanol having 4 carbon atoms, and at least one of them can be used alone or in combination. Methanol is most preferred because methanol dissolves two inorganic compounds best. Molybdenum compounds and caustic soda are water-soluble salts, which are relatively soluble in water but poorly soluble in lower alcohols. However, molybdenum compounds and caustic soda can be dissolved in small amounts in methanol and ethanol. However, methanol and ethanol, which are preferred in the present invention, are mixed well without phase separation to such a degree that they are almost transparent or nearly transparent when added in small amounts. Molybdenum compounds and / or caustic soda are added to lower alcohols such as methanol or ethanol and saturated at room temperature, and then the same amount of alcohol is added, filtered and mixed with waste cooking oil and naphtha, or dissolved at room temperature or below with saturated solubility. Can be used. In a basic study of the present invention, the solubility of ammonium molybdate and caustic soda in industrial methanol and ethanol was measured at room temperature, respectively. Ammonium molybdate was measured in about 0.1 g / 100 ml (solution volume) in methanol and in ethanol. About 0.02g / 100ml was dissolved and caustic soda was dissolved in methanol about 2.0g / 100ml and about 1.5g / 100ml in ethanol. Thus, methanol is less preferred for dissolving the two inorganic compounds used as combustion promoters, as methanol is more suitable than ethanol and the solubility in propanol and butanol is further reduced. Phosphomolybdic acid is dissolved in more than 5g per 100ml solution volume in methanol and ethanol, so 0.1g to 5g in 100ml lower alcohol can be used. However, when the alcohol solution having a high concentration of phosphomolybdic acid is used, the color of the mixture is severely changed and a precipitate is formed in the mixed fuel oil. In this case, it is preferable to filter or use a low concentration if possible. Molybdenum compounds and caustic soda mixed with fuel oil promote the combustion during combustion to increase thermal efficiency, reduce air pollutants, and remain as catalysts within the year. However, when a large amount of the alcohol mixture solution is added in the fuel oil composition of the present invention, it is preferable to use an appropriate amount because phase separation occurs or alcohol is dispersed and dissolved in the waste cooking oil and naphtha mixture. The lower alcohol saturated with the molybdenum compound and / or caustic soda as the component (C) may use 0.01 to 10 parts by weight, preferably 0.1 to 3 parts by weight, more preferably 0.5 to 2 parts by weight.

The fuel oil composition of the present invention is based on waste edible oil, and is composed of gasoline, kerosene (or petroleum), light oil, heavy oil, waste oil refined and decomposed oil, waste plastic refined and decomposed oil other than the above components, and 20: 1 to 1:20. You can mix them in any ratio. In this case, rather than using kerosene, diesel or the like, air pollutants are reduced and economically preferable. The mixture obtained by saturating an inorganic compound such as molybdenum compound and / or caustic soda in a lower alcohol is well dispersed in a waste cooking oil and a naphtha solvent mixture at 3 parts by weight or less without a surfactant, but for long-term storage or a large amount of alcohol mixed solution. If used, surfactants can be added to prevent phase separation. As surfactant, anionic, nonionic, and cationic can be used, and can be used alone or in combination of two or more. Nonionic surfactants prepared by ethoxylating alkyl, aryl and alkylaryl alcohols among the surfactants are preferred in the present invention and cationic interfaces containing amines to remove gums or sticky substances attached to soot or pipelines in the combustion chamber. The use of active agents is also preferred.

And antioxidants, cleaning agents, combustion promoters, antibacterial agents, preservatives, fluidity improvers, and metal activity inhibitors added to existing heating oils or gasoline and diesel oils (or diesel). Sediment formation inhibitors, multipurpose additives, and the like can also be added to and used in the fuel oil of the present invention.

In the process of refining the waste cooking oil of the present invention, the filtration process may use any known process, and the mixing process may also be used in any mixing device or mixing method such as a disperger, an emulsion mixer, and an impeller mixer.

The following examples illustrate and describe the present invention in detail and do not limit the present invention.

In the following examples the final physical properties of the asphalt composition were measured by the method given below.

Viscosity: Brookfield viscometer

Density: KS M 2002

Combustion Analysis: Kane-May KM9006 Combustion Analyzer, Kane International, UK

For combustion testing, purchase an oil boiler (Rinnai, model ROB 103T) on the market and place the combustion analyzer probe at the center of the flue 2 meters above the beginning of the year, three times at 1 minute intervals from 5 minutes after commencement of combustion. After the measurement, the average value was used. The concentrations of air pollutants such as sulfur oxides (SO _x ), nitrogen oxides (NO _x ) and carbon monoxide (CO) tended to decrease as the combustion operation time elapsed. It is inferred that in the early stage of combustion after ignition, the concentration of contaminants is high and then gradually decreases.

Examples 1-4

Waste cooking oil is a waste of cooking oil used in restaurants, which is obtained by filtering and refining carbonized material, food waste and other suspended substances using cotton wool. Gasoline purchased commercial gasoline engine (SK) and used for exciting paint Enamel thinner was used. The enamel thinner used is mainly toluene (or xylene). The combustion-promoting methanol solution A was prepared by adding 1 g of molybdenum compound ammonium molybdate and 5 g of caustic soda to 100 ml of industrial methanol, stirring it sufficiently, filtering with a filter paper (standard 5A), and diluting it with the same amount of methanol (100 ml). . The combustion-promoting methanol solution B used 0.2 g of phosphomolybdic acid dissolved in 100 ml of methanol without filtration.

Comparative Example 1

Kerosene used commercially available boiler kerosene (SK) for heating.

Comparative Example 2

Used cooking oil and gasoline were the same as in the examples.

Comparative Example 3

Used cooking oil and the same thing as the exciting example was used.

Table 1 shows the combustion analysis results of the fuel oil composition prepared by the present invention and commercial kerosene.

Density, viscosity and combustion analysis results according to the composition (parts by weight) of Examples and Comparative Examples Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Waste Cooking Oil 65 65 65 65 65 65 gasoline 34 34 35 excited 34 34 35 Combustion Promotion Methanol Solution A One One Combustion Accelerator Methanol Solution B One One Kerosene 100 Density (g / cm ³ ) 0.849 0.844 0.850 0.848 0.835 0.846 0.849 Viscosity (cP) 2.9 2.9 3.2 3.1 1.9 2.8 3.2 SO _x (ppm) 0 0 0 0 0 0 0 NO _x (ppm) 35 32 30 35 33 36 34 CO (ppm) 80 70 123 69 82 110 340 Combustion gas temperature ( ^o C) 192 197 198 193 186 190 185

As can be seen from the trademark Table 1, the density of the fuel oil composition according to the invention is slightly larger than kerosene but can be seen to be about the same. The dynamic viscosity measured by Brookfield viscometer is slightly larger than kerosene, but it has decreased considerably from 2.8 to 3.2 cP compared to 35.3 cP (centipoise) of waste cooking oil. There was no. Using a mixture of gasoline (or naphtha) or an enamel thinner and an alcohol mixture in which molybdenum compounds and caustic soda were dissolved as a combustion accelerator, carbon monoxide generated by waste cooking oil could be greatly reduced, which was slightly larger than kerosene (Example 3). Significantly fewer results (Examples 1, 2 and 4) were shown. Carbon monoxide, especially from waste oil and thinner mixtures (comparative 3), was greatly reduced by the combustion-promoting methanol mixtures A and B. Both sulfur oxides (SO _x ) and nitrogen oxides (NO _x ) showed similar values within the margin of error. The flue gas temperature was determined by compositions containing methanol solution in which the combustion promoter was dissolved (Examples 1 through 4), including kerosene (Comparative Example 1), waste cooking oil and gasoline (Comparative Example 2), waste cooking oil and enamel. It appears that there is a supporting effect by coming out higher than thinner (Comparative Example 3).

Therefore, the fuel oil composition of the present invention is similar to or better in environment and combustibility than commercial kerosene by using the combustion-promoting aid component. According to the present invention, the fuel oil contains more than 60 parts by weight of waste cooking oil so that it is possible to utilize waste cooking oil, which has been disposed or incinerated or recycled only as fertilizer, feed and soap, as an economic energy source.

In addition, the fuel oil according to the present invention can use a combustor such as conventional heating oil (boiler kerosene and diesel) can be used without installing a separate device.

Claims (12)

30 to 90 parts by weight of the filtered refined waste oil; 1 to 60 parts by weight of naphtha, gasoline or thinner; And A fuel oil composition comprising 0.01 to 10 parts by weight of a lower alcohol solution in which a molybdenum compound or caustic soda or a mixture thereof is dissolved. The fuel oil composition of claim 1, wherein the waste cooking oil is at least one waste animal and vegetable oil selected from the group consisting of soybean oil, castor oil, cottonseed oil, palm oil, paulownia oil, and fish oil. The method of claim 1, wherein the naphtha is a distillation of crude oil at atmospheric pressure, and includes gasoline, light naphtha, heavy naphtha and petroleum solvents (or thinners), which are used directly or in combination with other organic compounds. Milk composition. The fuel oil composition of claim 1, wherein the molybdenum compound is at least one selected from the group consisting of ammonium molybdate, sodium molybdate and phosphomolybdic acid. The fuel oil composition of claim 1, wherein the lower alcohol is at least one selected from the group consisting of methanol, ethanol, propanol and butanol. The fuel oil composition of claim 1, wherein the amount of the waste cooking oil is 50 to 80 parts by weight. The fuel oil composition of claim 1, wherein the amount of naphtha is 10 to 50 parts by weight. The fuel oil composition of claim 1, wherein the amount of the alcohol mixture solution is 0.5 to 2 parts by weight. The fuel oil composition according to claim 1, wherein the concentration of the molybdenum compound or caustic soda or a mixture thereof in the alcohol mixture solution is 0.001% to 20% by weight. The fuel oil composition of claim 1, further comprising at least one selected from the group consisting of kerosene, diesel fuel, waste oil refined oil or cracked oil and waste plastic refined and cracked oil. The fuel oil composition of claim 1, further comprising at least one selected from the group consisting of anionic surfactants, cationic surfactants, and nonionic surfactants. The fuel oil composition of claim 1, further comprising at least one selected from the group consisting of antioxidants, rust inhibitors, detergents, antibacterial agents, preservatives, fluidity improvers, metal activity inhibitors, deposit formation inhibitors, and multipurpose additives.