KR20210042558A - Hydrogen sulfide removal fiber filter comprising acid mine drainage sludge, hydrogen sulfide removal device comprising the same, and method for manufacturing the same - Google Patents

Abstract

In the present specification, a fiber filter for removing hydrogen sulfide containing acidic acid mine drainage sludge, a hydrogen sulfide removal device including the same, and a method for manufacturing the same are disclosed. An object of the present invention is to economically and efficiently remove hydrogen sulfide using acidic acid mine drainage sludge containing divalent to trivalent metals and metalloids.

Description

Fiber filter for removing hydrogen sulfide including acidic mine drainage sludge, hydrogen sulfide removal device including the same, and a manufacturing method thereof {HYDROGEN SULFIDE REMOVAL FIBER FILTER COMPRISING ACID MINE DRAINAGE SLUDGE, HYDROGEN SULFIDE REMOVAL DEVICE COMPRISING THE SAME, AND METHOD FOR MANUFACTURING THE MANUFACTURING THE SAME}

The present invention relates to a fiber filter for removing hydrogen sulfide including acidic mine-drained sludge, an apparatus for removing hydrogen sulfide including the same, and a method of manufacturing the same. More specifically, the present invention relates to a fiber filter for removing hydrogen sulfide based on electrospinning, including an acidic mine drainage sludge obtained by sedimenting and drying high-concentration acidic mine drainage generated inside an abandoned mine, a hydrogen sulfide removal device including the same, and a manufacturing method thereof. About.

Sewage sludge generated in the process of treating domestic wastewater in a sewage treatment plant is methane (CH ₃ ), carbon dioxide (CO ₂ ), hydrogen sulfide (H ₂ S) in the process of decomposing organic matter by anaerobic digestion reaction by microorganisms after concentration. , Digestion gas containing siloxane, etc. The bio-methane gas generated in this way is used as a fuel to generate electricity or as an energy source, and thus resource recycling and eco-friendly alternative energy technology is required. However, when the digestive gas is used as it is for the use of biomethane gas, hydrogen sulfide produced as an impurity is extremely toxic to the body, corrodes power generation facilities, and is oxidized to SOx, which is the cause of acid rain during combustion, causing air pollution.

Composition of sewage sludge anaerobic digestion gas Methane (Vol%) Carbon dioxide (vol %) Hydrogen sulfide (ppm) Other impurities 60~70 30~35 500~2,000 Siloxane, etc.

With the composition as described above, a desulfurization process, which is a process of removing odors and removing hydrogen sulfide from the digestion gas, must be essential.

Currently, in Korea, hydrogen sulfide is regulated as a designated odor substance according to the Air Conservation Act, and the emission from workplaces in industrial areas is 0.2 ppm or less, and emissions from workplaces in other areas are regulated to be 0.06 ppm or less.

Domestic hydrogen sulfide removal technology uses adsorption mechanisms such as activated carbon and iron oxide adsorbents, resulting in low removal efficiency and uneconomical cost, leading to an increase in the production cost of biomethane gas. Therefore, materials and processes with higher removal efficiency and economy than existing adsorbents are required.

Korean Patent Publication 10-2014-0136286 (published on November 28, 2014) Korean Patent Registration 10-1451910 (registered on Oct. 10, 2014)

An object of the present invention is to economically and efficiently remove hydrogen sulfide by using acid mine drainage sludge containing di- or trivalent metals and metalloids.

It is an object of the present invention to effectively use digestion gas in a sewage/wastewater treatment plant through value creation of acidic mine drainage sludge, which is a waste generated through active treatment and purification of acidic mine drainage generated from abandoned mines, and securing economic efficiency through manufacturing cost reduction. It has its purpose.

It is an object of the present invention to manufacture a fiber filter based on an electrospinning method, thereby maximizing the surface area of an added material to increase removal efficiency than a powdery raw material.

In order to achieve the above object, an exemplary embodiment of the present invention includes an electrospun fiber, and the electrospun fiber includes an acidic photo-drainage sludge and a fiber-forming polymer, providing a fiber filter for removing hydrogen sulfide. .

In an exemplary embodiment of the present invention, a metal mesh network; And a fiber filter for removing hydrogen sulfide described above.

In an exemplary embodiment of the present invention, a method for manufacturing a fiber filter for removing hydrogen sulfide described above, comprising: preparing a spinning solution including an acidic photo-acid drainage sludge and a fiber-forming polymer; And electrospinning the spinning solution to produce electrospun fibers.

The fiber filter for removing hydrogen sulfide of the present invention can effectively and economically adsorb hydrogen sulfide when reacting with an anaerobic digestion gas by preparing a new adsorbent including acidic mine drainage sludge.

The present invention is eco-friendly in terms of reuse of waste by-products generated during the purification process of waste generated during mining.

The present invention can maximize the removal efficiency of a small amount of additive material in the form of a powder by using an electrospinning method.

1 is a photograph of dried acidic mine-drained sludge as a raw material for a fiber filter for removing hydrogen sulfide according to an embodiment of the present invention.
2 is a schematic configuration diagram of an apparatus for manufacturing a fiber filter for removing hydrogen sulfide according to an embodiment of the present invention.
3A-E are a scanning electron microscope (SEM) image for each content of a fiber filter for removing hydrogen sulfide manufactured according to an embodiment of the present invention, and FIG. 3A is a comparative example, and FIG. 3B is an example 1 and FIG. 3C is a scanning electron microscope image of Example 2, FIG. 3D is Example 3, and FIG. 3E is Example 4. FIG.
4 is a schematic configuration diagram of an apparatus for measuring hydrogen sulfide removal efficiency of a fiber filter for removing hydrogen sulfide manufactured according to an embodiment of the present invention.
5 is a graph showing comparison data before and after removal of hydrogen sulfide of a fiber filter for removing hydrogen sulfide prepared according to an embodiment of the present invention, and showing the result at a concentration of about 10 ppm of hydrogen sulfide.
6A-B are photographs of a front surface 6a and a rear surface 6b of a fiber filter for removing hydrogen sulfide manufactured according to an embodiment of the present invention.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

The embodiments of the present invention disclosed in the text are illustrated for purposes of explanation only, and the embodiments of the present invention may be implemented in various forms and should not be construed as being limited to the embodiments described in the text. .

The present invention is not intended to limit the present invention to a specific disclosed form, as various changes may be added and various forms may be added, and all changes, equivalents, or substitutes included in the spirit and scope of the present invention It should be understood to include.

In the present specification, when a certain part "includes" a certain component, it means that other components may be further included rather than excluding other components unless specifically stated to the contrary.

Fiber filter for removing hydrogen sulfide

In exemplary embodiments of the present invention, a fiber filter for removing hydrogen sulfide is provided, which includes an electrospun fiber, and the electrospun fiber includes an acidic photo-drainage sludge and a fiber-forming polymer.

The fiber filter for removing hydrogen sulfide according to the present invention is manufactured by using a spinning solution in which acidic mine-drained sludge flowing out of a waste mine is added to a solution in which a polymer for fiber formation is dissolved, so that manufacturing cost can be reduced and electricity Through entanglement and lamination between the spun fibers, the surface area of the acid mine drainage sludge is increased, and the ability to remove hydrogen sulfide is maximized.

In the present specification, "mine drainage" refers to water that flows out of a pit, has a high content of heavy metals, and has a low pH, so acidic mine drainage must be neutralized and oxidized to have an appropriate pH before flowing into river water and groundwater, and dissolved iron in large amounts. In this case, in order to adjust the pH, the alkali neutralizing agent process causes the precipitation of “acid mine drainage sludge” containing a large amount of Fe.

In an exemplary embodiment, the acidic photo-acid drainage sludge contains a metal or metalloid element having a divalent or higher value, and when the acid-dried photo-acid drainage sludge is analyzed by X-ray flourescence spectrometry (XRF), As shown in Table 2 below, the content of iron (Fe) in the divalent or higher metal or metalloid element may be 70% or more.

Acid mine drainage sludge XRF analysis results Element Fe S Ca Si Al Mn Mg Other Total AMDs (%) 82.8 0.82 10.20 2.42 1.47 1.21 0.24 0.85 100.0

In an exemplary embodiment, the average particle diameter of the acidic mine-drained sludge may be 0.3 to 2.0 μm. Acid mine drainage sludge with excellent hydrogen sulfide adsorption function can be uniformly dispersed in the electrospun fibers by using acidic mine drainage sludge dried in powder form after active treatment with strong basic substances.

In an exemplary embodiment, the acidic photoacid drainage sludge may be included in an amount of 10 to 30% by weight, for example, 20 to 30% by weight, and preferably 25 to 30% by weight based on the total weight of the electrospun fiber. have. When the content of the acidic mine-drained sludge is less than 10% by weight or more than 30% by weight, the hydrogen sulfide adsorption capacity may be reduced, and in particular, when it is more than 30% by weight, the surface area of the acidic acidic acid-drained sludge may be reduced, thereby reducing the hydrogen sulfide removal capacity.

The fiber-forming polymer may be used without particular limitation as long as it is capable of forming fibers together with acidic photo-drained sludge.

Specifically, it is preferable to use a polymer that is insoluble in a common organic solvent and thus exhibits excellent chemical resistance as well as hydrophobicity and does not have a fear of shape deformation due to moisture in a high humidity environment, and a specific example thereof is polyurethane (poly urethane, PU), polyamide (NYLON 6), polyimide (PI), polybenzoxazole (PBO), polybenzimidazole (PBI), polyamideimide (PAI), polyethylene terephthalate (polyethyleneterephtalate), polyethylene (PE), polypropylene (PP), copolymers thereof, or mixtures thereof may be used. Among them, polyurethane or polyamide has high tensile strength and excellent thermoformability. It is preferable because it can exhibit a more excellent absorbent elastic effect, and more preferably polyacrylonitrile.

In an exemplary embodiment, the electrospun fibers include acidic photoacid drainage sludge and polyacrylonitrile, and _{the weight ratio of acidic photoacid drainage sludge and polyacrylonitrile (C 3} H ₃ N) is 1: 1 to 1: 5 May be, for example, 1: 2 to 1: 4 or 1: 2 to 1: 3.

In this case, the electrospun fiber may further include a functional additive for forming fibers, and may further include, for example, a curing agent, a caking agent, a conventional absorbent material, and the like.

In an exemplary embodiment, the diameter of the electrospun fiber may be 1.0 to 2.0 μm.

In an exemplary embodiment, the electrospun fibers may be arranged irregularly and discontinuously in three dimensions to form a web. At this time, the web may have an optimized thickness and porosity to exhibit the maximum hydrogen sulfide removal effect through the control of the diameter and density of the fibers.

In exemplary embodiments of the present invention, a metal mesh network; And a fiber filter for removing hydrogen sulfide described above.

In an exemplary embodiment, the device for removing hydrogen sulfide includes an injection gas concentration measuring unit; And an exhaust gas concentration measuring unit.

As shown in FIG. 4, one side of the hydrogen sulfide removal fiber filter includes an injection gas concentration measuring unit that measures the hydrogen sulfide concentration in the gas injected from the outside of the device, and the other side measures the hydrogen sulfide concentration in the gas passing through the hydrogen sulfide removal fiber filter. By including the exhaust gas concentration measuring unit, it is possible to measure the degree to which hydrogen sulfide is removed in real time.

In exemplary embodiments of the present invention, an air filter including the aforementioned fiber filter for removing hydrogen sulfide is provided.

Method for manufacturing a fiber filter for removing hydrogen sulfide

In exemplary embodiments of the present invention, a method for manufacturing a fiber filter for removing hydrogen sulfide described above, comprising: preparing a spinning solution comprising acidic photo-drainage sludge and a fiber-forming polymer; And electrospinning the spinning solution to produce electrospun fibers.

2 is a schematic configuration diagram of an apparatus for manufacturing a fiber filter for removing hydrogen sulfide according to the present invention.

The method of manufacturing a fiber filter by electrospinning makes it easy to control the diameter and pore size of the fiber, and it is possible to manufacture a filter for various purposes according to the material to be added. When electrospinning is used, the reaction surface area can be maximized compared to the method of solidifying and applying the previously dried acidic mine drainage sludge, so the absorption capacity per weight of the adsorbent is excellent. In addition, since it is manufactured as a module, it is easy to scale-up because it can be replaced with filters and structured in multiple layers.

First, the acidic mine drainage discharged from the pit is collected and precipitated by adding a strong base such as sodium hydroxide to form a sludge, and after the reaction, the sludge is collected and air-dried, thereby obtaining an acidic mine drainage sludge as shown in FIG. 1.

Thereafter, it is possible to prepare a spinning solution together with a fiber-forming polymer, and then, using an electrospinning device as shown in FIG. 2, to prepare an electrospun fiber. At this time, the step of preparing the spinning solution may be carried out according to a conventional mixing process, and the acidic photoacid drainage sludge and the polymer for fiber formation are the same as described above.

As a solvent included in the spinning solution, any conventional organic solvent capable of dissolving the above-described polymer may be used without particular limitation. Specifically, NMP (N-Methyl-2-Pyrrolidone), DMF (dimethyl formamide), DMAc (dimethyl acetamide), DMSO (dimethyl sulfoxide), THF (Tetrahydrofuran), etc. can be used, preferably DMF (dimethyl formamide) Can be

The organic solvent is preferably included in a range so that the electrospinning composition has a viscosity suitable for electrospinning, and specifically, may be included in an amount such that the spinning solution has a viscosity of 450 to 700 cP.

By controlling the conditions at the time of electrospinning, the diameter of the fiber can be optimized to a range in which the maximum hydrogen sulfide removal effect can be obtained. In addition, the surface area of the acid mine drainage sludge is increased through entanglement and lamination between fibers, and the ability to remove hydrogen sulfide can be maximized.

In an exemplary embodiment, the electrospinning may be carried out under a voltage of 15 to 20 kV.

In an exemplary embodiment, the electrospinning may be performed by discharging the spinning solution at a rate of 1 mL/hr.

Specifically, during the electrospinning, the electric field may be applied at 20 kV, and the electrospinning rate may be 1 mL/hr.

At this time, the spinning solution may be electrospun onto the surface of a stainless steel metal mesh (100 mesh) to produce electrospun fibers, and when the spinning solution is directly electrospun onto the stainless steel metal mesh, there is no need for a separate peeling process. It can be used immediately as a filter, and has the advantage of convenient replacement.

The present invention will be described in more detail through the following implementation. However, the examples are for illustrative purposes only, and the scope of the present invention is not limited thereto.

Example

Example One

Acid mine drainage from the mine of the H mine, a coal mine in Taebaek, Gangwon-do, was collected and precipitated by adding a strong base such as sodium hydroxide to make sludge. After the reaction, the sludge was collected and air-dried. Thereafter, the air-dried sludge was crushed and then sieved through 325 mesh to obtain an acidic mine-drained sludge in a powder form of 45 μm or less (see FIG. 1).

In a weight ratio as shown in Table 3 below, a spinning solution for fiber formation was prepared by mixing acidic photoacid drainage sludge having an average diameter of 45 μm or less in a mixed solvent of dimethylformamide and polyacrylonitrile as a solvent.

After transferring the prepared spinning solution for fiber formation to a syringe, it was spun at a rate of 1 mL/hr using a quantitative syringe pump on a plate of an electrospinning apparatus to which an electric field was applied at 20 kV.

As a result of the electrospinning, a filter including fibers having an average diameter of 1.6 μm was prepared as shown in FIGS. 6a (front) and 6b (rear).

Example 2 to 4

A filter was manufactured in the same manner as in Example 1, except that the content of the acidic photoacid drainage sludge contained in the fiber-forming spinning solution was varied and used as shown in Table 2 below.

Comparative example

A filter was manufactured in the same manner as in Example 1, except that acidic photo-drained sludge was not used when the spinning solution for fiber formation was prepared.

Filter production by content of acid mine drainage sludge Polymer (weight) Solvent (weight) Additive (weight) Example 1 Polyacrylonitrile (2.0 g) Dimethylformamide (18 g) Acid mine drainage sludge (0.25g) Example 2 Polyacrylonitrile (2.0 g) Dimethylformamide (18 g) Acid mine drainage sludge (0.50 g) Example 3 Polyacrylonitrile (2.0 g) Dimethylformamide (18 g) Acid mine drainage sludge (0.75 g) Example 4 Polyacrylonitrile (2.0 g) Dimethylformamide (18 g) Acid mine drainage sludge (1.00 g) Comparative example Polyacrylonitrile (2.0 g) Dimethylformamide (18 g) -

Test example

Test example 1: Observation of fiber filter

In order to evaluate the hydrogen sulfide absorption and removal effect of the absorbent according to an embodiment of the present invention, the fiber filters prepared in Comparative Examples and Examples 1, 2, 3, 4 were analyzed and observed using a scanning electron microscope, and the results Is shown in Figures 3a to 3e.

Referring to this, compared to the comparative example (Fig. 3a), in the case of Examples 1, 2, 3, and 4 (Figs. 3b-3e), it can be seen that iron sludge is added to the fiber made by electrospinning.

Test example 2: Acid mine drainage Sludge Hydrogen sulfide depending on the content Removal ability evaluation

As shown in FIG. 4, after mixing hydrogen sulfide and nitrogen using a mass flow controller (MFC), a concentration of hydrogen sulfide was constantly injected at 10 ppm, and Example 1 in the middle of a column made of a pyrex material having a diameter of 6 cm. The amount of hydrogen sulfide decreased by inserting the fiber filters of -4 and Comparative Example was shown in real-time online analysis through a gas analyzer.

As a result of the analysis, as shown in FIG. 5, it can be seen that the fiber filter of Example 1-4 (0.25, 0.50, 0.75, 1.00 g), compared to the Comparative Example (0.00 g), has excellent hydrogen sulfide removal ability. The fiber filter prepared in Example 3 (0.75 g) showed optimal absorption and removal effects for hydrogen sulfide through repeated experiments.

As described above, specific parts of the present invention have been described in detail, and it is obvious that these specific techniques are only preferred embodiments for those of ordinary skill in the art, and the scope of the present invention is not limited thereby. something to do. Accordingly, it will be said that the substantial scope of the present invention is defined by the appended claims and their equivalents.

Claims (13)

Including electrospun fibers,
The electrospun fiber is a fiber filter for removing hydrogen sulfide that includes acidic photo-drained sludge and a fiber-forming polymer. The method of claim 1,
The acidic mine drainage sludge contains a divalent or higher metal or metalloid element,
When analyzing the acid-dried mine-drained sludge by X-ray flourescence spectrometry (XRF), the content of iron (Fe) in the divalent or higher metal or metalloid element is 70% or more, for removing hydrogen sulfide Fiber filter. The method of claim 1,
The average particle diameter of the acidic mine drainage sludge is 0.3 to 2.0 ㎛, a fiber filter for removing hydrogen sulfide. The method of claim 1,
The acidic photoacid drainage sludge is contained in an amount of 10 to 30% by weight based on the total weight of the electrospun fiber, a fiber filter for removing hydrogen sulfide. The method of claim 1,
The electrospun fibers include acidic photo-drained sludge and polyacrylonitrile,
The weight ratio of the acidic photoacid drainage sludge and polyacrylonitrile is 1: 1 to 5, a fiber filter for removing hydrogen sulfide. The method of claim 1,
The diameter of the electrospun fibers is 1.0 to 2.0 ㎛, a fiber filter for removing hydrogen sulfide. The method of claim 1,
The electrospun fibers are three-dimensionally irregular and discontinuously arranged to form a web, a fiber filter for removing hydrogen sulfide. Metal mesh net; And
A hydrogen sulfide removal device comprising a; a fiber filter for removing hydrogen sulfide according to any one of claims 1 to 7 formed on the metal mesh network. The method of claim 8,
The device for removing hydrogen sulfide includes an injection gas concentration measuring unit; And an exhaust gas concentration measuring unit. As a method for producing a fiber filter for removing hydrogen sulfide according to any one of claims 1 to 7,
Preparing a spinning solution containing an acidic photoacid drainage sludge and a fiber-forming polymer; And
Electrospun fiber filter manufacturing method comprising; electrospinning the spinning solution to produce electrospun fibers. The method of claim 10,
The electrospinning fiber filter manufacturing method that is carried out under a voltage of 15 to 20 kV. The method of claim 10,
The electrospinning method of manufacturing an electrospun fiber filter is carried out by discharging the spinning solution at a rate of 1 mL/hr. An air filter comprising a fiber filter for removing hydrogen sulfide according to any one of claims 1 to 7.

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