KR101077511B1 - Manufacturing method of bio-absorbent using collagen of raw hide and bio-absorbent therefrom - Google Patents

Abstract

 The present invention provides a method for producing a biosorbent using collagen of animal hides and the biosorbent, wherein the collagen fibers of the solid waste generated in the leather manufacturing process are immobilized with vegetable tannin to produce a biosorbent having excellent adsorption performance for heavy metal ions. It is about.

The present invention comprises the steps of pulverizing the solid waste of animal hides, which are collagen-containing raw materials, deliming and degreasing the pulverized raw materials, and immersing the delimed and degreasing raw materials in a pickle solution containing vegetable tannins. Immobilization step of binding the vegetable tannins with collagen in the raw material, sea island step of releasing the fibrous tissue of the collagen immobilized with vegetable tannins, and pulverized fibrous tissue of collagen immobilized vegetable tannins through the sea island step It provides a method for producing a bio-adsorbent using the collagen of animal skin made by the step of forming a bio-adsorbent and a bio-adsorbent prepared accordingly.

Biosorbent, vegetable tannins, immobilized, collagen, leather

Description

Manufacturing method of bio-adsorbent using collagen of animal skin and its bio-adsorbent {Manufacturing method of bio-absorbent using collagen of raw hide and bio-absorbent therefrom}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a biosorbent, and in particular, to a collagen fiber of solid waste generated in the process of leather manufacturing with vegetable tannins, to prepare a biosorbent having excellent adsorption performance of heavy metal ions, etc. It relates to a production method and a biosorbent thereof.

Unlike the textile industry, domestic leather manufacturing processes use hides and skins derived from animal bodies as main raw materials, so shaving scraps, felt scraps, and buffing dusts, depending on the process characteristics. Solid wastes such as

At present, domestic and specialized research institutes are continuously conducting R & D to recycle such solid wastes as resources, and have some effectiveness, but most of them are commercialized for limited use. Hundreds to thousands of tons per day Many difficulties are encountered in efficiently recycling solid wastes. Therefore, by recycling the collagen contained in the solid waste generated in the leather manufacturing process as an adsorbent, the development of an adsorbent that can contribute to the recycling of solid waste by effectively and eco-friendly removal of organic and inorganic substances, especially heavy metals contained in waste water, etc. It is becoming.

On the other hand, activated carbon and synthetic zeolite have been used as adsorbents for metal ions in the past, and chitosan and various inorganic materials are widely used for adsorption removal of metal ions. However, these conventional adsorbents have excellent adsorption capacities, but are relatively inexpensive, and thus economical, and their adsorption efficiency is limited due to various phase equilibrium characteristics and inefficiency of regeneration.

The present invention was developed in view of the above-mentioned conventional situation and problems, and an object thereof is to prepare a biosorbent having excellent adsorption performance on heavy metal ions and the like by using collagen fibers in solid wastes generated during leather manufacturing. The present invention provides a method for producing a biosorbent using collagen of animal hides and a biosorbent thereof.

The present invention for achieving the above object, the step of pulverizing the solid waste of animal hides, which is a raw material containing collagen, the step of demineralizing and degreasing the pulverized raw material, and the demineralized raw material of vegetable tannin Immobilization step of immersing in the pickle solution contained to bind the vegetable tannins with the collagen in the raw material, the sea island step of releasing the fibrous tissue of the collagen immobilized vegetable tannins, and the collagen immobilized vegetable tannins It provides a method for producing a bio-adsorbent using the collagen of animal hides, comprising the step of pulverizing the fibrous tissue of the final bio-adsorbent.

Here, the solid waste of the animal hide is preferably crushed to a size of 1 to 5 mesh.

In addition, the demineralization and degreasing of the pulverized raw material, 150 to 200% water, ammonium chloride 2.0 to 2.5%, ammonium sulfate 1.0 to 1.5%, degreasing agent 0.5 based on the weight of the pulverized raw material 100% (hereinafter, by weight%) It may be made through the process of leaving for 70 to 90 minutes in a solution of 25 ~ 35 ℃ mixed ~ 1.0%.

In addition, the pickle solution of the immobilization step is 100 to 150% water, 5 to 8% sodium chloride, 0.5 to 1.0% formic acid, and 0.6 to 0.8 sulfuric acid based on 100% (hereinafter, by weight) of the delimed and degreased raw material weight. %, 0.5-1.0% sodium formate, 2.5-3.0% sodium bicarbonate, 0-3% penetrant, 5-15% vegetable tannin, and the delimed and degreased raw material has a temperature of 25-35 ° C., pH 4 It is preferable to be immersed in the said pickle solution of -7 for 14-16 hours.

In addition, it is preferable that the fibrous tissue of collagen immobilized with vegetable tannins subjected to the sea island step is pulverized to a size of 5 to 10 mesh to form a final biosorbent.

The present invention provides a biosorbent prepared by the above production method.

According to the present invention configured as described above, the bio-adsorbent having a very good adsorption performance, such as heavy metals can be produced by recycling the solid waste generated in the leather manufacturing process. Therefore, by providing a bio-adsorbent which is very advantageous in terms of environmental and economical aspects, it is expected to contribute significantly to the development of environmental related industries, including wastewater treatment.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the following embodiments are provided to those skilled in the art to fully understand the present invention, and may be modified in various forms, and the scope of the present invention is limited to the embodiments described below. It doesn't happen.

In the present invention, by recycling the collagen fiber matrix derived from solid waste, which is 50% or more of the raw material weight generated during the leather manufacturing process, various cationic heavy metals such as Cu (II) and Pb (II) contained in the waste water are filtered. To produce a biosorbent.

Raw material, which is a raw material of leather, is composed of collagen protein's natural fiber tissue, and it has excellent adsorption property, and when used as a biosorbent as a natural material, it has a very good performance in adsorbing and removing organic and inorganic materials. Known. In the present invention, by binding to the collagen (vegetable tannin) of vegetable tannins, the plant tannins generally have a structurally adjacent multiple phenolic hydroxyl (phenolic hydroxyl) has a special affinity for most metal ions. . Therefore, vegetable tannin can be usefully applied as an adsorbent component for removing various metal ions in an aqueous solution. However, the use of vegetable tannin as an adsorbent as it is determined that there is an obvious limitation in applying because the vegetable tannin is water-soluble due to its structural characteristics, the present invention has applied a method of denaturation and immobilization of vegetable tannin for insoluble matrixing.

Considering the case where the conventional application of vegetable tannin is used as an adsorbent for removing heavy metals, the vegetable tannin is adsorbed to remove heavy metals by insoluble precipitation through a modified fluidization reaction with several aldehyde compounds such as formaldehyde and glutaraldehyde. It can be seen that it is used as a medium. For example, Japanese Patent Laid-Open No. 3-206494 (U.S. Patent No. 07 / 631,946) dissolves tannin in an aldehyde aqueous solution, adds ammonia to this to form a precipitate, and then matures the precipitate to use as an adsorbent.

In contrast, the present invention is based on the mechanism principle of binding vegetable tannins to collagen fibers of solid wastes produced during the manufacture of leather to introduce immobilized tannins. Fig. 1 shows the chemical structure of immobilizing vegetable tannin on collagen. The ideal immobilized reaction coupling model would strongly induce covalent bonding of vegetable tannins with collagen in leather tissues, resulting in the presence of a hydroxyl group of tannins almost free, thus providing a ligand for metal ion adsorption ( Ligand) increases efficiency. In general, vegetable tannins are known to be very effective in removing heavy metals because their basic structure is an aromatic polyphenol condensate and has a plurality of adjacent hydroxyl groups. These vegetable tannins have been applied to the manufacture of thick leather and strong physical shoes such as work shoes and hiking boots, and has the effect of giving the leather a fullness and proper texture. Acid-assisted tannins have a bleaching effect, a bactericidal effect, and a pale shade effect, while buffing leather has been applied for the purpose of providing a smoothing effect on the surface. As such, the characteristics of animal protein structure can be used as efficient media because it is applied to insoluble matrix of adsorption media by applying the characteristics such as ligand of vegetable tannin and enhancement of heat resistance (durability). Will be.

The following describes in more detail a method for producing a biosorbent using collagen of animal hides according to the present invention.

First, the solid waste of animal skin (leather), which is a raw material containing collagen, that is, fleshing scrap, shaving scrap, felt scrap, buffing dust, etc. After washing, it is crushed. In particular, it is desirable to grind the raw material to a size of 1 to 5 mesh so that the contaminants attached to the surface of these raw materials can be easily removed and the process efficiency (bonding ratio) can be maximized to fix the later plant tannins. Do. Figure 2 (a), (b), (c) is a photograph showing the state of pulverizing the raw material using a felt scrap, a meat grinder, one of the raw materials, respectively crushed raw materials in order.

The raw materials generally contain calcined lime (Ca (OH) ₂ ), sodium sulfide (Na ₂ S), etc., which not only exhibit strong alkalinity but also alkaline swelling of the fiber protein. It is necessary to physically and chemically remove lime, which is an impurity, in a range not included. That is, the process of deliming and degreasing the pulverized raw material, 150 to 200% of water, 2.0 to 2.5% of ammonium chloride (Ammonium Chloride), ammonium sulfate based on the weight of the pulverized raw material 100% (hereinafter, by weight%) (Ammonium Sulfate) It is possible to remove more than 90% of the lime and fat contained in the raw material by leaving it for 70 to 90 minutes in a solution of 25 to 35 ℃ mixed with 1.0 to 1.5%, 0.5 to 1.0% degreasing agent. . The degreasing agent and chemicals as described above can be seen through experiments that the deliming and degreasing efficiency is optimal at the content ratio as described above. There was no significant change and the reaction time was limited to 90 minutes.

Subsequently, the delimed and degreased raw material is immersed in a pickle solution containing vegetable tannin to undergo the immobilization step of binding the vegetable tannin with collagen in the raw material. The pickle solution of this immobilization step is 100 to 150% water, 5 to 8% sodium chloride (NaCl) and 0.5 to 1.0% formic acid based on 100% (hereinafter, by weight) of the delimed and degreased raw material. Sulfuric acid (Sulfuric Acid) 0.6-0.8%, sodium formate (HCOONa) 0.5-1.0%, sodium hydrogen carbonate (NaHCO ₃ ) 2.5-3.0%, penetrant 0-3%, vegetable tannin 5-15%. At this time, the temperature of the pickle solution is 25 ~ 35 ℃, pH is 4 ~ 7 is appropriate, by immersing the delimed and degreased raw material in the pickle solution for 14 to 16 hours, vegetable tannins effectively penetrate into the collagen to bind Be sure to Thus, when plant tannin is bound to collagen and fixed, it exhibits excellent heat resistance (chemical resistance) and durability against heavy metal ions. The sulfuric acid may be used to have an acidity of pH 2.6-2.8, sodium hydrogen carbonate may be used to pH 4.5-4.9, the naphthalene (Naphthalene) penetrant may be applied as the penetrant. As the vegetable tannin, larch tannin, mimosa tannin, bayberry tannin, and the like illustrated in FIGS. 3 (a), (b) and (c) may be applied. In addition, it is also possible to apply tannins derived from quebracho (quebracho), chessnut (chestnut), tara (tara) and the like.

Subsequently, through the islanding step of releasing the fibrous tissue of the collagen immobilized with vegetable tannins, the islanding process can improve the recovery of fibers and maximize the surface area of the tissue to improve the adsorption efficiency of heavy metals. . Figure 4 (a) is a photograph showing the Niagara beater (Niagara beater) that is a device for performing the sea island process, Figure 4 (b) is a picture showing the fibers that are seamed.

Subsequently, the fibrous tissues of the collagen immobilized with vegetable tannins subjected to the islanding step are pulverized using a disk mill or the like to form a final biosorbent. The pulverization size is 5 to 10 mesh to improve the adsorption efficiency of heavy metals. It can be maximized. Figures 5 (a), (b), (c), (d) is a milling state of the mill, the fibrous tissue of the collagen is immobilized vegetable tannin, and a magnified image thereof, photographs showing the packaged products.

Tables 1 to 3 below show the effects of the type, the amount of use and the additives of the vegetable tannins and the use of glutaraldehyde-based tannin supplements (GT-50) for the addition of hydroxyl, based on the process described above. , Examples are shown according to the use of naphthalene-based penetrant (Ukatan GM 0-3%) for increasing the binding efficiency of vegetable tannins and leather tissue (collagen).

TABLE 1

Example 1 Example 2 Example 3 Example 4 PH of pickle solution 4.6 Vegetable tannins Mimosa 15% Mimosa 15% Mimosa 15% Mimosa 10% Penetrant - GM 1.5% GM 1.5% GM 1.5% Tannin supplements - - - GT-50 1.5% Response time / temperature 14 hours / 30 ℃ Heat resistance (℃) 76 82 80 79 Water Resistance-Hot Water Dissolution 1.8% 0.2% or less 0.2% or less 0.2% or less Fiber extraction yield 96% 97% 98% 97%

TABLE 2

Example 5 Example 6 Example 7 Example 8 PH of pickle solution 4.6 Vegetable tannins Mimosa 15% Chestnut 15% Mimosa 15% Mimosa 10% Penetrant GM 3% GM 1.5% Tannin supplements - - - DLE 5% Response time / temperature 14 hours / 30 ℃ Heat resistance (℃) 78 77 76 84 Water Resistance-Hot Water Dissolution 0.2% or less 0.2% or less 0.2% or less 0.2% or less Fiber extraction yield 98% 97% 98% 98%

TABLE 3

Example 9 Example 10 Example 11 Example 12 PH of pickle solution 5.6 Vegetable tannins Mimosa 15% Mimosa 10% 10% Chestnut 10% Chestnut Penetrant - GM 1.5% GM 1.5% GM 1.5% Tannin supplements - - - DLE 5% Response time / temperature 14 hours / 30 ℃ Heat resistance (℃) 80 78 79 82 Water Resistance-Hot Water Dissolution 1.2% 0.2% or less 0.2% or less 0.2% or less Fiber extraction yield 97% 97% 97% 98%

FIG. 6 is a graph showing the adsorption removal rate of Cu (II) ions according to pH change for some of the above embodiments of the biosorbent prepared according to the method of the present invention. As the pH was increased, the adsorption capacity increased, indicating a typical cationic adsorption tendency. This tendency is due to the fact that the deprotonation of ligands having coordination properties to heavy metals with respect to the surface of the biosorbent prepared by the present invention increases as the pH increases, so that the fraction with more negative charge increases, thereby increasing the amount of positive charge. This phenomenon appears because the adsorption of Cu (II) is more advantageous, and the removal mechanism for the heavy metal is considered to occur mainly through the formation of a surface complex such as <Formula>.

<Formula>

In particular, the diesel adsorbents of Example 6 and Example 11 showed superior Cu (II) adsorption capacity at the same pH condition than those of other adsorbents. For these two adsorbents, at least 80% of the initial injection copper concentration (5 × 10 ⁻⁴ M, 31.8 ppm) was removed at pH 4. This removal rate means that 12.71 g of Cu (II) is removed per kg of adsorbent. In particular, at pH 5 and above, all of the adsorbents showed almost complete Cu (II) removal.

As described above, the bio-adsorbent prepared by immobilizing the collagen fiber of the solid waste generated in the process of manufacturing leather with vegetable tannin according to the method of the present invention can recycle 100% of the solid waste, which is eco-friendly and economically very beneficial. It will be a breakthrough biosorbent.

In the above described the present invention based on the preferred embodiment, the present invention is not limited to the above embodiment, various modifications by those skilled in the art within the scope of the technical idea of the present invention This is possible.

1 is a diagram showing the chemical structure of immobilized vegetable tannin in collagen.

Figure 2 (a) is a photograph showing a felt scrap that is one of the raw materials applied to the present invention.

Figure 2 (b) is a photograph showing a state of grinding the raw material using a meat grinder according to the present invention.

Figure 2 (c) is a photograph showing a raw material ground in accordance with the present invention.

Figure 3 (a) is a structural formula for larch tannin as a vegetable tannin applied to the present invention.

Figure 3 (b) is a structural formula for mimosa tannins as vegetable tannins applied to the present invention.

(3c) is a structural formula for bayberry tannin as a vegetable tannin applied to the present invention.

Figure 4 (a) is a photograph showing a Niagara beater which is an apparatus for performing the sea island process of the present invention.

Figure 4 (b) is a picture showing the fibers resolved according to the present invention.

Figure 5 (a) is a photograph showing a disk mill which is a grinding apparatus applied to the present invention.

Figure 5 (b) is a photograph showing the milled state of the fibrous tissue of collagen immobilized vegetable tannin according to the present invention.

FIG. 5C is an enlarged photograph of FIG. 5B.

Figure 5 (d) is a photograph showing a packaged product of the bio-adsorbent prepared according to the present invention.

6 is a graph showing the adsorption removal rate of Cu (II) ions according to pH change for some of the embodiments of the biosorbent prepared according to the method of the present invention.

Claims (6)

Pulverizing the solid waste of animal skin, which is a raw material containing collagen, to a size of 1 to 5 meshes; Demineralization and degreasing of the pulverized raw material, water 150-200%, ammonium chloride 2.0-2.5%, ammonium sulfate 1.0-1.5%, degreasing agent 0.5-1.0% based on 100% by weight of the pulverized raw material (hereinafter, by weight%) Deliming and degreasing the pulverized raw material through a process of leaving for 70 to 90 minutes in a mixed solution of 25 ~ 35 ℃; 100 to 150% water, 5 to 8% sodium chloride, 0.5 to 1.0% formic acid, 0.6 to 0.8% sulfuric acid, 0.5 to 1.0% sodium formate, based on 100% by weight of the delimed and degreased raw material The deliming at a temperature of 25-35 ° C., pH 4-7, of a pickle solution comprising 2.5-3.0% sodium hydrogen, 0-3% naphthalene penetrant, 5-15% vegetable tannins containing multiple phenolic hydroxyls, and Immobilizing the degreased raw material for 14 to 16 hours to bind the vegetable tannins containing the multiple phenolic hydroxyls with collagen in the raw material; Sea island step of releasing the fibrous tissue of the collagen to which the vegetable tannin is immobilized; The method of producing a bio-adsorbent using the collagen of animal hides comprising the step of pulverizing the fibrous tissue of the collagen is immobilized vegetable tannins to the size of 5 ~ 10 mesh to the final bio-adsorbent. delete delete delete delete A biosorbent prepared from the process of claim 1.

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