KR20060057558A - Method of preparing emulsified fuel from waste material - Google Patents

Abstract

The present invention relates to a method for producing an emulsified fuel using waste liquid, and more particularly, to prepare a mixed liquid by mixing a low sulfur oil and an inorganic salt composition with the waste liquid, and heating the mixture to obtain a mixed solution by applying an ultrasonic wave to a primary emulsion treatment. And a method for producing an emulsified fuel, which is prepared by mixing at high speed and performing secondary emulsification, adding an acid aqueous solution, and then filtering the same. It can be processed without causing pollution and can be manufactured as an alternative energy source, thus preventing environmental pollution and economic effects.

Waste Oil, Waste Cooking Oil, Inorganic Salt, Emulsified Fuel, Environmental Pollution, Alternative Energy

Description

METHODS OF PREPARING EMULSIFIED FUEL FROM WASTE MATERIAL}

The present invention can treat waste liquids, such as waste oils and cooking oils, generated at various industrial sites and homes without causing environmental pollution, and can be manufactured as raw materials of alternative energy, using waste liquids that can prevent environmental pollution and obtain economic effects. It relates to a method for producing an emulsified fuel.

Alternative energy is classified into solar energy, biomass, wind power, hydropower, fuel cell, coal liquefaction, gasification, marine energy, waste energy and other than coal, petroleum, nuclear power and natural gas. It means the flowable fuel mixed with the material by.

Among them, waste energy refers to the processing of oil with high energy content among the combustible wastes generated at the workplace or home by pyrolysis, manufacturing solid fuel, technology for manufacturing flammable gas by gasification, and heat recovery by incineration. It refers to renewable energy that produces solid fuels, liquid fuels, gaseous fuels, waste heat, etc. through treatment methods and makes them available as energy for industrial production activities. Such waste energy can be commercialized in a relatively short period of time, and it is possible to solve the waste environmental problem that threatens human rights by utilizing waste resources as active energy resources.

Waste alternative energy is used for ionization, pyrolysis and purification of waste oils such as solid fuel (RDF) automobile waste lubricating oil, which is a solid fuel manufactured by shredding, separating, drying and molding combustible wastes such as paper, wood and plastic. Steam generation and power generation by recovery of incineration heat from plastic pyrolysis fuel oil and flammable waste oil, which is a clean fuel oil produced by pyrolysing polymer waste such as recycled oil, refining oil, plastic, synthetic resin, rubber and tires It is mainly divided into four types of waste incineration heat used as heat sources such as cement kiln and iron ore kiln.

Regarding the waste oil refined oil, which is one of the alternative waste energy, the amount of waste oil is estimated based on the sales volume of new oil, which is usually sold for application to automobiles or industrial fields, and is set at 70% of sales volume in Korea. Since these waste oils are not consumables unlike general fuel oils, they can be used as useful resources, and thus, they have been studied for their efficient use from early days, and many of them are recycled as regenerated refined oils or fuel oils.

However, these waste oils may contain heavy metal compounds such as Pb, Cd, Cr, Cu, Zn, chlorine compounds such as Cl and Br, sulfur compounds, etc. due to their own decomposition or external contamination. When exposed, organic acids can form due to oxidation of the waste oil, which can lead to ecological disasters such as soil degradation and groundwater contamination.

Along with the waste oil, waste oil of the final sludge form from the noodle factory, waste oil of the sludge form when cooking oil, waste oil of the sludge discharged from a soap plant, sludge waste of various fried or fried chicken The treatment of waste cooking oils, such as cooking oil, is also a major problem in terms of environment and ecology.

Korean Patent Laid-Open Publication No. 99-70659 (published date, September 15, 1999), "Fuel Recovery Method of Waste Oil and Its Regeneration Apparatus" allows ions formed by a functional ceramic installed with a magnet to act on the molecules of the waste oil. The present invention relates to a method and apparatus for regenerating diesel fuel by raising the negative potential of the molecule by activation, which merely lowers the viscosity of waste oil suitable for a diesel engine. In addition, since the waste oil having a low viscosity is filtered by a conventional filter, there is a risk of damaging the engine and environmental pollution due to incomplete combustion.

Republic of Korea Patent Publication No. 99-79052 (published date, November 5, 1999) "method and apparatus for the regeneration treatment of waste cooking oil" to remove the impurities using a filter, and to add esters by adding alkaline substances as methanol and catalyst After removal of free alkali and debris by natural precipitation, water is mixed to separate methyl ester and glycerin. And finally, by heating to a predetermined temperature to evaporate the water, and through the purification process to make a fuel. However, high-viscosity waste cooking oil is filtered through a conventional filter, and impurities are still present, and depending on natural phenomena such as esterification, separation of methyl ester and glycerin, and purification process, the processing time becomes longer and productivity is lowered. There is a problem.

It is an object of the present invention to treat waste oils and cooking oils generated in various industrial sites and homes without causing environmental pollution, and to manufacture emulsified fuel which is a raw material of alternative energy to prevent environmental pollution and to obtain economic effects. It is to provide a manufacturing method.

In order to achieve the above object, the present invention

a) mixing the low sulfur oil and inorganic salt composition in the waste liquid and heating to prepare a mixed liquid,

b) vacuum mixing while applying ultrasonically to the obtained mixture, and performing primary emulsion treatment,

c) secondary emulsification by mixing at high speed;

d) provides a method of producing an emulsified fuel comprising the step of adding an aqueous acid solution and then filtering.

Hereinafter, the present invention will be described in more detail.

The method according to the present invention produces an emulsified fuel which is a raw material of alternative energy without causing environmental pollution in treating waste oils and cooking oils generated at various industrial sites and homes in the related art, thereby obtaining environmental pollution prevention and economic effects. The emulsified fuel has excellent dispersion stability even without using an emulsifier, which is essentially used to prevent oil and oil separation of oil fuel, so that oil and water separation does not occur for a long time.

Hereinafter, the method for producing an emulsified fuel according to the present invention will be described for each step.

Step a) Mixing Step

In step a), the waste liquid containing waste oil and / or waste cooking oil to be treated in the reactor and the low sulfur oil and the inorganic salt composition are mixed at a constant ratio, and then heated to a high temperature.

The waste liquid may be used waste oil and waste cooking oil discharged from various industrial facilities and homes. In this case, waste oil refers to engine waste oil, gear oil waste oil, and waste oil from cutting tools that are discharged from various vehicles and ships, but it is generally impossible to separate and collect, and it is difficult to store and transport crude oil sludge waste oil of refinery. And the like. The waste cooking oil is waste oil of the final sludge form from the noodle factory, waste oil of sludge form when cooking oil, waste oil of sludge discharged from a soap factory, sludge waste from various fried or fried chicken Cooking oil and the like.

The waste oil and the waste cooking oil are used to remove impurities by pretreatment, for example, to remove impurities using a filter press.

The low sulfur oil is preferably a fuel containing less than 1% sulfur. Since sulfur in low sulfur oil is converted to sulfur oxide which is the main cause of environmental pollution after combustion, it is preferable to use a fuel containing less sulfur if possible.

Wherein the inorganic salt composition NaCO ₃ 20 to 80 parts by weight based on 100 parts by weight of water, NaHCO ₃ 10 to 20 parts by weight, CaCl ₂ 50 to 90 parts by weight, NaCl 10 to 90 parts by weight, and MgCl ₂ 50 to 80 parts by weight Include. The inorganic salt composition has a basic alkali metal chloride by a chemical reaction when mixed with the waste liquid of the waste oil or waste cooking oil in which a higher fatty acid ester is present to act as an emulsifier. As a result, water and waste oil (oil component) naturally form an emulsion to prevent oil-water separation for a long time without using an emulsifier.

In the present invention, 50 to 150 parts by weight of low sulfur oil, preferably 80 to 120 parts by weight, and 50 to 150 parts by weight of inorganic salt composition, preferably 80 to 120 parts by weight, based on 100 parts by weight of waste liquid.

In this case, the mixing may be performed at 70 to 100 ° C. for 0.5 to 1 hour to form a uniform mixed solution.

Step b) Ultrasonic Application Primary Emulsification

In step b), the mixed solution containing the waste liquid, the low sulfur oil and the inorganic salt composition is stirred at 70 to 100 ° C. under a reduced pressure of 0.01 to 0.5 torr to perform a primary emulsification process.

Through the emulsification treatment, the specific gravity of the mixed solution is lowered, so that the mixing is performed well, and ionic bonds between the water, the inorganic salt, and the waste liquid (oil component) in the mixed solution are effectively formed, and thus a uniform emulsion can be obtained without the occurrence of oil and water separation.

At this time, the primary emulsification treatment should maintain an effective pressure and the proper rotation speed of the rotary blade, it is preferable to perform a strong stirring at a speed of 100 to 200 rpm for 0.1 to 2 hours under the pressure, specific conditions of the reactor It can be varied according to various experimental conditions such as size, stirrer performance and content of composition to be treated, and can be controlled within the above range by a person skilled in the art.

At this time, 10 ~ 40KHz, 100 ~ 3000W ultrasonic waves are applied to increase the emulsification. The application of ultrasonic waves promotes the molecular motion of the waste oil to be pulverized into smaller particles as well as to increase the ionic binding capacity of the inorganic salts to achieve a more uniform emulsion.

Step c) secondary emulsification

In step c), the mixed liquid obtained by the primary emulsification treatment is mixed at high speed to prepare the liquid fuel by secondary emulsification treatment.

Emulsification that mixes at 1,000 to 3,000 rpm, more preferably at 1,500 to 2800 rpm, to pulverize the water particles in the fuel and the particles of the waste liquid (oil components) to a smaller dispersion, resulting in a uniform dispersion and no oil-water separation for a long time. Manufacture fuel.

At this time, the secondary emulsification is performed at the same temperature as the primary emulsification, or at 70 to 100 ° C.

Step d) Add acid aqueous solution and filter

In step d), an acid aqueous solution having a pH of 3.0 to 5.5 is added to the secondary emulsion-treated liquid fuel, and then filtered through a column packed with an adsorbent to prepare an emulsion fuel according to the present invention.

Free fatty acids are easy to oxidize and deteriorate, and once deteriorated, the kinematic viscosity of the fuel rises and peroxides are generated, resulting in lower fuel efficiency. Accordingly, in the present invention, the pH is adjusted by adding an acid aqueous solution to the liquid fuel, and then passed through a column filled with an adsorbent to remove free fatty acids contained in the fuel.

The acid aqueous solution has a pH of 3.0 to 5.5 and is prepared using at least one acid selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid and acetic acid. At this time, the acid aqueous solution and the liquid fuel is preferably mixed in a volume ratio of 1: 0.5 to 0.5 to 1.

The filtration uses a column packed with a conventional adsorbent, preferably chitosan. At this time, chitosan can be purchased and used commercially available, it is used in the form of powder, granules or pellets.

The adsorbent can easily adsorb the free fatty acid contained in the liquid fuel, and can produce a higher purity emulsified fuel by adsorbing various heavy metals.

The emulsified fuel according to the present invention prepared as described above does not generate oil and water segregation even when stored for a long time without using an emulsifier, which is distinguished from that in which conventional emulsified fuels essentially use an emulsifier to secure water stability. do. In addition, the emulsified fuel is very high purity to remove heavy metals, including free fatty acids, containing less than 1.0% by weight of sulfur in the total composition. In addition, the specific gravity is 0.88 to 0.97, the kinematic viscosity of 200 to 350 cp (40 ℃), the calorific value of 9,600 to 12,000 kcal / kg, it can be preferably used as an emulsified fuel showing a bright red flame during combustion.

As described above, the emulsified fuel according to the present invention is used for heating of facility oils, such as fuel oil for boilers, glass greenhouses and vinyl houses, for baths, cogeneration plants, thermal power plants, ceramic products manufacturing plants, cement manufacturing plants, and other industrial heating plants. It can be used as fuel oil and fuel oil for home heating.

Hereinafter, preferred examples are provided to aid in understanding the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited by the examples.

Example 1

The waste cooking oil was passed through a filtration apparatus to remove impurities, and then 10 kg was injected into a mixer equipped with a temperature controller and an agitator. 8 kg of bunker C oil and 6 kg of an inorganic salt composition were injected thereto, followed by mixing at 80 rpm for 30 minutes at 100 rpm to prepare a mixed solution. At this time, as the inorganic salt composition, a mixture of 150 g of NaCO _3, 150 g of NaHCO ₃ , 400 g of CaCl ₂ , 100 g of NaCl, and 400 g of MgCl ₂ was used as the inorganic salt composition.

The mixed solution was transferred to a reactor equipped with a vacuum apparatus and subjected to primary emulsification by stirring at 150 rpm for 10 minutes at 0.5 torr and 80 ° C. while applying an ultrasonic wave of 30 kHz. Subsequently, high-speed stirring was performed for 30 minutes at 1500 rpm at the same temperature under normal pressure to obtain a liquid fuel by secondary emulsification.

Next, an aqueous hydrochloric acid solution having a pH of 4.0 was added to the liquid fuel in a volume ratio of 1: 1, followed by stirring, and then an emulsified fuel according to the present invention was prepared by passing a column filled with chitosan.

Experimental Example 1: Measurement of Physical Properties

Physical properties were measured to see if the emulsion fuel prepared in Example 1 can be used as a fuel. As a result, the content of sulfur (S) was 0.8% by weight and the calorific value was 99,000 kcal / kg, which satisfies the standard of emulsified fuel proposed by the Waste Management Act Enforcement Regulation (Ministry of Environment Notice No. 97-77). In addition, specific gravity was 0.92 and kinematic viscosity was measured at 287 cp (40 ℃).

Experimental Example  2: storage stability measurement

In order to determine the storage stability of the emulsified fuel prepared in Example 1, the emulsified fuel was left for 90 days at -10 ℃, 5 ℃ and 45 ℃ each was visually confirmed whether the separation of oil and water obtained the following Table 1 Shown in

 10 days later  60 days later  90 days later  -10 ℃  ◎  ◎  ○  5 ℃  ◎  ◎  ◎  45 ℃  ◎  ◎  ◎    Storage stability ◎: No precipitation, ○: Good △: Partial precipitation occurs ×: Precipitation occurs

Referring to Table 1, the emulsified fuel according to the present invention has no oil-water separation for 90 days, no sediment is generated, and the emulsified fuel according to the present invention has excellent dispersion and storage stability without using an emulsifier. It was confirmed.

Therefore, according to the present invention, after mixing waste liquid, low sulfur oil, and inorganic salt composition, primary and secondary emulsification treatment and purification were performed to prepare an emulsified fuel that does not generate oil and water separation even after long-term storage without using an emulsifier. The emulsified fuel can be used as a substitute for various fuels, and thus, waste oils generated at various industrial sites and homes can be used as raw materials for alternative energy without causing environmental pollution.

Claims (14)

a) mixing the low sulfur oil and inorganic salt composition in the waste liquid and heating to prepare a mixed liquid, b) vacuum mixing while applying ultrasonically to the obtained mixture, and performing primary emulsion treatment, c) secondary emulsification by mixing at high speed; d) a method of producing an emulsified fuel comprising the step of filtration after adding an acid aqueous solution. The method of claim 1, The emulsified fuel has a sulfur content of less than 1% by weight, specific gravity of 0.88 to 0.97, the calorific value is 9,600 to 12,000 kcal / kg manufacturing method of the emulsified fuel. The method of claim 1, The emulsified fuel has a kinematic viscosity of 200 to 350 cp (40 ℃), the calorific value is 9,600 to 12,000 kcal / kg manufacturing method of the emulsified fuel. The method of claim 1, The waste liquid is a method of producing an emulsified fuel to further perform a step of removing impurities using a filter press before step a). The method of claim 1, The mixed solution of step a) comprises 50 to 150 parts by weight of low sulfur oil, and 50 to 150 parts by weight of inorganic salt composition with respect to 100 parts by weight of waste liquid. The method of claim 1, The waste liquid of step a) is a method of producing an emulsified fuel to remove impurities by pre-treating waste oil and waste cooking oil discharged from various industrial facilities and homes. The method of claim 1, The low sulfur oil is a method for producing an emulsified fuel containing less than 1% sulfur. The method of claim 1, Wherein the inorganic salt composition NaCO ₃ 20 to 80 parts by weight based on 100 parts by weight of water, NaHCO ₃ 10 to 20 parts by weight, CaCl ₂ 40 to 90 parts by weight, NaCl 10 to 90 parts by weight, and MgCl ₂ 40 to 80 parts by weight Method for producing an emulsified fuel containing. The method of claim 1, Step a) is a method of producing an emulsified fuel that is carried out at 70 to 100 ℃. The method of claim 1, Wherein step b) is carried out under reduced pressure of 0.01 to 0.5 torr at 70 to 100 ℃. The method of claim 1, Wherein step c) is carried out under a stirring speed of 1,000 to 3,000 rpm method of producing an emulsified fuel. The method of claim 1, The acid solution of step d) is a method of producing an emulsified fuel having a pH of 3.0 to 5.5. The method of claim 1, The acid aqueous solution of step d) is a method of producing an emulsified fuel containing at least one acid selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid and acetic acid. The method of claim 1, Filtration of step d) is carried out by passing through a column filled with chitosan emulsified fuel production method.