Organic matter adsorbent, and method for producing an organic matter adsorbent.

Abstract

To provide an adsorbent that has high adsorption capacity for organic matter and is also highly safe for living organisms. [Solution] An organic matter adsorbent comprising mineral particles as an active ingredient, wherein the surface of the mineral particles is coated with a protein and / or polysaccharide, and the protein and / or polysaccharide is one or more selected from collagen, elastin, desmosine or isodesmosine-containing proteins and glycosaminoglycans, and a method for producing the same.

Description

Technical Field

[0001] The present invention relates to an organic substance adsorbent having mineral particles as an active ingredient and having a high adsorption ability for organic substances such as organic fluorine compounds represented by perfluoroalkyl compounds and polyfluoroalkyl compounds, and a method for producing the same.

Background Art

[0002] Materials for efficiently removing trace organic pollutants in the environment and technologies for removing pollutants using such materials have been developed. For example, adsorbent materials treated with ions, salts, oxides, hydroxides, or carbonates of calcium, magnesium, strontium, or barium (see Patent Document 1), porous polymer materials containing a plurality of crosslinked cyclodextrins (see Patent Document 2), and the like are known.

[0003] The inventor of the present invention has hitherto developed a water quality improving treatment agent containing powder of natural porous ore (see Patent Document 3) and a water quality improving treatment agent containing clinoptilolite, kaolinite, montmorillonite, etc. (see Patent Document 4).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0005] Among organic pollutants, environmental pollution caused by organofluorine compounds, such as perfluoroalkyl and polyfluoroalkyl compounds, has become a social problem. Therefore, there has been a need for adsorbents that possess high adsorption capacity for these organic substances while also being highly safe for living organisms. [Means for solving the problem]

[0006] The present invention provides an organic matter adsorbent comprising mineral particles as an active ingredient, wherein the surface of the mineral particles is coated with a protein and / or polysaccharide, and the protein and / or polysaccharide is one or more selected from collagen, elastin, desmosine or isodesmosine-containing proteins and glycosaminoglycans.

[0007] Organic substances can be organofluorine compounds, and organofluorine compounds can be perfluoroalkyl compounds and polyfluoroalkyl compounds.

[0008] Another aspect of the present invention is an organic matter adsorbent in which the mineral particles are composed of one or more selected from clinoptilolite, kaolinite, montmorillonite, lomontite, perlite, quartz, pozzolanic, macubanite, monazite, and bastnäsite, and the mineral particles include one or more selected from light rare earth elements, neodymium, and dysprosium.

[0009] Another aspect of the present invention is an organic matter adsorbent comprising mineral particles consisting of clinoptilolite, kaolinite, montmorillonite, lomontite, perlite, quartz, pozzolanic acid, macubanite, and monazite and / or bastnäsite.

[0010] Another aspect of the present invention is an organic matter adsorbent in which the surface charge of the mineral particles is 0.05 mV to 0.1 mV.

[0011] The present invention provides a method for producing an organic matter adsorbent. The production method of the present invention comprises the steps of providing mineral particles, coating the surface of the mineral particles with a protein and / or polysaccharide, and irradiating the coated mineral particles with plasma, wherein the protein and / or polysaccharide is selected from collagen, elastin, desmosine or isodesmosine-containing proteins, and glycosaminoglycans.

[0012] The step of irradiating with plasma according to the present invention may be the step of irradiating with plasma under a reducing atmosphere or a substantially vacuum atmosphere. [Effects of the Invention]

[0013] The organic matter adsorbent obtained in the present invention exhibits extremely high adsorption capacity, particularly for organofluorine compounds such as perfluoroalkyl compounds and polyfluoroalkyl compounds, and is highly safe for living organisms. [Brief explanation of the drawing]

[0014] [Figure 1] This is a scanning electron microscope image of the surface of the organic matter adsorbent produced in the example. [Modes for carrying out the invention]

[0015] The present invention relates to an organic matter adsorbent containing mineral particles as an active ingredient and a method for producing the same. The present invention will be described in detail below based on embodiments of the invention, but the present invention is not limited to the embodiments shown below.

[0016] The organic matter adsorbent of the present invention efficiently adsorbs organofluorine compounds. In particular, the organic matter adsorbent of the present invention can efficiently adsorb perfluoroalkyl compounds and polyfluoroalkyl compounds, collectively known as PFAS, among organofluorine compounds. By adsorbing PFAS contained in water and / or soil, the organic matter adsorbent of the present invention removes PFAS from water and / or soil.

[0017] That is, the present invention is an organic matter adsorbent used for the removal of organic fluorine compounds from water quality and / or soil, preferably for the removal of perfluoroalkyl compounds and polyfluoroalkyl compounds. Further, the present invention is an organic fluorine compound remover containing mineral particles as an active ingredient, and also relates to a perfluoroalkyl compound and polyfluoroalkyl compound remover, that is, a PFAS remover.

[0018] The present invention contains mineral particles as an active ingredient. The mineral particles contained in the present invention are mineral particles whose surfaces are coated with protein and / or polysaccharide. The protein and / or polysaccharide used in the present invention is not limited as long as the mineral particles coated on the surface can efficiently adsorb organic matter. In one embodiment, the protein is a protein containing collagen, elastin, desmocine or isodesmocine, etc., and the polysaccharide can be glycosaminoglycan.

[0019] Further, the mineral particles contained in the present invention are mineral particles having a surface charge. The surface charge is preferably a positive surface charge. In one embodiment, the surface charge is 0.01 mV or more, can be 0.01 mV to 1 mV, or can be 0.05 mV to 0.1 mV. Preferably, the surface charge can be a permanent or semi-permanent surface charge.

[0020] The mineral particles, which are the active ingredient in the organic matter adsorbent of one embodiment, are composed of one or more minerals selected from clinoptilolite, kaolinite, montmorillonite, laumontite, perlite, quartz, pozzolan, makubansite, monazite, and bastnasite.

[0021] Clinoptilolite is also called clinoptilolite zeolite, is a kind of naturally occurring silicate mineral, and is also known as a kind of zeolite. It has a microporous structure of silicon dioxide and alumina tetrahedrons and is known to have an effect of removing active oxygen and pollutants.

[0022] Kaolinite, also known as kaolinite, is a type of silicate mineral. It is formed when feldspar, such as granite, decomposes due to weathering. The chemical formula for kaolinite is Al2Si2O5(OH)4, and it is a mineral with a layered structure consisting of layers of silica tetrahedra and alumina octahedrons.

[0023] Montmorillonite, also known as montmorillonite, is a type of silicate mineral. It is found in hydrothermal altered rocks. It is characterized by its high swelling properties. It has a 2:1 layered structure in which silica tetrahedrons and alumina octahedrons are alternately stacked, and it is known to expand when water and cations enter between the layers.

[0024] Loemontite is a type of silicate mineral also known as stilbite. Like montmorillonite, loemontite has a 2:1 layered structure in which silica tetrahedrons and alumina octahedrons are alternately stacked. However, loemontite is known to have relatively small interlayer distances and low swelling properties.

[0025] Perlite is a general term for glassy volcanic rocks, and is a natural mineral whose main component is silicon dioxide. It is known to be advantageous for the adhesion of microorganisms and organic matter due to its light weight and excellent porosity.

[0026] Quartz, also known as silica, is a natural mineral whose main component is silicon dioxide. It is known for its excellent wear resistance, heat resistance, and chemical stability.

[0027] Pozzolanes are natural minerals rich in silicon dioxide, primarily obtained from volcanic ash and other volcanic rocks. They are important minerals used to improve the strength and durability of concrete and cement.

[0028] Macvanite is a natural mineral of volcanic origin, composed mainly of silicon dioxide and aluminum oxide, with a small amount of iron oxide. It is porous and known to have high adsorption capacity for organic matter.

[0029] Monazite, also known as monazite, is a phosphate mineral containing rare earth elements such as cerium, lanthanum, yttrium, neodymium, samarium, and thorium. Along with bastnäsite, it can be included in mineral particles of one embodiment as a source of rare earth elements, as described later.

[0030] Bastnäsite, also known as bastnässite, is a carbonate mineral containing rare earth elements such as cerium, lanthanum, neodymium, yttrium, samarium, and thorium. Along with monazite, it can be included in mineral particles of one embodiment as a source of rare earth elements, as described later.

[0031] In one embodiment, the mineral particles contain rare earth elements. Preferably, the rare earth elements are one or more selected from cerium, lanthanum, neodymium, yttrium, samarium, thorium, and dysprosium, and these rare earth elements can be supported in the mineral particles on porous minerals such as zeolites, or on minerals such as monazite and bastnäsite.

[0032] In one embodiment, the mineral particles contain light rare earth elements. Light rare earth elements are lanthanides with atomic weights smaller than gadolinium, and specifically include lanthanum, cerium, praseodymium, neodymium, promethium, samarium, and europium.

[0033] In one embodiment, the mineral particles contain neodymium and / or dysprosium. Neodymium and dysprosium are used as raw materials for magnets. These elements are known to have the ability to adsorb elements such as phosphorus in water and / or soil.

[0034] One embodiment of the organic matter adsorbent comprises mineral particles consisting of clinoptilolite, kaolinite, montmorillonite, lomontite, perlite, quartz, pozzolanic acid, macubanite, and monazite and / or bastnäsite, and containing neodymium and dysprosium.

[0035] Another embodiment of the organic matter adsorbent comprises mineral particles consisting of 65 to 75 parts by weight of clinoptilolite, 5 to 15 parts by weight of kaolinite, 3 to 10 parts by weight of montmorillonite, 1 to 3 parts by weight of lomontite, 1 to 3 parts by weight of perlite, 1 to 3 parts by weight of quartz, 5 to 9 parts by weight of pozzolanicite, 1 to 3 parts by weight of macubanite, and 0.05 to 0.2 parts by weight of monazite and / or bastnäsite, and containing 0.005 to 0.02 parts by weight of neodymium and 0.005 to 0.02 parts by weight of dysprosium.

[0036] Furthermore, the mineral particles contained in the organic matter adsorbent of the present invention are mineral particles whose surfaces are coated with protein and / or polysaccharide. The protein coating the surface may be a protein containing collagen, elastin, desmosine, or isodesmosine, and the polysaccharide coating the surface may be a glycosaminoglycan. By coating the surface of the mineral particles with protein and / or polysaccharide, the mineral particles can be given remarkable organic matter adsorption capacity.

[0037] One embodiment of the organic matter adsorbent contains mineral particles as an active ingredient, which are coated on the surface with one or more selected from collagen, elastin, desmosine or isodesmosine proteins and glycosaminoglycans, comprising 65 to 75 parts by weight of clinoptilolite, 5 to 15 parts by weight of kaolinite, 3 to 10 parts by weight of montmorillonite, 1 to 3 parts by weight of lomontite, 1 to 3 parts by weight of perlite, 1 to 3 parts by weight of quartz, 5 to 9 parts by weight of pozzolan, 1 to 3 parts by weight of macubanite, and 0.05 to 0.2 parts by weight of monazite and / or bastnäsite, and which also contain 0.005 to 0.02 parts by weight of neodymium and 0.005 to 0.02 parts by weight of dysprosium, and which are coated on the surface with 0.002 to 0.01 parts by weight of collagen, elastin, desmosine or isodesmosine proteins and glycosaminoglycans.

[0038] Furthermore, the present invention provides a method for producing an organic matter adsorbent. The production method of the present invention comprises the steps of: providing mineral particles; coating the surface of the mineral particles with a protein and / or polysaccharide; and irradiating the coated mineral particles with plasma.

[0039] In one embodiment, the step of providing mineral particles provides mineral particles comprising one or more selected from clinoptilolite, kaolinite, montmorillonite, loamontite, perlite, quartz, pozzolan, macabanite, monazite, and bastnäsite. In another embodiment, mineral particles containing one or more selected from light rare earth elements, neodymium, and dysprosium are provided. In yet another embodiment, the step of providing mineral particles provides mineral particles comprising clinoptilolite, kaolinite, montmorillonite, loamontite, perlite, quartz, pozzolan, macabanite, and monazite and / or bastnäsite, and containing neodymium and dysprosium.

[0040] Mineral particles are prepared from pulverized raw materials obtained by crushing each raw material. The particle size of the pulverized raw materials is not limited, but may pass through a mesh of 100-500 or 300-400.

[0041] Mineral particles are prepared by calcining a mixed powder obtained by mixing each raw material, which is then heated in a series of different temperature zones. In one embodiment, mineral particles are prepared by a first heating step of heating the pulverized raw material in a first temperature zone, a second heating step of heating the raw material heated in the first heating step in a second temperature zone, and a third heating step of heating the raw material heated in the second heating step in a third temperature zone. Here, the pulverized raw material may be one or more selected from clinoptilolite, kaolinite, montmorillonite, lomontite, perlite, quartz, pozzolanic acid, macubanite, monazite, bastnäsite, neodymium, and dysprosium.

[0042] In one embodiment, the first heating step may be heating at 110-130°C for 5 minutes, the second heating step may be heating at 260-370°C for 5 minutes, and the third heating step may be heating at 410-470°C for 5 minutes. Each heating step may involve heating while stirring the raw materials. Furthermore, after each heating step is completed, a cooling step may be included in which the heated raw materials are cooled to room temperature.

[0043] Next, the surface of the mineral particles prepared as described above is coated with protein and / or polysaccharide. By stirring the prepared mineral particles in the presence of protein and / or polysaccharide powder, coated mineral particles are obtained. In one embodiment, the mineral particles are coated by stirring them with 0.0001 to 0.1% by weight, 0.001 to 0.01% by weight, or 0.002 to 0.0033% by weight of protein and / or polysaccharide relative to the mineral particles.

[0044] In one embodiment, the protein may be collagen, elastin, a protein containing desmosine or isodesmosine, and the polysaccharide may be a glycosaminoglycan. Alternatively, the protein and / or polysaccharide may be a powder obtained by freeze-drying them. In another embodiment, these proteins and / or polysaccharides may be mixed with other polymers and used to coat the surface of mineral particles.

[0045] Next, the mineral particles coated with protein and / or polysaccharide are irradiated with plasma. The mineral particles irradiated with plasma have an electric charge imparted to their surface by the plasma, becoming charged particles. In one embodiment, the mineral particles irradiated with plasma become positively charged, specifically with a surface charge of 0.01 to 1.0 mV, 0.02 to 0.5 mV, or 0.05 to 0.1 mV.

[0046] The plasma irradiation conditions are not limited as long as mineral particles with the appropriate charge can be produced, but irradiation should be performed at a high-frequency output of 50 to 500 W for 5 to 120 seconds, preferably at 100 to 300 W for 10 to 60 seconds. Irradiation at lower power and shorter durations may not yield the desired modification effect, while irradiation at higher power and longer durations is undesirable as it may lead to reduced workability and deterioration of the substrate.

[0047] In one embodiment, the step of irradiating with plasma may be the step of irradiating with plasma under a reducing atmosphere or a near-vacuum atmosphere. A reducing atmosphere refers to an environment in which oxygen is absent or present in small amounts, and in large amounts of reducing gases such as hydrogen and carbon monoxide, or inert gases such as helium and argon. By preventing oxidation by plasma irradiation, mineral particles with desired properties can be obtained.

[0048] A near-vacuum atmosphere refers to a low vacuum atmosphere, a medium vacuum atmosphere, or a high vacuum atmosphere, specifically a vacuum degree of 1 × 10⁻⁶. -5 Pa~1×10 4 Pa, 1 × 10 -3 Pa~1×10 3 Pa, or 1 × 10 -1 Pa~1×10 2 It could be a vacuum atmosphere of Pa.

[0049] Plasma is generated by applying a voltage in a reducing atmosphere or a near-vacuum atmosphere. Specifically, plasma is generated by applying a voltage of several thousand to tens of thousands of volts in an atmosphere containing a reducing gas or an inert gas to induce an ionization reaction. In one embodiment, the plasma is generated by applying a voltage of 10,000 to 30,000 volts, or 18,000 to 20,000 volts.

[0050] The irradiation time of the mineral particles with plasma is not limited, but if the irradiation time is too short, the properties imparted by the plasma may be insufficient, and if the irradiation time is too long, the proteins and / or polysaccharides coated on the surface may be excessively carbonized. In one embodiment, the plasma irradiation time is 10 to 40 seconds and 20 to 30 seconds.

[0051] One embodiment of the present invention is an organic matter adsorbent comprising mineral particles as an active ingredient, wherein the mineral particles are mineral particles obtained by irradiating mineral particles whose surface is coated with protein and / or polysaccharide with plasma. Another embodiment is an organic matter adsorbent comprising mineral particles as an active ingredient, wherein the mineral particles are mineral particles obtained by irradiating mineral particles whose surface is coated with protein and / or polysaccharide with plasma such that the surface charge is 0.05mV to 0.1mV.

[0052] Another embodiment of the manufacturing method of the present invention includes a step of firing the plasma-irradiated mineral particles. The firing temperature in this step may be 1000°C to 1500°C, 1050°C to 1150°C, or 1100°C. This step can melt the components in the mineral particles and strengthen the particle structure.

[0053] Another embodiment of the manufacturing method of the present invention includes a step of shaping mineral particles irradiated with plasma. One embodiment of this step involves mixing the mineral particles with an additive such as a binder, and shaping the mixed mineral particles using a press molding machine, an extrusion molding machine, or the like. The mineral particles can be shaped into tablets, pellets, chips, discs, blocks, or the like. [Examples]

[0054] The present invention will now be described in more detail based on the examples, but the present invention is not limited to these examples.

[0055] 1. Manufacturing of Examples and Comparative Examples The organic matter adsorbent of the example was prepared. 70 parts by weight of clinoptilolite, 10 parts by weight of kaolinite, 5 parts by weight of montmorillonite, 2 parts by weight of lomontite, 2 parts by weight of perlite, 1 part by weight of quartz, 6 parts by weight of pozzolanic acid, 2 parts by weight of macubanite, 0.065 parts by weight of monazite, 0.035 parts by weight of bastnäsite, 0.01 parts by weight of neodymium, and 0.01 parts by weight of dysprosium were mixed and heated to obtain mineral particles. These mineral particles were stirred with 0.002 to 0.0033 parts by weight of freeze-dried collagen powder and the same amount of sap, etc., to coat the surface of the mineral particles with collagen. Furthermore, the plasma generated by applying a voltage of 18,300 V under a reducing atmosphere was irradiated to obtain mineral particles with a surface charge of 0.07 mV. These were calcined at 1100 °C to obtain the organic matter adsorbent of the example.

[0056] A comparative organic matter adsorbent was prepared. 70 parts by weight of clinoptilolite, 10 parts by weight of kaolinite, 5 parts by weight of montmorillonite, 2 parts by weight of lomontite, 2 parts by weight of perlite, 1 part by weight of quartz, 6 parts by weight of pozzolanic acid, 2 parts by weight of macubanite, 0.1 parts by weight of light rare earth elements, 0.01 parts by weight of neodymium, and 0.01 parts by weight of dysprosium were mixed and heated to obtain mineral particles. These mineral particles were mixed with 0.002 to 0.0033 parts by weight of freeze-dried hemp powder and the same amount of sap, etc., and stirred. This mixture was calcined at 1100°C to obtain the comparative organic matter adsorbent.

[0057] The surface of the manufactured organic matter adsorbent was observed using a scanning electron microscope. As shown in Figure 1, it was confirmed that proteins and other substances were coated on the surface of the mineral particles.

[0058] 2. Evaluation of the organic matter adsorption capacity of the examples and comparative examples. The organic matter adsorption capacity of the examples and comparative examples was evaluated. In addition to the mineral particles described above (Comparative Example 1), commercially available coconut shell activated carbon (Comparative Example 2) was used as the comparative example. 0.05 g of either the example or comparative example was added to 400 mL of a test solution containing a high amount of PFAS, and the mixture was shaken at room temperature for 24 hours using a shaker (MW-SRV, manufactured by Miyamoto Riken Kogyo Co., Ltd.). The examples and comparative examples were removed by filtration through a 0.2 μm membrane filter to obtain the filtrate. Perfluorooctanesulfonic acid (hereinafter referred to as PFOS), perfluorooctanoic acid (hereinafter referred to as PFOA), and perfluorohexanesulfonic acid (hereinafter referred to as PFHxS) contained in the test solution and filtrate were quantified according to the method specified in Japanese Industrial Standard K0450-70-10.

[0059] PFOS at 525 μg / L, PFOA at 381 μg / L, and PFHxS at 101 μg / L were detected in the test solution. The table below shows the concentration of each substance in the filtrate obtained by adding the example or comparative example, the adsorption rate of each substance contained in the test solution, and the adsorption amount per unit weight of the example and comparative example. The example showed a high adsorption rate of 95% or more for all PFAS, including PFOS, PFOA, and PFHxS. The example demonstrated superior adsorption capacity for all PFAS compared to Comparative Example 1, which contained mineral particles with a similar mineral composition to the example, and Comparative Example 2, which was commercially available activated carbon.

[0060] [Table 1]

Claims

1. An organic matter adsorbent having mineral particles as an active ingredient, The surface of the mineral particles is coated with protein and / or polysaccharide, The protein and / or polysaccharide is one or more selected from collagen, elastin, desmosine or isodesmosine-containing proteins and glycosaminoglycans. Organic matter adsorbent.

2. The organic matter adsorbent according to claim 1, wherein the organic matter is an organofluorine compound.

3. The organic matter adsorbent according to claim 2, wherein the organofluorine compound is a perfluoroalkyl compound and a polyfluoroalkyl compound.

4. The mineral particles consist of one or more selected from clinoptilolite, kaolinite, montmorillonite, lomontite, perlite, quartz, pozzolanic, macubanite, monazite, and bastnäsite. The organic matter adsorbent according to any one of claims 1 to 3, wherein the mineral particles include neodymium and dysprosium.

5. The organic matter adsorbent according to claim 4, wherein the surface charge of the mineral particles is 0.05 mV to 0.1 mV.

6. The organic matter adsorbent according to claim 5, wherein the mineral particles consist of clinoptilolite, kaolinite, montmorillonite, lomontite, perlite, quartz, pozzolanic acid, macubanite, and monazite and / or bastnäsite.

7. A method for producing the organic matter adsorbent described in claim 1, The steps of providing mineral particles and The steps include coating the surface of the mineral particles with a protein and / or polysaccharide, The steps include irradiating the coated mineral particles with plasma, Includes, The protein and / or polysaccharide is selected from collagen, elastin, desmosine or isodesmosine-containing proteins, and glycosaminoglycans. Manufacturing method.

8. The step of irradiating with plasma is a step of irradiating with plasma under a reducing atmosphere or a substantially vacuum atmosphere. The manufacturing method according to claim 7.

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