KR102217064B1 - Biodiesel purification system capable of performing cleaning or replacement determination of tablet resins using electrical conductivity - Google Patents

Abstract

The present invention relates to a biodiesel purification system which performs purification of impurities, such as a catalyst, methanol and glycerin contained in biodiesel, by using a resin for purification, after the production of biodiesel, and carries out cleaning or replacement of the resin for purification through the determination of the contamination of the resin for purification by using electrical conductivity during the purification. The biodiesel purification system which allows determination of cleaning or replacement of a resin for purification using electrical conductivity according to the present invention increases the production rate of biodiesel through the determination of the timing of the replacement by using electrical conductivity, produces high-purity biodiesel, and performs purification of biodiesel with the resin for purification many times to provide high biodiesel purification efficiency. In addition, two purification tanks are provided in each purification unit, and when one purification tank cannot work, purification can be performed continuously by using the other purification tank. Further, cleaning of the resin for purification with methanol and removal of methanol remaining in the cleaned resin for purification with biodiesel can be carried out with ease, thereby facilitating the cleaning of the resin for purification.

Description

Biodiesel purification system capable of performing cleaning or replacement determination of tablet resins using electrical conductivity}

In the present invention, catalysts and non-sulfur substances such as glycerin contained in biodiesel prepared after biodiesel are prepared are purified using a purification resin, and contamination of the purification resin is measured using electrical conductivity in the purification process. It relates to a biodiesel purification system capable of performing washing or replacement determination of a purification resin using electrical conductivity for washing or replacing of.

Petroleum is produced as a raw material such as lubricating oil, naphtha, liquefied petroleum gas, gasoline, diesel, heavy oil, and asphalt, and is used for various purposes across all industries, but with the organization of petrileum exporting contries (OPEC). The estimated reserves of non-member countries are 1.3 trillion barrels, which can be mined for about 50 years, and due to climate change and environmental pollution caused by oil depletion and carbon dioxide emissions that occur in the future, de-oil policies are taking place around the world. Accordingly, while replacing petroleum, the development of eco-friendly alternative energy is actively taking place.

As a representative alternative energy for fossil fuels, biodiesel is a biofuel that will replace diesel, and unlike diesel, it is an oxygenated fuel containing about 10% oxygen. Due to the oxygen contained in biodiesel during combustion Since more complete combustion occurs, air pollutants are emitted more than 40-60% less than diesel, attracting attention as an eco-friendly fuel and alternative energy for petroleum.

Biodiesel is a representative eco-friendly energy that replaces diesel by processing fat components of plants or animals into similar physical properties to diesel, and its manufacturing technologies include alkali catalyst method, acid catalyst method, lipase enzyme reaction method, and supercritical methanol method. The manufacturing technology used is a process of producing purified fatty acid methyl ester through esterification after adding alcohol to oil extracted from plants by an alkali catalyst method.

In more detail, it is converted into ester and glycerol by reacting alcohol with vegetable oil or animal fat. In the presence of an alkali catalyst, the bond between carbon and oxygen bonded to carbon among the C=O bonds of triglycerides is broken, and the CH3O- group of methanol is It is a fatty acid methyl ester prepared by transesterification method in which vegetable oils and fats are bonded to carbon of C=O. A catalyst, methanol, and fat (raw material) are introduced into the reactor and prepared through separation (glycerin), neutralization, and purification processes. The catalyst used at this time can be both an acid catalyst and a base catalyst, but a basic catalyst with excellent reaction activity It has been used, and is produced by reacting a lower alcohol and fat and oil under a homogeneous catalyst of a strong base such as potassium hydroxide or a strong acid such as sulfuric acid.

On the other hand, biodiesel crude oil prepared by the above-described methods contains impurities such as methanol, ethanol, catalyst, and glycerin used for the chemical reaction process, so it is difficult to use it as a raw material. Therefore, it is used after satisfying the usable quality standards by performing a process of purifying the manufactured biodiesel.

Purification of biodiesel includes water washing, distillation, adsorbent, chemical treatment, and so on.Since water washing uses water, the process is complicated and time-consuming, and it has disadvantages that a large amount of wastewater is generated. Purification has problems such as installation of a distillation device and complicated distillation. On the other hand, purification using an adsorbent removes several impurities at the same time and has the advantage of not generating wastewater, but has a problem in that it is difficult to determine the timing of washing or replacing the adsorbent.

On the other hand, in the case of fats and oils (raw materials) mentioned above, high acids and raw materials such as waste cooking oil or food are used, so refined materials for removing foreign substances in the raw materials, increasing the catalytic reaction rate, and decoloring are used in biodiesel production. Looking at the prior art, Korean Patent Registration No. 10-0798605 (January 28, 2008) decolorizes crude biodiesel under a heterogeneous adsorbent, removes foreign substances, and maintains colored raw materials that perform refining processes to increase the content of fatty acid alkyl esters. In the manufacturing process of biodiesel, a method for purifying biodiesel using a heterogeneous adsorbent is provided, and Korean Patent No. 10-1285828 (2013.07.12.) provides a biodiesel raw material oil having a high acid value and low fatty acids that does not cause saponification. It provides a pretreatment method for biodiesel raw material oil comprising a step of reacting at 30 ~ 150°C by simultaneously adding a buffer solution and an adsorbent, and removing the buffer solution and an adsorbent after the reaction is completed. No. 10-0831072 (2008.05.20.) relates to a purification method during the manufacturing process of biodiesel from oils and fats. More specifically, crude biodiesel in which excess alcohol is removed and glycerin is sufficient. heterogeneous can extinguisher (H ⁺⁾ and hydroxyl groups (OH ^-) under the catalyst removal step of the neutralization step, a monovalent or divalent metal ion (K ^+, NA ^+, Ca ^{2 +,} Mg ^{2 +)} of, and the glycerol It provides a method for purifying biodiesel using a heterogeneous catalyst comprising a removal step.

Looking at the above prior art, when producing biodiesel, an adsorbent is used as a purification material to remove foreign substances, decolorize and remove foreign substances from colored raw materials, or prevent saponification in the biodiesel production process using an adsorbent. However, since contamination of the adsorbent occurs in a system in which biodiesel production is continuously performed, there is a problem that the adsorbent or refining material must be replaced periodically, but the timing of determining the replacement is unclear.

Korean Patent Registration No. 10-0798605 (January 28, 2008) Korean Patent Registration No. 10-1285828 (2013.07.12.) Korean Patent Registration No. 10-0831072 (2008.05.20.) Korean Patent Registration No. 10-1314133 (2013.10.04.)

The technical problem to be achieved by the present invention is that the biodiesel produced through the esterification or transfer esterification process contains methanol or ethanol, a catalyst, and a small amount of glycerin, so it is difficult to use immediately and therefore has to undergo an additional purification process. To solve the problem that it is difficult to determine whether the adsorbent is contaminated during the purification process, it is to provide a biodiesel purification system capable of washing or replacing a resin for purification using electrical conductivity using electrical conductivity.

In order to solve the above problems and achieve the object, a biodiesel purification system capable of washing or replacing a purification resin using electrical conductivity according to an embodiment of the present invention is the first storage system containing biodiesel. Tank (V-301), the first purification unit (R-302, R-303), the first purification unit is filled with resin for purification, and biodiesel is introduced from the first storage tank (V-301) The second storage tank (V-304) into which the biodiesel first purified from the purification units (R-302, R-303) is introduced, is filled with resin for purification, and from the second storage tank (V-304). The second purification unit (R-305, R-306) into which biodiesel is introduced, and a third storage tank into which the second purified biodiesel is introduced from the second purification unit (R-305, R-306) (V-307), a biodiesel tank (V-308) into which purified biodiesel is introduced from the third storage tank (V-307), and the first purification unit (R-302, R-303) When the refining resin filled in the secondary refining section (R-305, R-306) is contaminated, methanol is added to wash the refining resin, and the methanol tank (V-309) storing the input methanol is And the determination of the cleaning and replacement of the refining resin is performed by sensing electrical conductivity inside the first storage tank (V-301), the second storage tank (V-304), and the third storage tank (V-307). Sensors are attached and installed, and after biodiesel is filled in each tank, the voltage recognized by applying a power of 9V is measured and the measured value is stored in the database as a reference value. If the measurement is high compared to the reference value, the resin for purification filled in the first purification unit (R-302, R-303) and the second purification unit (R-305, R-306) is washed or replaced.

The first purification unit (R-302, R-303) and the second purification unit (R-305, R-306) consist of two purification tanks, respectively, so that one purification tank cannot be used for biodiesel purification. Alternatively, when washing or replacing the resin filled in one purification tank, the biodiesel process may be performed with the other.

The refining resin is a polymer resin, and at least one selected from activated clay, zeolite, activated carbon, bentonite, silicalite, vermiculite, and potassium silicate may be added and used.

The purification resin is washed from the methanol tank (V-309) storing methanol. The first purification units (R-302, R-303) and the second purification units (R-305, R) need to be washed. Wash by passing methanol through the purification tank of -306).

The refining resin after washing is removed by injecting biodiesel stored in the third storage tank (V-307) into methanol remaining in the refining resin during the washing process, and the biodiesel used at this time is a separation tank (E-351). ), and then sent to the first storage tank (V-301), and the methanol used in the washing process and the separated methanol are sent to the methanol tank (V-309) for reuse.

Glycerin discharged during the cleaning process of the refining resin is sent to a glycerol tank (V-353).

Methanol was vacuum evaporated from the used methanol and glycerin flowing into the separation tank (E-351) to separate methanol, and the separated methanol was stored in a separation methanol storage tank (V-352), and then a methanol tank (V-309). ) And reused, and the biodiesel remaining after methanol removal is sent to the first storage tack (V-301) for reuse, and the glycerin precipitated at the bottom is sent to the glycerol tank (V-353). Provides a biodiesel purification system capable of performing cleaning or replacement determination of resin for purification.

As described above, the biodiesel purification system capable of performing washing or replacement determination of the purification resin using electrical conductivity according to the present invention has the following effects.

(1) In the present invention, the biodiesel production rate is increased by grasping the replacement timing of the refining resin using electrical conductivity, and high purity biodiesel is produced.

(2) In the present invention, biodiesel purification efficiency is high by performing the process of purifying biodiesel with a refining resin multiple times, and when a purification tank is not available, the other The purification process can be continuously performed using.

(3) In the present invention, the process of washing the resin for purification with methanol and removing methanol remaining in the washed resin for purification with biodiesel is simple, so that the washing process of the resin for purification is conveniently performed.

1 is a flow chart of a biodiesel purification system capable of performing washing or replacement determination of a purification resin using electrical conductivity according to a preferred embodiment of the present invention.
2 is a perspective view illustrating the shape of an electrical conductivity sensor according to an embodiment of the present invention.
3 is a perspective view illustrating an apparatus of a biodiesel purification system according to a preferred embodiment of the present invention.
4 is a plan view illustrating an apparatus of a biodiesel purification system according to a preferred embodiment of the present invention.
5 is a front view illustrating an apparatus of a biodiesel purification system according to a preferred embodiment of the present invention.
6 is a rear view illustrating an apparatus of a biodiesel purification system according to a preferred embodiment of the present invention.
7 is a cross-sectional view and a plan view illustrating an apparatus of a biodiesel purification system according to a preferred embodiment of the present invention.

The name of the present invention is "a biodiesel purification system capable of performing cleaning or replacement determination of a purification resin using electrical conductivity", and detailed contents are described so that the skilled person can easily understand, and a separate description that can be sufficiently inferred is omitted. If necessary, examples and drawings are described. In addition, terms defined in the present specification and claims are not limited to interpretation, and may vary according to the intention or custom of the operator, and should be interpreted as meanings and concepts consistent with the technical idea of the present invention.

As used herein, the meaning of "comprising" specifies a specific characteristic, region, integer, step, action, element and/or component, and other specific characteristic, region, integer, step, action, element, component and/or It does not exclude the presence or addition of the military.

All terms including technical and scientific terms used in the present specification have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. The terms defined in the dictionary are additionally interpreted as having a meaning consistent with the related technical literature and the presently disclosed content, and are not interpreted in an ideal or very formal meaning unless defined.

In one aspect of the present invention,

1 is a flow chart of a biodiesel purification system capable of performing washing or replacement determination of a purification resin using electrical conductivity according to a preferred embodiment of the present invention, and FIG. 3 is a biodiesel purification system according to a preferred embodiment of the present invention. A perspective view illustrating an apparatus of a purification system, FIG. 4 is a plan view illustrating an apparatus of a biodiesel purification system according to a preferred embodiment of the present invention, and FIG. 5 is a biodiesel purification system according to a preferred embodiment of the present invention Is a front view illustrating an apparatus of, FIG. 6 is a rear view illustrating an apparatus of a biodiesel purification system according to a preferred embodiment of the present invention, and FIG. 7 is a biodiesel purification system according to a preferred embodiment of the present invention. The biodiesel purification system of the present invention will be described in detail below with reference to FIGS. 1 and 3 to 7 with a cross-sectional view and a plan view illustrating an apparatus (tank) of the first and second purification units in the apparatus.

In a purification system for purifying biodiesel produced through an esterification process with a resin for purification,

The purification system

The first storage tank (V-301) containing biodiesel for the first time, the first purification unit (R-302, R) filled with refining resin, and into which biodiesel is introduced from the first storage tank (V-301). -303), a second storage tank (V-304) into which the first purified biodiesel is introduced from the first purification unit (R-302, R-303), a resin for purification is filled, and the second Secondary purification units (R-305, R-306) into which biodiesel is introduced from the storage tank (V-304), and the bio-purified from the second purification units (R-305, R-306) A third storage tank (V-307) into which diesel is introduced, a biodiesel tank (V-308) into which purified biodiesel is introduced from the third storage tank (V-307), and the first purification unit (R- 302, R-303) and the second purification unit (R-305, R-306) are contaminated when methanol is added to wash the resin for purification. Consists of including a methanol tank (V-309),

For the determination of washing and replacement of the resin for purification, an electric conductivity sensor is attached and installed inside the first storage tank (V-301), the second storage tank (V-304), and the third storage tank (V-307). After the biodiesel is filled in each tank, a power of 9V is applied to measure the recognized voltage, and the measured value is stored in the database as a reference value.

Subsequently, if the measured value during biodiesel purification is measured higher than the reference value, the tablets filled in the first purification unit (R-302, R-303) and the second purification unit (R-305, R-306) Wash or replace the solvent.

Looking again at the biodiesel purification system, a first purification unit (R-302) consisting of two purification tanks filled with a resin for purification in a first storage tank (V-301) in which biodiesel produced through an esterification process is stored. , R-303), after primary purification with refining resin, injecting into the second storage tank (V-304), and the two filled with refining resin in the second storage tank (V-304). It is injected into the second purification unit (R-305, R-306) consisting of four purification tanks, is then sent to the third storage tank (V-307), and finally purified biodiesel is delivered to the biodiesel tank ( V-308).

2 is a perspective view illustrating the shape of an electrical conductivity sensor according to a preferred embodiment of the present invention. The first storage tank (V-301), the second storage tank (V-304) and the third storage tank (V -307) has an electric conductivity sensor installed inside. When the electric conductivity sensor applies a voltage of 9V to the biodiesel, the biodiesel containing no impurities is recognized as close to 0V. Therefore, in the process of purifying a new biodiesel for purification, if the measured value is high compared to the value measured during the previous biodiesel purification, the resin for purification is washed or replaced.

In addition, the electric conductivity detection sensor is provided with a detection sensor at the lower end of the plurality of frames, and the shape of the detection sensor may be a rectangular parallelepiped, a circular shape, or various shapes.

The refining resin is washed by sending methanol from the methanol tank (V-309) to the first purification units (R-302, R-303) and the second purification units (R-305, R-306). Impurities remaining in the refining resin are removed, and methanol remaining in the refining resin in the process of washing the refining resin is removed with biodiesel in the third storage tank (V-307).

The first purification unit (R-302, R-303) and the second purification unit (R-305, R-306) consist of two purification tanks, respectively, so that one purification tank cannot be used for biodiesel purification. Alternatively, when washing or replacing the resin filled in one purification tank, the biodiesel process may be performed with the other.

It has been described that the first purification units R-302 and R-303 and the second purification units R-305 and R-306 are provided with two purification tanks, but it may be composed of a plurality of three or more, If one of the purification tanks is difficult to use, the remaining purification tanks are used to purify the biodiesel.

The refining resin is a polymer resin, and at least one selected from activated clay, zeolite, activated carbon, bentonite, silicalite, vermiculite, and potassium silicate may be added and used.

The resin for purification and the mixture to be added have a particle size of 0.1 to 30 mm, and 1 to 30% by weight of fats and oils (raw materials) or fats and fats mixed with methanol (raw materials) are used. When the mixing ratio is less than 1%, the effect of the refining resin is insufficient, and when the mixing ratio is more than 30%, the amount of biodiesel production is reduced.

The purification resin is washed from the methanol tank (V-309) storing methanol. The first purification units (R-302, R-303) and the second purification units (R-305, R) need to be washed. Wash by passing methanol through the purification tank of -306).

The refining resin after washing is removed by injecting biodiesel stored in the third storage tank (V-307) into methanol remaining in the refining resin during the washing process, and the biodiesel used at this time is a separation tank (E-351). ), and then sent to the first storage tank (V-301).

Methanol after washing of the refining resin is sent to a separation tank (E-351) to remove impurities and reuse. The biodiesel used to remove methanol remaining in the refining resin is used in a separation tank (E-351). After separating from methanol, it is sent to the first storage tank (V-301) and used after purification.

Looking at the separation of methanol, biodiesel, and glycerin in the separation tank (E-351) in more detail, after washing the resin for purification with methanol, the methanol used for washing is sent to the separation tank (E-351). In the tank (E-351), not only methanol, but also glycerin and a small amount of biodiesel adhered to the refining resin are introduced. At this time, in the separation tank (E-351), the methanol is separated by vacuum evaporation and stored in the separated methanol storage tank (V-352), and then sent to the methanol tank (V-309) to be reused for washing the resin for purification, and the remaining biodiesel And glycerin are separated using the difference in specific gravity, and the biodiesel is sent to the first storage tank (V-301), and the glycerin is discharged to the glycerol tank (V-353).

Glycerin discharged during the cleaning process of the refining resin is sent to a glycerol tank (V-353).

In a further aspect,

The electrical conductivity sensor is moved from the top to the bottom of the biodiesel stored in the first storage tank (V-301), the second storage tank (V-304) and the third storage tank (V-307) to reduce the high voltage. By applying an electric current, impurities such as finely mixed glycerin can be removed by coagulation reaction, and voltage is applied evenly to the entire biodiesel by applying voltage while moving from the lower surface of each storage tank to a predetermined upper position.

In addition, in the first storage tank (V-301), the second storage tank (V-304), and the third storage tank (V-307), a water level detection sensor using a buoy is installed to flow into each storage tank. You can measure the amount of

As described above, the biodiesel refining system capable of performing the cleaning or replacement determination of the refining resin using the electrical conductivity according to the present invention increases the biodiesel production rate by grasping the replacement time of the refining resin using the electrical conductivity. High purity biodiesel is produced, and biodiesel purification efficiency is high by performing the process of purifying biodiesel with a purification resin multiple times, and a single purification tank is used by placing a plurality of purification tanks in each purification section. When it is not possible, the purification process can be continuously performed using the other one, and the process of washing the purification resin with methanol and removing methanol remaining in the washed purification resin with biodiesel is a simple cleaning process for the purification resin. Is carried out easily.

As described above, although the present invention has been described by the limited embodiments and drawings, the present invention is not limited thereto, and the technology to which the present invention belongs is various within the scope of equality of the spirit of the invention and the claims to be described below. Of course, modifications and variations are possible.

V-301: first storage tank V-308: biodiesel tank
R-302, R-303: primary purification unit V-309: methanol tank
V-304: second storage tank V-353: glycerol tank
R-305, R-306: 2nd refining unit E-351: Separation tank
V-307: 3rd storage tank V-352: Separated methanol storage tank

Claims (6)

In a purification system for purifying biodiesel produced through an esterification process with a resin for purification,
The purification system
The first storage tank (V-301) containing biodiesel for the first time, the first purification unit (R-302, R) filled with refining resin, and into which biodiesel is introduced from the first storage tank (V-301). -303), a second storage tank (V-304) into which the first purified biodiesel is introduced from the first purification unit (R-302, R-303), a resin for purification is filled, and the second Secondary purification units (R-305, R-306) into which biodiesel is introduced from the storage tank (V-304), and the bio-purified from the second purification units (R-305, R-306) A third storage tank (V-307) into which diesel is introduced, a biodiesel tank (V-308) into which purified biodiesel is introduced from the third storage tank (V-307), and the first purification unit (R- 302, R-303) and the second purification unit (R-305, R-306) when the refining resin is contaminated, methanol is added to wash the refining resin and a methanol tank storing methanol (V-309) is included,
For the determination of washing and replacement of the resin for purification, an electric conductivity sensor is attached and installed inside the first storage tank (V-301), the second storage tank (V-304), and the third storage tank (V-307). After the biodiesel is filled in each tank, a power of 9V voltage is applied to measure the recognized voltage, and the measured value is stored in the database as a reference value.
Subsequently, if the measured value during biodiesel purification is measured higher than the reference value, the tablets filled in the first purification unit (R-302, R-303) and the second purification unit (R-305, R-306) A biodiesel purification system capable of washing or replacing the resin for purification using electrical conductivity, characterized in that the resin is washed or replaced. The method of claim 1,
The first purification unit (R-302, R-303) and the second purification unit (R-305, R-306) consist of two purification tanks, respectively, so that one purification tank cannot be used for biodiesel purification. Alternatively, a biodiesel purification system capable of washing or replacing the resin for purification using electrical conductivity, characterized in that when the resin filled in one purification tank is washed or replaced, the process of biodiesel can be performed with the other. . The method of claim 1,
The resin for purification is a polymer resin, and cleaning or replacement of the resin for purification using electrical conductivity, characterized in that one or more selected from activated clay, zeolite, activated carbon, bentonite, silicalite, vermiculite, and potassium silicate can be added and used. Biodiesel purification system that can perform judgment. The method of claim 1,
The purification resin is washed from the methanol tank (V-309) storing methanol. The first purification units (R-302, R-303) and the second purification units (R-305, R) need to be washed. A biodiesel purification system capable of washing or replacing the resin for purification using electrical conductivity, characterized in that washing is carried out by passing methanol through the purification tank of -306). The method of claim 4,
The refining resin after washing is removed by injecting biodiesel stored in the third storage tank (V-307) into methanol remaining in the refining resin during the washing process, and the biodiesel used at this time is a separation tank (E-351). ) From methanol and then sent to the first storage tank (V-301), and the methanol used in the washing process and the separated methanol are sent to the methanol tank (V-309) for reuse. A biodiesel purification system capable of washing or replacing the resin for purification. The method of claim 4,
The biodiesel purification system capable of washing or replacing the resin for purification using electrical conductivity, characterized in that the glycerin discharged during the cleaning process of the purification resin is sent to a glycerol tank (V-353).

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