KR20140006540A - Oil adsorbent using by-products of leather and method of producing the same - Google Patents

Abstract

The present invention relates to an oil absorbent manufactured by using leather waste and a manufacturing method thereof. The manufacturing method comprises: a step of immobilizing collagen ingredients by collecting solid waste generated in a leather manufacturing process, removing fat and mineral from the solid waste and treating the solid waste with vegetable tannin; a step of pulverizing absorbents containing the collagen ingredients by winding off the fibrous tissues of the collagen in which the vegetable tannin is immobilized and pulverizing the fibrous tissues into 5-10 mesh; and a step of manufacturing urethane foam absorbents by selecting polyurethane foam as a carrier of the pulverized collagen absorbent and making the polyurethane foam include the collagen absorbent. [Reference numerals] (AA,CC,EE) X 50 times; (BB,DD,FF) X 100 times

Description

Oil Adsorbent Using By-products of Leather and Method of Producing the Same}

The present invention relates to an oil adsorbent manufactured using leather waste and a method of manufacturing the same, and more particularly, it is possible to adsorb and remove oil by processing leather waste which is inevitably generated during the leather manufacturing process, and the article again. It relates to a urethane foam adsorbent for adsorption removal of oil that can be recycled and used repeatedly, and a method of manufacturing and using the same.

In the domestic leather manufacturing process, raw materials of animals are used as the main raw materials, and according to the progress of the leather manufacturing process, a large amount of solid waste such as felt scrap, shaving scrap, and trimming scrap is generated. Doing. At present, in order to treat (recycling) such solid wastes, domestic research institutes continue to conduct research to some extent.

However, due to the commercialization of the limited use of leather, there are many difficulties in the efficient recycling of solid waste generated from hundreds to thousands of tonnes per year, most of which relies on landfill as industrial waste. As a result, the waste disposal cost of leather companies increases day by day, which is a significant burden, and environmental pollution caused by industrial waste is also becoming more serious.

On the other hand, environmental pollution caused by oil at home and abroad can be made on land or at sea, but it is mainly done at sea. Especially, the oil is transported without permission, or the oil spill is caused by a fire or collision of a ship. can do.

The methods of purifying oil pollution include natural decomposition, sediment purification, biological treatment, chemical treatment and surface adsorption. The natural decomposition method or the natural purification method by deposition is to use the natural decomposition by ultraviolet rays or soil microorganisms in the natural state, it occurs over a long time, it can not be said to be a useful method. The biological treatment method is a method of collecting and culturing microorganisms having excellent degradability for oil, and then rapidly decomposing oil using the microorganisms, but it is difficult to separate and cultivate such microorganisms and is difficult for the general public to use. . On the contrary, the chemical treatment method uses a chemical that decomposes oil, which has the advantage of quickly removing the oil, but has a disadvantage of causing another secondary pollution. will be.

On the other hand, in recent years, the development of technology for environmentally friendly on-site treatment method is actively progress. Currently, oil spill accidents are treated using chemical fiber cloth or emulsifier, but such treatment technology impairs the removal efficiency and secondary pollution problem, so it is urgent to develop new oil absorbent technology to cope with oil pollution effectively.

[Document 1] Korean Patent No. 10-704929 "Trivalent iron-deposited activated carbon for removing heavy metals and organic substances and its manufacturing method" (2007. 4. 2.); [Document 2] Republic of Korea Patent No. 10-1077511 "Method of producing biosorbent using collagen of animal skin and its biosorbent" (2011. 10. 21.).

The present invention is to solve the above problems of the prior art, it is possible to significantly reduce the secondary environmental pollution caused by the leather waste itself by using a large amount of leather waste generated in Korea, the existing synthetic fiber adsorption cloth Compared with oil absorption, it can be used again and again after the first use, and the purpose is to provide a urethane foam adsorbent for adsorption removal of oil produced using leather waste, and a method of manufacturing and using the same.

In order to achieve the above object, the present invention comprises the steps of collecting, degreasing and demineralizing solid waste generated in the manufacturing process of leather and treating with vegetable tannin to fix the collagen component; Pulverizing the fibrous tissue of the collagen to which the vegetable tannins are immobilized and pulverizing the fibrous tissue to a size of 5 to 10 mesh to powder the adsorbent containing the collagen component; Selecting a polyurethane foam as the carrier of the powdered collagen adsorbent, and comprising the collagen adsorbent in the polyurethane foam to prepare a foamed urethane adsorbent.

In the present invention, the step of preparing the expandable urethane adsorbent is added to the collagen adsorbent while mixing and stirring the polyol and isocyanate according to the equivalent, and the water used as the blowing agent is added immediately before mixing and the mixing is completed in a short time. It is preferable to weigh and use a polyol: isocyanate: collagen adsorbent = 100 weight part: 55-57 weight part: 15 weight part-25 weight part as a raw material thrown in. After entering the reactor, the stirring speed may proceed in a conventional manner, and even in the case of reaction temperature, it may be carried out in the usual temperature range. The blowing agent is preferably used 1.5 parts by weight to 3.0 parts by weight with respect to 100 parts by weight of polyol.

Urethane foamed adsorbent for adsorption removal of oils according to the present invention can be used as a useful resource for the solid waste that has been discarded as industrial waste, it is possible to recycle the industrial waste, moreover, landfill of industrial waste or industrial waste There is an advantage to prevent secondary pollution due to fire extinguishing.

Urethane foam adsorbent for adsorption removal of oil according to the present invention has an advantage that can replace the conventional product, because the oil adsorption performance is superior to the conventional product.

In addition, the urethane foamed adsorbent for adsorption removal of oil according to the present invention has elasticity and flexibility, and thus can be reused repeatedly. Therefore, the urethane foamed adsorbent for oil adsorption removal is not a one-time product like a conventional oil adsorbent. .

1 is an enlarged electron micrograph of the microbubble of the PE foam,
2 is an enlarged electron micrograph of the microbubble of the PU foam.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. It is to be noted that the accompanying drawings are only for explaining the technical idea of the present invention in detail and that the technical idea of the present invention is not limited thereto and that various modifications are possible.

The urethane foamed adsorbent for adsorption removal of oils according to the present invention includes the step of collecting and degreasing and deliming solid waste generated in the manufacturing process of leather and treating it with vegetable tannin to fix the collagen component.

The present invention collects solid waste consisting of felt scrap, shaving scrap, and trimming scrap generated in the manufacturing process of leather, and degreasing and demineralizing it. The solid waste of leather is preferably at least 50% of the raw material weight. Raw materials, which are the raw materials of leather, are composed of collagen protein's natural fiber tissue, and have excellent adsorption properties, so that when used as a biosorbent as a natural substance, it has excellent performance in adsorption and removal of organic and inorganic substances. It is known.

In the present invention, the felt scrap obtained from the solid waste and the like are chopped to a size of 5 mm or less, and degreased and demineralized. The degreasing and deliming method can be carried out in a conventional manner. Degreasing from solids removes fat components such as grease, and deliming removes lime components and the like. The degreasing and deliming method is 150-200 parts by weight of water, 2.0-2.5 parts by weight of ammonium chloride, 1.0-1.5 parts by weight of ammonium sulfate, 0.5-1.0 parts by weight of degreasing agent and the like based on 100 parts by weight of solid waste pulverized in the same manner as in the prior art. To prepare a degreasing solution, it can be carried out by leaving the solid waste is deposited for 70 to 90 minutes while the degreasing solution is maintained at a temperature of 25 ~ 35 ℃.

In the present invention, the collagen is immobilized by treating with vegetable tannin after degreasing and deliming from solid waste. Normally, vegetable tannins have structurally adjacent multiple phenolic hydroxyls, and thus are believed to have functional groups capable of hydrogen bonding. In this respect, it is estimated that it can be usefully used as an adsorbent that can adsorb oil contaminated on land or at sea. However, the use of vegetable tannin as an adsorbent as it is, it is determined that there is a clear limit to apply because the vegetable tannin is water-soluble due to its structural characteristics, the present invention applies a method of denaturation and immobilization of vegetable tannin for insoluble matrixing. Through this, it is possible to overcome the limitation due to the water solubility of collagen.

Conventionally, vegetable tannins have been used to remove heavy metal ions to remove heavy metal ions. However, it has not been found to be used for oil adsorbents as in the present invention. Examples of the conventional heavy metal removal adsorbents include a case in which vegetable tannin is used as an adsorbent for removing heavy metals by insoluble precipitation through a modified fluidization reaction with some aldehyde compounds such as formaldehyde and glutaraldehyde. It can be illustrated. For example, Japanese Patent Laid-Open No. 3-206494 (US Pat. No. 07 / 631,946) dissolves tannin in an aqueous aldehyde solution, adds ammonia to this to form a precipitate, and then matures the precipitate to use as an adsorbent.

In the present invention, the demineralized and degreased raw material is immersed in a tannin solution containing vegetable tannin to bind vegetable tannin with collagen in the raw material. The tanning solution of the immobilization step is based on 100 parts by weight of the delimed and degreased solid waste, 100 to 150 parts by weight of water, 5 to 8 parts by weight of sodium chloride (NaCl), 0.5 to 1.0 parts by weight of formic acid, and 0.6 to 0.8 sulfuric acid. It may comprise a weight part, 0.5-1.0 weight part of sodium formate, 2.5-3.0 weight part of sodium bicarbonate, and 5-15 weight part of vegetable tannins. At this time, the temperature of the tanning solution is 25 to 35 ℃, pH is 4 to 7 is appropriate, it is preferable to immerse the delimed and degreased raw material in the tanning solution for 14 to 16 hours. As the vegetable tannin, larch tannin, mimosa tannin, bayberry tannin, kebracho, quebracho, chessnut, tara, and the like may be applied. Among the above, mimosa tannin is more preferable.

By reacting vegetable tannins with the collagen of solid waste in this way, it is possible to combine the effects of ligands of vegetable tannins and enhancement of heat resistance (durability) to achieve insoluble matrix formation of adsorption media and to improve the characteristics of animal protein structure. By transforming into three-dimensional fibrous form, it can be used as a raw material of efficient adsorbent.

The present invention includes the step of pulverizing the fibrous tissue of the collagen to which the vegetable tannin is immobilized and grinding the fibrous tissue to a size of 5 to 10 mesh to powder the adsorbent containing the collagen component.

In the present invention, it is preferable to unwind the fibrous tissue of collagen together with the insoluble matrixing tendency of collagen while undergoing the immobilization step of the collagen component. This is because through the islanding process, it is possible to improve the recovery rate of the collagen particles and to improve the adsorption efficiency by maximizing the surface area of the collagen tissue. The sea island process can be performed using a Niagara beater.

The present invention forms the final bio-adsorbent by grinding the fibrous tissue of collagen subjected to the islanding step using a disk mill or the like. The collagen fibers mean that the vegetable tannin is immobilized. The size of the pulverized particles is preferably about 5 to 10 me. The pulverized particles contain a collagen component immobilized with vegetable tannin, and perform the function as oil absorbent.

The present invention includes the step of selecting a polyurethane foam as a carrier of the powdered collagen adsorbent and preparing the expandable urethane adsorbent by including the collagen adsorbent in the polyurethane foam.

The present invention, in order to utilize the powdered collagen adsorbent more industrially more useful, using a foamed synthetic resin as a carrier, using the fine bubbles of the foamed synthetic resin as the adsorption space of contaminated oil, The collagen component contained in the carrier is used as an oil adsorbent. In this case, when the collagen component adsorbs the contaminated oil, the contaminated oil is attracted to the adsorption space formed by the fine bubbles of the expandable synthetic resin and filled, thereby serving as an oil adsorbent.

According to the present invention, after adsorbing the contaminated oil, the adsorbent can be squeezed and squeezed, and the contaminated oil can be adsorbed and removed again using the adsorbent. This repeated use of the adsorbent according to the present invention is estimated to overcome the limitations that cannot be achieved in the case of conventional adsorbents of waste using collagen. When this is explained further, when the squeezing of the adsorbent is squeezed, the contaminated oil existing in the adsorption space formed by the microbubbles of the expandable synthetic resin is removed, and the adsorption space is present as an empty space again. . When the once-used foamed urethane adsorbent is placed on the contaminated oil again, the collagen component contained in the foamed urethane attracts the contaminated oil again, and the contaminated oil is again inside the empty adsorption space. It will be filled.

On the other hand, when the collagen component immobilized with the tannin component is produced in the form of small grains, a method for recovering and recycling the small grain-shaped ring once used as an adsorbent is currently developed. It is not. Accordingly, the present invention includes the above-mentioned powdered collagen adsorbent therein with a foamable synthetic resin as a carrier in order to repeatedly reuse the oil adsorbent.

In the present invention, it is preferable to limit the foamable synthetic resin to polyurethane foam. Effervescent synthetic resin is a synthetic resin commonly referred to as plastic that forms fine bubbles inside its structure by blowing agent, and according to the material of synthetic resin, PVC (polyvinyl chloride), PE (polyethylene), PP (polypropylene), EVA (ethylene vinyl) Foams such as acetate), PS (polystyrene), PU (polyurethane), TPR (thermoplastic rubber) and the like. At this time, the most common and technically stable and commercialized among the above-mentioned foams are PE foam, PS foam and PU foam.

In the present invention, it is preferable that the microbubbles of the expandable synthetic resin form an open cell structure. The microbubbles of the expandable synthetic resin have a closed type that forms a structure in which the shapes of each individual bubble are closed to each other, and an open type of a structure in which the shapes of each individual bubble are open to each other.

In the case of the closed type, since the bubbles are closed to each other, no other foreign matter can enter the once formed bubble, and typically air entered at the time of initial formation is present inside the cell. The cell structure of this type is mainly formed from the PE foam and the PS foam, and has a very high heat insulating property as its physical property. Therefore, the closed type synthetic resin foam is mainly used as a heat insulating material.

On the other hand, in the case of the open type, since the bubbles are open to each other, once the cell is formed, other materials can enter the inside of the cell, and depending on the situation, other materials may be replaced. do. This type of cell structure is mainly formed in the PU foam, which has a very low heat insulating property as its physical property, and contains water in use, and the heat insulating property tends to become worse. Therefore, the open type synthetic resin foam can not be used as a heat insulating material, a special use is not well developed today, and is mainly used as a cushioning packaging material.

In the present invention, it is preferable that the microbubbles of the expandable synthetic resin form an open cell structure. In the case of an open cell structure, the inside of the open cell can be utilized as a space for adsorbing and storing contaminated oil. When the microbubbles of the expandable synthetic resin form a closed cell structure, even if the situation in which the collagen component adsorbs and attracts the contaminated oil arrives, the cell structure is closed so that the oil can be adsorbed only on the surface thereof. This is because the oil cannot be adsorbed to the inside thereof.

In the present invention, in order to examine the cell structure of the micro-bubbles of the expandable synthetic resin, 90 g of LDPE and 10 g of natural rubber were selected as the base polymer as the PE foam, and 1 g of stearic acid was added thereto, and the mixture was uniformly mixed in the kneader. The homogeneously mixed synthetic resin was again put into a roll mill, and at the same time, 12 g of blowing agent (JTR) and 0.9 g of ferroside-based recipe (DCP) were added as a crosslinking agent. At this time, 20g, 30g, 75g of the collagen powders obtained above were added and foamed, respectively.

In order to obtain a foamed PE synthetic resin and to confirm the structure of its fine bubbles, the effect of the content of the collagen powder was observed by an electron scanning microscope.

1 is an enlarged electron micrograph showing the micro-bubbles of the PE foam, showing the structure of each cell is closed with each other, when the collagen powder input amount of 20g, 30g, 75g, respectively, It denoted by a), (b), (c), and has shown the magnification of 50 times and the magnification of 100 times, respectively.

As can be seen in FIG. 1, when the foamable synthetic resin is selected as the PE series, it is understood that the cell structure of the microbubble is closed, which is not suitable as an oil absorbing material.

Meanwhile, in the present invention, in order to examine the cell structure of the micro-bubbles of the polyurethane-based expandable synthetic resin, 100 g of polyol, which is a polyhydric alcohol, and 56 g of isocyanate are added, and 0.95 g of tertiary amine, which is a catalyst, is further added. Stirring was performed at a rate of about 100 rpm at a temperature of ℃. In the course of uniformly stirring, the collagen powder obtained above was charged with 10 g, 20 g, and 30 g, respectively, and slowly swelled as the reaction mixture foamed.

In order to obtain the foamed PU foam and to confirm the structure of its fine bubbles, the effect of the content of the collagen powder was observed with an electron scanning microscope.

2 is an enlarged electron micrograph of the microbubble of the PU foam, showing that the structure of each cell is open to each other. In the case where the collagen powder input amounts were 10 g, 20 g, and 30 g, respectively, these were labeled as (a), (b), and (c), respectively, and 50-fold magnification and 100-fold magnification were shown, respectively.

As can be seen in FIG. 2, when the foamable synthetic resin is selected as the PU series, it is understood that the cell structure of the microbubble is open, which is very suitable as the oil adsorbent material. In addition, when compared with the above-mentioned FIG. 1, it can be seen that the size of the fine bubbles is much larger and clearly observed.

On the other hand, when the expandable synthetic resin is a polystyrene (PS) series, the cell structure of the microbubble has a typical closed type, and shows good thermal insulation due to the closed cell structure. It is not confirmed by this.

As a result, the present invention was confirmed that the polyurethane series is most suitable as the foamable synthetic resin.

In the present invention, the step of preparing the expandable urethane adsorbent is added to the collagen adsorbent while mixing and stirring the polyol and isocyanate according to the equivalent, and the water used as the blowing agent is added immediately before mixing and the mixing is completed in a short time. It is preferable to weigh and use a polyol: isocyanate: collagen adsorbent = 100 weight part: 55-57 weight part: 15 weight part-25 weight part as a raw material thrown in. After use in the reactor, a catalyst and a blowing agent commonly used may be used, and the inside of the reactor should be mixed uniformly, stirred for uniform mixing, and the stirring speed may be performed in a conventional manner, and It is preferable to maintain the urethane reaction temperature.

The present invention, in order to confirm the adsorption performance of the oil by the polyurethane foam adsorbent, on the basis of the same polyurethane foam, the urethane foam adsorbent was prepared by varying the composition ratio of the collagen powder, respectively.

After preparing each of the polyurethane foam adsorbents according to the content of the collagen powder, it is classified as shown in Table 1 below. At this time, pure water was used as the blowing agent, which was used only for the amount around 20 g of the collagen powder content observed to have the best adsorption performance.

                                                          (Unit: g) Foam adsorbent
division  Polyol Isocyanate  Collagen powder  catalyst  blowing agent  U-0   100  56.25    -   -     -  U-1   100  56.25   10  0.938     -  U-2   100  56.25   20  0.938     -  U-3   100  56.25   30  0.938     -  U-4   100  56.25   40  0.938     -  U-5   100  56.25   50  0.938     -  U-2-15   100  55.20   15  0.938   1.5  U-2-20   100  55.20   20  0.938   2.0  U-2-25   100  55.20   25  0.938   3.0

The present invention, in order to confirm the adsorption performance of oil by each of the polyurethane foam adsorbents, to produce a specimen based on the same criteria, through which to check whether the oil adsorption cloth quality standards of the Ministry of Knowledge Economy.

The present invention is to select kerosene and bunker B oil as the adsorption performance of oil, and to experiment with this on land, whether or not the adsorption performance is changed by reuse, and the experiment in the water phase.

For reference, the oil absorbent cloth quality standards of the Ministry of Knowledge Economy are presented in Table 2 below.

Oil Absorption Cloth Quality Standard  division   1 species    2 species  Temperature  No remarkable change such as softening and hardening  Oil absorption  10g / 1g or more and 1g / 1cm 3 or more  6g / 1g or more and 0.8g / 1cm 3 or more  Absorption  1g / 1g or less, 0.1g / 1cm 3 or more concussion
 damage When it falls into pieces or when the specimen is taken out,
No defects such as remaining  sedimentation  A portion of the specimen floated on the surface of the water  Oil resistance  No significant deformation such as shrinkage, expansion or melting  weight Mat shape: 0.5 ~ 3 kg
Roll shape: 20-100 kg
Cushion shape: 5-30 times the weight of the product

-  burglar  No break          -  Seal         -  No break  Incineration  Hydrogen cyanide 0.8 ml / 1g or less  Extraction Remaining  The average value of the remaining amount of extraction is more than 90%

※ Ministry of Knowledge Economy, KS K 1600 Oil Absorption Cloth

The present invention, in order to confirm the adsorption performance of the oil by each of the polyurethane foam adsorbent, kerosene was selected, and the "adsorption performance of kerosene" was examined as follows.

First, kerosene was filled into the interior of the container with a flat bottom, and a layer of kerosene was formed at 5 millimeters. On the other hand, the polyurethane foam adsorbent according to Table 1 was cut to 5 X 5 centimeters, and a specimen formed with a thickness of 5 millimeters was prepared. Each of the specimens was placed on the surface layer of kerosene inside the vessel and its adsorbed amount was measured for each time period. At this time, the oil adsorption pad of A company currently distributed in Korea for the performance comparison of the polyurethane foam adsorbent according to the present invention was denoted as commercially available 1 (1.4 mm thick) and commercially available 2 (1.8 mm thick).

The results of the measurement by the experiment are shown in Table 3 below.

Comparison results of adsorption performance of kerosene Foam adsorbent
  Oil absorption over time (g / g)  2 minutes  5 minutes  10 minutes  30 minutes  60 minutes  180 minutes  Commercially available 1   8.84   9.68   9.65  10.17  10.39  11.15  Commercially available 2   9.47  10.81  11.20  11.64  11.72  11.85  U-0   3.98   4.37   4.53   4.73   4.77   5.00  U-1   4.55   4.65   4.69   4.71   5.64   5.71  U-2   6.55   6.53   6.53   7.78   7.77   8.81  U-3   6.28   6.44   6.50   6.48   6.45   7.53  U-4   5.88   5.97   6.01   6.45   6.35   6.42  U-5   4.61   4.73   4.81   4.86   4.71   5.88  U -2-15   9.76   9.83   9.94   9.97  10.03  10.05  U-2-20  14.07  14.53  14.67  14.65  14.55  14.66  U-2-25  10.28  10.16  10.17  10.23  10.32  10.35

As a result, it was found that the adsorption performance of kerosene was best when the collagen powder was contained in about 15 g to 25 g, and it was evaluated that the adsorption performance was better than that of conventional commercial products. In particular, it was found that when the blowing agent was included, the adsorption performance was greater. At this time, it can be seen that the adsorption amount at the time when the first 5 minutes had elapsed and the adsorption amount at the time when a considerable time had elapsed thereafter did not differ significantly.

In addition, when the collagen powder contained about 15g ~ 25g, it was confirmed that the oil adsorption cloth quality standards (KS K 1600) of the Ministry of Knowledge Economy.

The present invention, in order to confirm the adsorption performance of the oil by each of the polyurethane foam adsorbent, "Bunker B oil" was selected and examined the adsorption performance. Experimental conditions were carried out in the same manner as the experimental conditions of kerosene mentioned above, and the results of the experiments are shown in Table 4 below.

Comparison results of adsorption performance of bunker B oil Foam adsorbent
  Oil absorption over time (g / g)  5 minutes  15 minutes  30 minutes  1 hours  3 hours  6 hours  Commercially available 1  11.99  12.17  12.13  12.52  13.37  13.20  Commercially available 2  12.96  13.28  13.84  13.98  14.82  15.01  U-0   4.81   5.42   5.69   5.81   6.05   6.16  U-1   6.05   6.18   6.36   6.52   6.61   6.82  U-2  10.07  10.14  10.41  10.32  10.50  10.841  U-3   8.05   8.16   8.27   8.49   8.63   8.90  U-4   6.70   6.74   6.81   6.87   7.05   7.27  U-5   6.06   6.10   6.25   6.37   6.48   6.79  U -2-15   9.91   9.95  10.01  11.08  11.67  11.87  U-2-20  14.92  15.09  15.30  15.34  15.75  15.99  U-2-25  13.88  10.16  14.04  14.18  14.21  14.28

As a result of the measurement, it was found that the adsorption performance of bunker B oil was the best when the collagen powder was contained in about 15 g to 25 g, and it was evaluated that the adsorption performance was better than that of conventional commercial products.

In addition, when the collagen powder contained about 15g ~ 25g, it can be seen that the oil adsorption cloth quality standards of the Ministry of Knowledge Economy (KS K 1600).

The present invention has been examined by checking the adsorption amount of kerosene over eight orders in order to check whether the respective polyurethane foam adsorbents can be reused repeatedly and in such a case, the adsorption performance.

The conditions of the experiment were to remove the oil by prior adsorption, and after 5 minutes had elapsed, the adsorbed oil absorption was measured under the same conditions again. The results of the measurement by the experiment are shown in Table 5 below.

Comparison of measurement of oil absorption during reuse of kerosene Foam adsorbent
  Number of times due to reuse (oil absorption: g / g)   Primary   Secondary   Third   4th   5th   6th  7 tea  8th  Commercially available 1  9.59   4.58   4.79   4.71   4.98   4.43   4.64  4.53  Commercially available 2  10.68   5.90   6.30   5.84   5.86   6.43   6.31  5.95  U-0   5.35   2.21   1.77   2.40   2.45   2.06   2.28  2.43  U-1   4.76   2.84   3.02   2.88   3.64   3.27   3.40  3.22  U-2   7.66   5.20   5.58   5.68   5.62   5.76   5.86  5.82  U-3   5.66   4.31   4.84   4.89   4.70   5.02   5.00  4.95  U-4   5.29   3.46   3.24   3.49   3.65   3.33   3.29  3.45  U-5   3.11   2.62   2.81   2.68   2.91   2.95   2.93  2.90  U -2-15  10.15   9.87   8.36   8.00   8.18   7.80   7.68  7.21  U-2-20  12.06   9.76   9.41   9.30   9.76   9.49   9.17  9.42  U-2-25  10.37   8.53   8.13   8.48   8.75   8.34   8.56  8.98

As a result of the measurement, when 20 g of collagen powder was included and no blowing agent was used, the adsorption rate was relatively high. However, the adsorption rate was significantly lower than that of the blowing agent was included.

On the other hand, in the case of containing a blowing agent, in the range of 15 g to 25 g of collagen powder, the amount of adsorption did not change significantly even after repeated use several times, and the oil adsorption cloth quality standard (KS K 1600) of the Ministry of Knowledge Economy It was found that did not deviate significantly from.

In addition, as compared with the conventional products, the amount of adsorption was much higher, and it was confirmed that the amount of change was small even when repeated use.

In order to confirm whether or not the respective polyurethane foam adsorbents can be used by efficiently adsorbing oil in an environment such as the sea, and to confirm the adsorption performance under such an environment, the "Adsorption amount of kerosene in the water phase" is tested. I checked by.

The conditions of the experiment were to form a 100 millimeter layer of water inside the vessel with a flat bottom and kerosene on a 5 millimeter layer thereon. Here, the specimens of the polyurethane foam according to the present invention were cut to 5 x 5 centimeters, respectively, and formed into a thickness of 5 millimeters to produce them. Each of the specimens was placed on the surface layer of kerosene inside the vessel and its adsorbed amount was measured for each time period. In this case, commercially available 1 (thickness 1.4 millimeters) and commercially available 2 (thickness 1.8 millimeters) used the same products as mentioned above, and were indicated in the same manner.

The results of the measurement by the experiment are shown in Table 6 below.

Comparison of Measurement of Adsorption Performance of Kerosene in Water Phase Foam adsorbent
  Oil absorption over time (g / g)  5 minutes  15 minutes  30 minutes  1 hours  3 hours  6 hours  Commercially available 1  10.21  10.27  10.39  11.00  11.05  11.08  Commercially available 2  10.25  10.45  10.96  11.09  11.28  11.44  U-0   3.88   4.48   4.85   4.89   5.11   5.18  U-1   4.13   5.26   5.65   6.42   6.76   6.79  U-2   8.05   8.81   9.32   9.61   9.92  10.04  U-3   6.07   7.75   7.96   8.53   8.64   8.82  U-4   5.23   5.97   6.53   6.68   7.13   8.52  U-5   4.54   5.42   6.06   6.57   7.08   7.05  U -2-15   9.22   9.51   9.79  10.08  10.28  10.29  U-2-20  14.36  14.34  15.30  14.63  15.04  15.71  U-2-25  11.30  11.96  11.77  12.68  13.29  13.30

As a result, the adsorption performance of kerosene in the water phase was found to be the best when the collagen powder was contained in about 15g to 25g, and it was evaluated that the adsorption performance was better than that of a commercially available product.

The present invention, in order to confirm the efficient adsorption performance of crude oil in each of the polyurethane foam adsorbents in an environment such as the sea, the "Adsorption amount of bunker B oil in the water phase" was examined and examined by experiment.

Experimental conditions were carried out in the same manner as the adsorption performance of kerosene in the water phase mentioned above, and the results of the measurement by the experiment is shown in Table 7 below.

Comparison of Measurement of Adsorption Performance of Bunker B Oil in Water Phase Foam adsorbent
  Oil absorption over time (g / g)  5 minutes  15 minutes  30 minutes  1 hours  3 hours  6 hours  Commercially available 1  12.27  12.43  12.64  12.88  12.76  13.56  Commercially available 2  12.93  13.05  13.26  13.53  13.91  14.20  U-0   4.92   5.48   6.01   5.97   6.11   6.21  U-1   6.50   6.53   6.64   6.73   6.89   7.03  U-2   9.64   9.67   9.80   9.99  10.00  11.18  U-3   8.41   8.50   8.64   8.82   8.93   9.20  U-4   7.27   7.33   7.45   7.48   7.65   7.80  U-5   6.75   6.84   6.95   7.09   7.20   7.37  U -2-15  10.83  11.07  11.22  11.28  11.41  11.51  U-2-20  14.68  14.69  14.86  15.03  15.41  15.68  U-2-25  14.28  14.31  14.34  14.60  14.69  15.16

As a result of the measurement, it was found that the adsorption performance of bunker B oil was the best when the collagen powder was contained in about 15 g to 25 g, and it showed that the adsorption performance was superior to that of a commercially available product.

In addition, when the collagen powder contained about 15g ~ 25g, it was confirmed that the oil adsorption cloth quality standards (KS K 1600) of the Ministry of Knowledge Economy.

Although the polyurethane foam adsorbent according to the present invention and the manufacturing method thereof have been described in detail, this is only for describing the most preferred embodiments of the present invention, and the present invention is not limited thereto, and according to the appended claims The range is determined and defined.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope of the present invention.

Claims (5)

Collecting and degreasing and deliming the solid waste generated during the manufacture of the leather and treating it with vegetable tannin to fix the collagen component;
Pulverizing the fibrous tissue of the collagen to which the vegetable tannins are immobilized and pulverizing the fibrous tissue to a size of 5 to 10 mesh to powder the adsorbent containing the collagen component;
Selecting a polyurethane foam as a carrier of the powdered collagen adsorbent, and preparing the foamed urethane adsorbent by including the collagen adsorbent in the polyurethane foam,
In the step of preparing the foamable urethane adsorbent, the collagen adsorbent is added while mixing and stirring the polyol and the isocyanate according to the equivalent, and the water used as the blowing agent is added immediately before mixing, thereby foaming simultaneously with the urethane reaction. Method for producing urethane foam adsorbent for adsorption removal of oil.
The method of claim 1,
The step of preparing the expandable urethane adsorbent is polyol: isocyanate: collagen adsorbent = 100 parts by weight: 55 to 57 parts by weight: 15 parts by weight to 25 parts by weight, characterized in that used for adsorption removal of oil Method for producing urethane foam adsorbent.
3. The method of claim 2,
The preparing step of the foamable urethane adsorbent is characterized in that using 1.5 parts by weight to 3.0 parts by weight of the blowing agent with respect to 100 parts by weight of the polyol, the production method of the urethane foam adsorbent for adsorption removal of oil.
A urethane foam adsorbent for adsorption removal of oils prepared according to any one of claims 1 to 3.
After preparing the urethane foam adsorbent for adsorption removal of oil prepared by any one of claims 1 to 3,
Adsorption and removal of soil or water contaminated oil using the urethane foam adsorbent for adsorption removal of oil,
A method of using an urethane foam adsorbent for adsorption removal of oil, characterized in that the adsorption removal method is repeatedly performed twice to eight times.

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