KR102325294B1 - 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 manufacturing method thereof are disclosed.

Description

Fiber filter for removing hydrogen sulfide including acid mine drainage sludge, device for removing hydrogen sulfide including same, and manufacturing method thereof

The present invention relates to a fiber filter for removing hydrogen sulfide containing acidic acid mine drainage sludge, a device for removing hydrogen sulfide including the same, and a method for manufacturing the same. More specifically, the present invention relates to a fiber filter for removing hydrogen sulfide based on electrospinning, comprising acidic acid mine drainage sludge obtained by precipitating and drying high-concentration acidic acid mine drainage generated inside an abandoned mine, a hydrogen sulfide removal device including the same, and a method for manufacturing the same it's about

Sewage sludge generated during the treatment of domestic sewage and wastewater in the sewage treatment plant is concentrated and then organic matter is decomposed by anaerobic digestion by microorganisms to methane (CH ₃ ), carbon dioxide (CO ₂ ), hydrogen sulfide (H ₂ S) Digestive gas containing , siloxane, etc. is generated. The biomethane gas generated in this way is used as a fuel to produce electricity or as an energy source, etc. There is a need for a resource recycling technology as an eco-friendly alternative energy. However, when the digestion gas is used as it is for the use of biomethane gas, hydrogen sulfide generated as an impurity is very toxic to the body, corrodes power generation facilities, and is oxidized to SOx, a causative material 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 above composition, the desulfurization process, which is a process for removing odors and removing hydrogen sulfide from the digestion gas, is essential.

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

The domestic hydrogen sulfide removal technology uses an adsorption mechanism such as activated carbon and iron oxide adsorbent, which causes a lot of economic cost due to low removal efficiency and uneconomical price formation, which leads to an increase in the production cost of biomethane gas. Accordingly, there is a need for materials and processes with higher removal efficiency and economic feasibility than conventional adsorbents.

Korean Patent Publication No. 10-2014-0136286 (published on November 28, 2014) Korean Patent Registration 10-1451910 (Registered on October 10, 2014)

It is an object of the present invention to economically and efficiently remove hydrogen sulfide using acidic acid mine drainage sludge containing divalent to trivalent metals and metalloids.

An object of the present invention is to effectively use the digestion gas in a sewage and wastewater treatment plant through the creation of value of acid mine drainage sludge, which is a waste generated through active treatment and purification of acid mine drainage generated in abandoned mines, and economic feasibility through reduction of manufacturing costs. it has its purpose

An object of the present invention is to manufacture a fiber filter based on the electrospinning method, and to maximize the surface area of the added material to increase the removal efficiency compared to the raw material in the form of powder.

In order to achieve the above object, an exemplary embodiment of the present invention includes an electrospun fiber, wherein the electrospun fiber includes an acidic acid mine drainage sludge and a polymer for fiber formation. It provides 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; provides a hydrogen sulfide removal device comprising.

In an exemplary embodiment of the present invention, there is provided a method for manufacturing a fiber filter for removing hydrogen sulfide described above, comprising the steps of: preparing a spinning solution containing acidic acid mine drainage sludge and a polymer for fiber formation; and electrospinning the spinning solution to produce an electrospun fiber; provides an electrospun fiber manufacturing method comprising.

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

The present invention is environmentally friendly in terms of reusing 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 powder by using the electrospinning method.

1 is a photograph of dried acidic acid mine drainage sludge, which is a raw material of 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 scanning electron microscope (SEM) images for each content of a fiber filter for hydrogen sulfide removal manufactured according to an embodiment of the present invention, FIG. 3A is a comparative example, and FIG. 3B is Example 1, 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 hydrogen sulfide removal manufactured according to an embodiment of the present invention.
5 is a graph showing the results at a hydrogen sulfide concentration of about 10 ppm as comparative data before and after hydrogen sulfide removal of a fiber filter for hydrogen sulfide removal manufactured according to an embodiment of the present invention.
6a-b are photographs of the front side (6a) and the back side (6b) of a fiber filter for removing hydrogen sulfide manufactured according to an embodiment of the present invention.

Hereinafter, preferred 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 the purpose of explanation only, and the embodiments of the present invention may be embodied 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, but is not intended to limit the present invention to a specific disclosed form, as various changes may be made and may have various forms, and all changes, equivalents or substitutes included in the spirit and scope of the present invention should be understood as including

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

Fiber Filter for Hydrogen Sulfide Removal

In exemplary embodiments of the present invention, it provides an electrospun fiber, wherein the electrospun fiber comprises an acidic acid mine drainage sludge and a polymer for fiber formation, a fiber filter for removing hydrogen sulfide.

The fiber filter for removing hydrogen sulfide according to the present invention is manufactured using a spinning solution obtained by adding acidic acid mine drainage sludge flowing out from the mine, which is a waste, to a solution in which a polymer for fiber formation is dissolved, so that manufacturing costs 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.

As used herein, "mine drainage" is water flowing out of the mine, high in heavy metal content, and low in pH. Therefore, acid mine drainage must be neutralized and oxidized to have an appropriate pH before flowing into river water and groundwater, and a large amount of dissolved iron Various heavy metals including

In an exemplary embodiment, the acidic acid mine drainage sludge contains a divalent or higher metal or metalloid element, and when analyzing the acidic dried mineral acid drainage sludge 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.

Results of XRF analysis of acid mine drainage sludge 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 acid mine drainage sludge may be 0.3 to 2.0 μm. By using the acidic acid mine drainage sludge dried in powder form after active treatment with a strong base material, acidic acid acid drainage sludge with excellent hydrogen sulfide adsorption function can exist in a uniformly dispersed state in the electrospun fibers.

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

As the fiber-forming polymer, it can be used without particular limitation as long as it can form fibers together with the acidic acid mine drainage sludge.

Specifically, it is preferable to use a polymer that is insoluble in common organic solvents and exhibits excellent chemical resistance as well as has hydrophobicity, so that there is no fear of shape deformation due to moisture in a high-humidity environment. PU), polyamide (NYLON 6), polyimide (PI), polybenzoxazole (PBO), polybenzimidazole (PBI), polyamideimide (PAI), polyethylene terephthalate (polyethyleneterephtalate), polyethylene (PE), polypropylene (polypropylene, PP), copolymers thereof, or mixtures thereof can be used. Among them, polyurethane or polyamide has high tensile strength and excellent thermoformability. It is preferable because it can exhibit an excellent absorbent elastic effect, and more preferably polyacrylonitrile.

In an exemplary embodiment, the electrospun fiber includes acidic photoacid drainage sludge and polyacrylonitrile, and _{the weight ratio of the 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.

At this time, the electrospun fiber may further include a functional additive for fiber formation, for example, may further include a curing agent, a caking additive, a conventional absorbent material, and the like.

In an exemplary embodiment, the electrospun fiber may have a diameter of 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. In this case, the web may have an optimized thickness and porosity to exhibit the maximum effect of removing hydrogen sulfide by controlling 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; provides a hydrogen sulfide removal device comprising.

In an exemplary embodiment, the device for removing hydrogen sulfide includes an injection gas concentration measurement unit; and an exhaust gas concentration measurement unit; may further include.

As shown in Figure 4, one side of the fiber filter for removing hydrogen sulfide includes an injection gas concentration measuring unit for measuring the concentration of hydrogen sulfide in the gas injected from the outside of the device, and on the other side, measuring the concentration of hydrogen sulfide in the gas passing through the fiber filter for removing hydrogen sulfide By including an exhaust gas concentration measuring unit that can measure the extent to which hydrogen sulfide is removed in real time.

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

Manufacturing method of fiber filter for hydrogen sulfide removal

In exemplary embodiments of the present invention, there is provided a method for manufacturing a fiber filter for removing hydrogen sulfide as described above, comprising the steps of: preparing a spinning solution containing acidic acid mine drainage sludge and a polymer for fiber formation; and producing an electrospun fiber by electrospinning the spinning solution.

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

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

First, acidic acid mine drainage flowing out from the mine is collected, and a strong base such as sodium hydroxide is added to precipitate it to form sludge, and after the reaction, the sludge is collected and air-dried to obtain acidic acid mine drainage sludge as shown in FIG. 1 .

After that, it is possible to prepare a spinning solution together with a polymer for fiber formation, and use 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 acid mine drainage sludge and the polymer for fiber formation are the same as described above.

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

The organic solvent is preferably included in a range such that the electrospinning composition has a viscosity suitable for electrospinning, and specifically, it 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 the electrospinning, the diameter of the fiber can be optimized in a range in which the maximum effect of removing hydrogen sulfide can be obtained. In addition, the surface area of the acidic 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 carried out 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 electrospun fiber can be prepared by electrospinning the spinning solution on the surface of the stainless metal mesh network (100 mesh). 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 practice. However, the examples are provided to illustrate the present invention, and the scope of the present invention is not limited thereto.

Example

Example One

Sludge was made by collecting acid mine drainage from the mine H mine in Taebaek-si, Gangwon-do, and precipitating it with a strong base such as sodium hydroxide. After the reaction, the sludge was collected and air dried. Thereafter, the air-dried sludge was crushed and sieved on a 325 mesh to obtain an acidic acid mine drainage sludge with a size of 45 μm or less (see FIG. 1).

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

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 the plate of an electrospinning device to which an electric field was applied at 20 kV.

As a result of the electrospinning, filters including fibers having an average diameter of 1.6 μm were 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 acidic acid mine 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 acid mine drainage sludge was not used in the preparation of the spinning solution for fiber formation.

Manufacture of filters for each acidic mine drainage sludge content Polymer (weight) solvent (weight) Additives (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: Observe the fiber filter

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

Referring to this, as compared with the comparative example (FIG. 3a), in the case of Examples 1, 2, 3, and 4 (FIG. 3b-3e), it can be confirmed that iron sludge was added to the fiber made by electrospinning.

test example 2: Acid mine drainage sludge Hydrogen sulfide according to content Removability evaluation

As shown in FIG. 4, after mixing hydrogen sulfide and nitrogen using a mass flow controller (MFC), the hydrogen sulfide concentration was uniformly injected at 10 ppm, and in Example 1 The real-time online analysis process was shown through a gas analyzer for the amount of hydrogen sulfide to be reduced by inserting the fiber filters of -4 and Comparative Examples.

As a result of the analysis, as shown in FIG. 5 , it can be confirmed that the fiber filters of Examples 1-4 (0.25, 0.50, 0.75, 1.00 g), compared to Comparative Example (0.00 g), have excellent hydrogen sulfide removal ability, especially 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 in detail a specific part of the content of the present invention, for those of ordinary skill in the art, this specific description is only a preferred embodiment, and it is clear that the scope of the present invention is not limited thereby. something to do. Accordingly, it is intended that the substantial scope of the present invention be defined by the appended claims and their equivalents.

Claims (13)

comprising electrospun fibers;
The electrospun fiber contains acidic acid mine drainage sludge and a polymer for fiber formation,
The weight ratio of the acidic acid mine drainage sludge and the polymer for fiber formation is 1: 1 to 5, a fiber filter for removing hydrogen sulfide. According to claim 1,
The acidic acid mine drainage sludge contains a divalent or higher metal or metalloid element,
When the acid mine drainage sludge is analyzed by X-ray flourescence spectrometry (XRF), the content of iron (Fe) among the divalent or higher metal or metalloid elements is 70% or more, a fiber filter for removing hydrogen sulfide . According to claim 1,
The average particle diameter of the acidic acid mine drainage sludge is 0.3 to 2.0 μm, a fiber filter for removing hydrogen sulfide. According to claim 1,
The acidic acid mine 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. According to claim 1,
The fiber-forming polymer is polyacrylonitrile, a fiber filter for removing hydrogen sulfide. According to claim 1,
The electrospun fiber has a diameter of 1.0 to 2.0 μm, a fiber filter for removing hydrogen sulfide. According to claim 1,
The electrospun fibers are three-dimensionally irregularly 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. 9. The method of claim 8,
The device for removing the hydrogen sulfide includes an injection gas concentration measuring unit; and an exhaust gas concentration measurement unit; which will further include a hydrogen sulfide removal device. As a method for manufacturing a fiber filter for removing hydrogen sulfide according to any one of claims 1 to 7,
Preparing a spinning solution containing an acidic acid mine drainage sludge and a polymer for fiber formation; and
Method for manufacturing a fiber filter for removing hydrogen sulfide, comprising a; manufacturing the electrospun fiber by electrospinning the spinning solution. 11. The method of claim 10,
The electrospinning will be carried out under a voltage of 15 to 20 kV, a method for manufacturing a fiber filter for removing hydrogen sulfide. 11. The method of claim 10,
The electrospinning is a method of manufacturing a fiber filter for removing hydrogen sulfide, which 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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