Oil adsorbent and method for producing the same

Abstract

To provide a cost-effective oil adsorbent with a high adsorption capability.SOLUTION: An oil adsorbent is obtained by drying a culture medium in which fungal hyphae have proliferated and grown internally. The culture medium may be a spent mushroom bed used in mushroom cultivation, or alternatively, a medium based on a chemical polymer, plant fiber, woody substrate, or porous solid material. Furthermore, the oil adsorbent, after adsorbing oil and being pulverized, can be formed into pellets and used as fuel. In addition, the oil adsorbent, after adsorbing vegetable oil or animal oil and being pulverized, can also be utilized as an auxiliary material for compost fermentation.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] This invention relates to an oil adsorbent that adsorbs oils such as animal and plant-derived oils and mineral oils such as petroleum, as well as its applications and manufacturing methods. Regarding. [Background technology]

[0002] In the past, rapid and effective recovery of oil has been an issue in road traffic accidents, marine accidents such as tanker accidents at sea, and oil leaks from boilers and machinery in factories and other facilities. Efficient recovery of oil using oil recovery equipment such as grease traps in wastewater from kitchens and food processing sites is also an important issue.

[0003] Furthermore, it is said that waste cooking oil from school cafeterias, restaurants, and homes is about 330,000 tons from businesses (70% of which is reused) and about 100,000 tons from homes, and how to dispose of this waste is an issue.Some of the waste cooking oil from homes is solidified, but the rest is poured down the drain, and neither is easy to reuse, and the latter causes environmental pollution, so proper collection and disposal is an issue.

[0004] In response to this problem, conventional methods have included recovering oil that has spilled onto floors by adsorbing it onto sawdust, or by adsorbing it onto oil absorbents made from foams made from minerals such as obsidian, cellulose fibers, or plant seed and grain powder.

[0005] Commercially available products are also known, such as those using polypropylene nanofibers or oil-added cellulose fibers, as adsorbents for oils that float up in grease traps and are primarily on the surface of the water.

[0006] Although not intended to adsorb oils in the above-mentioned situations, a technology that uses waste mushroom beds containing dead basidiomycete fungi as an adsorbent for recovering heavy metals contained in industrial wastewater and the like for the purpose of preventing environmental pollution and recycling rare metals is known from Patent Document 1. Furthermore, a technology that uses waste mushroom beds as boiler fuel by adding and mixing water and oil to the waste mushroom beds, drying them, and separating the oil is known from the waste mushroom beds. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-12272 [Patent Document 2] Japanese Patent Application Laid-Open No. 2010-119928 Summary of the Invention [Problem to be solved by the invention]

[0008] However, among the above oil adsorbents, sawdust generated during wood processing contains a large amount of moisture and also contains high-density fibers and resin even after drying, so there are limits to the amount and capacity of oil adsorption.

[0009] Furthermore, even if the product is sprayed onto the surface of oil that has leaked onto the floor and then absorbed, there is a large amount of oil remaining on the floor, making it difficult to recover oil that has seeped into cracks, recesses, and small areas.

[0010] Furthermore, adsorbents made from mineral raw materials, cellulose fiber materials, or plant seed husks are expensive and require large amounts of adsorbent, as will be described later, so they have issues such as not being particularly high in terms of adsorbent performance.

[0011] Although some of the above-mentioned surface oil sorbents have high adsorption performance, most of them do not have sufficient adsorption performance (especially the amount of adsorption per unit volume), are expensive, and have the disadvantage of being unable to adsorb oil that has adhered to rocks or plants in the event of an oil spill on the sea surface, or that has adhered to the surface of a grease trap.

[0012] In addition, the technologies of Patent Documents 1 and 2 utilize waste mushroom beds (culture medium) used in mushroom cultivation to adsorb heavy metals in liquids or to effectively utilize the waste mushroom beds as boiler fuel, but are not intended to adsorb oil. [Means for solving the problem]

[0013] The oil adsorbent or material using the same of the present invention for solving the above problems is characterized in that it is obtained by drying a culture medium in which fungal hyphae have propagated and grown.

[0014] Secondly, the culture medium is made from waste mushroom beds used for mushroom cultivation.

[0015] Thirdly, it is characterized by being made of a medium based on chemical polymers, plant fibers, wood substrates or porous solids.

[0016] Fourth, the oil adsorbent is crushed after absorbing oil and formed into pellets, which are then used as fuel.

[0017] Fifthly, the present invention is characterized as a compost fermentation aid made of an oil adsorbent that has adsorbed vegetable oil or animal oil and has been crushed.

[0018] Sixth, the present invention is characterized in that it is a livestock feed made of a crushed adsorbent that adsorbs vegetable oil.

[0019] Similarly, a method for producing an oil adsorbent is characterized in that, first, fungi are inoculated into a medium prepared by adding nutrients necessary for mycelial growth to a substrate made of a fiber aggregate or porous solid material consisting of a chemical polymer, plant fiber, or wood substrate, and the fungi are then cultured and dried.

[0020] Secondly, the waste mushroom bed used for mushroom cultivation is crushed to a predetermined particle size, and the fungi in the crushed culture medium are re-cultured and then dried. [Effects of the Invention]

[0021] The adsorbent and manufacturing method of the present invention configured as described above have the advantage that a high-performance waste oil adsorbent can be obtained at a low cost, and that waste mushroom beds produced in the mushroom bed cultivation of various mushrooms can be effectively recycled.

[0022] In particular, by utilizing the hydrophobicity of the fungal mycelium remaining in the waste mushroom bed, it avoids absorbing water and only absorbs oil, making it excellent at absorbing oil that is mixed on the water surface or in the water.

[0023] In addition, adsorbents that have absorbed oil can be used as fuel, making them useful as a high-calorie heat source. Adsorbents that have absorbed waste cooking oil can also be useful as a fermentation aid in the production of livestock feed and organic fertilizer, and may also have effective uses in the food industry. [Brief explanation of the drawings]

[0024] [Figure 1] Photographs (A) to (C) show the appearance of engine oil after it has been poured and spread on a tray and the adsorbent of the present invention and two types of commercially available mineral-derived adsorbents have been sprinkled on it and adsorbed. [Figure 2] (B-1) and (C-1) are enlarged photographs of parts of Figure 1(B) and (C), respectively. [Figure 3] (A) is a plan view (photograph) of the state in which waste cooking oil has been poured onto the water surface in the tray, (B) is a plan view (photograph) of the state in which the adsorbent of the present invention has been sprinkled on top of that, and (C) is a plan view (photograph) of the state in (B) of the same figure after the adsorbent has been collected and removed. [Figure 4] (A), (B), and (C) are photographs of the adsorbent tray after oil adsorption, showing the adsorption state (effect) of oil floating on the water surface by the adsorbent of the present invention and commercially available oil-added cellulose fibers and polypropylene nanofibers. [Figure 5] (A), (B), and (C) are photographs showing the steps of crushing waste mushroom beds, secondary culturing of fungi, and drying in a greenhouse (to kill the fungi) during the process of producing the adsorbent of the present invention, respectively. [Figure 6]1 is a table showing examples of functionality or performance evaluation of the adsorbent of the present invention by particle size. [Figure 7] 1 is a photograph of pellets of the adsorbent of the present invention after absorbing edible oil. DETAILED DESCRIPTION OF THE INVENTION

[0025] The following describes an oil sorbent, its applications, and a manufacturing method that utilizes a fungal bed medium. The oil sorbent of this invention utilizes a fungal bed as a medium for growing fungi that produce wood-decaying fungi such as edible mushrooms, for example, shiitake (Lentinula edodes), maitake (Grifola frondosa), oyster mushroom (Pleurotus ostreatus), and bunashimeji (Hypsizygus marmoreus), plant residue saprotrophs such as mushrooms (Agaricus bisporus), mycorrhizal fungi such as matsutake (Tricholoma matsutake), truffles (Tuber spp.), and porcini (Boletus edulis), but is not limited to these. While used waste fungal beds are primarily used, they are not necessarily limited to used fungal beds as long as dead fungal bodies can be used.

[0026] That is, since waste mushroom beds are continuously produced in large quantities at mushroom production sites, a stable supply of the material is ensured, and there is also the advantage that the waste can be recycled.

[0027] Mushroom cultivation beds (culture media) are generally composed of a substrate consisting of sawdust (wood substrate), nutrient sources such as grain flour and sugars, and, if necessary, supplementary nutrient sources such as seashells, calcium salts, and wood vinegar, as well as minerals and water.

[0028] As is widely known, these mushroom bed substrates undergo a mechanized manufacturing and cultivation process that is determined for each mushroom, including mixing, stirring, filling, sterilization, cooling, inoculation of the seed culture, mycelium cultivation, fruiting body development, and harvesting.

[0029] The waste mushroom bed maintains its shape, for example, a rectangular parallelepiped or cylindrical shape, depending on the type of mushroom to be cultivated, and retains moisture to maintain a constant moisture content. Furthermore, some growing mycelia remain in the waste mushroom bed even after the mushrooms are harvested, and as will be described later, in order for the mushroom bed to function effectively as an adsorbent, these mycelia must be dried.

[0030] For this reason, after harvesting, mushroom beds are first crushed in a general crusher to a final particle size of about 1-4 mm, taking into consideration factors such as increased contact with air, floating on the water surface, and oil adsorption, and are then classified as necessary. This classification removes dust that is harmful to the human body if inhaled and that is not suitable for oil adsorption or recovery.

[0031] It is then desirable to carry out secondary culture under controlled conditions of temperature, humidity, and oxygen content to allow the remaining viable bacteria to grow and increase in number as much as possible. The secondary cultured fungi are then dried to increase the hydrophobicity of their surfaces.

[0032] The secondary culture and drying may be carried out in a specially environment-controlled space, but can also be carried out in a normal indoor workshop, stockyard, greenhouse, etc., as shown in Figures 5(A) to (C).

[0033] In addition, when it is difficult to obtain waste mushroom beds, it is possible to manufacture special culture media for oil adsorbents. In this case, the culture medium base does not necessarily have to be wood, and chemical polymers, plant fibers, porous solids, etc., which are fibrous aggregates that can retain fungi and the nutrients necessary for their reproduction and growth, can be used.

[0034] Chemical polymers include polyethylene, polyester, polypropylene, etc., while porous solids include charcoal and mineral-derived materials such as activated carbon, zeolite, and perlite. Biodegradable polymers that decompose in compost, soil, and seawater are also useful for preventing environmental pollution caused by microplastics.

[0035] Examples of plant fibers include coco peat, coco peat husk, peat moss, crushed bamboo, paper, and cellulose fibers including rayon.

[0036] When a culture medium other than a waste mushroom bed is used for the oil adsorbent as described above, it is sufficient to add nutrients necessary for the growth of the mycelia and grow the mycelia in the culture medium to an extent that they can be used as an adsorbent, and then dry them at the stage of growth to make their surface hydrophobic, and there is no need to perform secondary culture of the fungi.

[0037] Furthermore, when chemical polymer fibers or the like are used as the culture medium substrate, it is not necessarily necessary to crush them. For example, the culture medium (substrate) can be formed into a sheet or mat, and oil that has spilled onto the floor or water surface can be absorbed by spreading it while floating along the floor or water surface.

[0038] Furthermore, for fungal species that form spores during cultivation, using a spore-forming deficient strain prevents the human body from inhaling the spores when handling the adsorbent, thereby preventing any health hazard. Furthermore, using edible mushroom fungi as the fungi can help ensure safety when the adsorbent is used as livestock feed or a vegetable compost fermentation aid. Therefore, even when chemical polymers, zeolites, or some porous minerals are used, those that can be used for livestock feeding or that naturally decompose in soil can be used in the same way as waste mushroom beds.

[0039] When fungi are inoculated and cultured on a fungal bed medium or a nutrient-supplemented substrate, hydrophobins are released from the surface of the hyphal cells into the extracellular water during the mycelial growth process. Hydrophobins are low-molecular-weight proteins, with one half hydrophobic and the other half hydrophilic. When the water dries out, they self-assemble on the surface of the hyphal cells to form an amphiphilic layer with the hydrophobic surface exposed on the outside.

[0040] This is thought to give the adsorbent of the present invention hydrophobic (lipophilic) properties. In addition, if the surface of a decomposed waste mushroom bed, porous solid material, or a sheet or mat made of fiber is lipophilic, the oil adsorption ability will increase due to capillary action.

[0041] The oil adsorbent of the present invention realizes oil adsorption by utilizing the hydrophobic groups on the surface of filamentous fungi and basidiomycetes, which repel water and adsorb oil.

[0042] The adsorbents of the present invention can adsorb all kinds of hydrophobic and lipophilic substances, including oils that undergo phase separation from water, such as animal and vegetable oils and mineral oils, petroleum, which is primarily composed of hydrocarbons, and essential oils, which are primarily composed of terpenes, as well as harmful substances that are hydrophobic.

[0043] 1. Oil adsorption applications and advantages of the adsorbent of this invention Next, we will explain the performance comparison between the target scenario in which the adsorbent of the present invention is used to adsorb oil and conventional oil adsorbents. (1) Oil spills on asphalt roads, etc. During collisions, oil often leaks onto asphalt roads. The leaked oil is treated using oil absorbents. Granular oil absorbents made from minerals are generally used, but they have the following problems: a. If the road surface is rough, the particles of the absorbent material are too large to absorb the oil in the gaps in the asphalt. b. Because of its large specific gravity, residue of the adsorbent tends to remain even after sweeping up after adsorption. c. It has the disadvantage of being milky white and the remaining adsorbent being visually very noticeable. In contrast, the waste mushroom bed adsorbent of the present invention contains fine particles and is therefore capable of adsorbing oil from gaps in asphalt, and because it has a low specific gravity, it can be removed by simply sweeping or cleaning for a short period of time. In addition, since the waste mushroom bed is generally brown, even if any is left behind, it is not visually noticeable and there is no concern that it will hinder the driver's attention. If treatment is to be carried out during rainy weather, waste mushroom bed with reduced hydrophobicity may be mixed in at a certain ratio and subjected to adsorption treatment.

[0044] (2) Oil absorption in grease traps A grease trap is a device used to remove oil and fat from wastewater in restaurants, kitchens, etc. Without this device, the oil contained in the wastewater can clog sewer pipes, causing environmental pollution and the breakdown of facilities such as septic tanks. Grease traps require regular cleaning using oil absorbents because oil and fat rise to the surface and accumulate, causing putrid odors if not removed. Many conventional adsorbents are fluffy and have difficulty adsorbing oil that has adhered to the walls of a grease trap. In contrast, it has been confirmed that the waste mushroom bed oil adsorbent is granular, so it easily adsorbs oil on the wall surface. It has also been confirmed that the oil adsorption capacity per volume of the oil adsorbent is 2 to 3 times higher than that of conventional polypropylene fiber or oil-added cellulose fiber.

[0045] (3) Oil spills in rivers and oceans When oil or petroleum products are spilled underwater or on the water surface, an oil boom is deployed outside the spill area to prevent the spilled oil from spreading. Oil sorbents are then used to collect floating oil inside and outside the oil boom. A problem with conventional sorbents is that fluffy materials have difficulty absorbing oil attached to rocks, sandy beaches, or plant matter. The oil sorbent of the present invention can also absorb oil adhering to gaps and plant matter. It also has a high oil absorption capacity per bulk volume, and since it does not contain chemical polymers or minerals when using a plant-based base material, it can naturally decompose if stored outdoors on land to prevent the oil from re-leaching.

[0046] (4) Oil pan An oil pan is used as a container to collect used oil when changing engine oil. A typical oil pan is a cardboard box filled with a plastic bag and nonwoven fabric that absorbs oil. However, using only nonwoven fabric makes it easy for oil to spill from the plastic bag, so care must be taken when handling it. By using the absorbent material of the present invention, the oil can be solidified into granules inside the plastic bag, preventing oil spillage.

[0047] (5) Treatment of used cooking oil Waste cooking oil is oil used in restaurants and at home during cooking. If not disposed of properly, it can cause environmental pollution by clogging drains and deteriorating septic tanks. For this reason, it is often discarded by turning it into solid oil pellets, or collected by waste disposal companies in the case of businesses. Collected waste cooking oil can be reprocessed and put to effective use in biodiesel fuel, animal feed, fertilizer, or soap. One issue is that oil solidified at home cannot be reused. Furthermore, it is difficult to reuse used cooking oil collected at businesses that has decayed or oxidized, or that contains a lot of foreign matter or moisture. Chlorine-based lubricating oil and water-based lubricating oil are also difficult to reuse. However, when used cooking oil is adsorbed using a used mushroom bed oil adsorbent, it can be used for a variety of purposes, including as fuel, a material to promote the composting of livestock manure, livestock feed, and a material to raise the temperature of home compost, making it possible to effectively utilize even used cooking oil that is difficult to reuse.

[0048] 2. Other uses of the adsorbent of the present invention The adsorbent of the present invention can be used not only as an adsorbent for oil but also as a resource for other uses as described below after adsorbing oil.

[0049] (1) Pellet fuel Materials that have absorbed oil can be used as fuel. They are particularly easy to handle when solidified into pellets. Generally, it is difficult to solidify materials containing oil into pellets, but if waste mushroom beds are mixed with oil-containing materials, they can be pelletized due to the adhesive properties of the waste mushroom beds. They have a calorific value that is 20-50% higher than regular wood pellets. Also, mixing oil:waste mushroom beds in a ratio of 5-15:95-85 makes them easier to mold.

[0050] (2) Composting promoter for livestock manure, etc. Fermentation temperatures at livestock manure treatment plants often do not rise sufficiently, resulting in immature compost production. Fermentation does not progress sufficiently, especially in winter. Adding waste cooking oil to manure can be considered effective because it increases the fermentation temperature over the long term, but because the oil is liquid, it actually inhibits the rise in fermentation temperature due to a lack of oxygen in the early stages of addition. In contrast, waste mushroom beds that have absorbed the oil are in a granular form, which allows oxygen to be supplied at the same time, making it possible to produce high-quality compost that has progressed sufficiently in a short period of time.

[0051] (3) Home compost temperature-raising material Used cooking oil raises the temperature of household compost by 10 to 20 degrees Celsius, accelerating the decomposition of food residues. Liquid used cooking oil is difficult to handle, and if it is solidified with additives, aerobic fermentation does not progress in the compost. Considering the mess that would result if the oil leaked, it is difficult to actively use it in compost. Furthermore, since used cooking oil generated from household cooking is small and dispersed, it is difficult to collect and reuse industrially. Oil-absorbed waste mushroom beds can be used at home as a material to raise the temperature of compost. Furthermore, because it is in a granular form, it can be thrown into fields and composted. Because household waste cooking oil is small and dispersed, it is difficult to collect it for industrial reuse. However, if it is absorbed and made into granules, it becomes easy to handle, and households can take it to collection points and reuse it for various purposes.

[0052] (4) Livestock feed The main components of wood are cellulose, hemicellulose, and lignin. Of these, lignin is extremely difficult to decompose and digest for many microorganisms and animals. Most mushrooms are white-rot fungi, which have a high ability to decompose lignin, so lignin in waste mushroom beds is highly decomposed. For this reason, waste mushroom beds can be used as livestock feed. However, some livestock may not eat them well, perhaps because they have a poor palate. Therefore, adding waste cooking oil or edible oil to waste mushroom beds is expected to improve their appetite, and waste mushroom beds that have absorbed the oil are expected to be high-quality livestock feed.

[0053] (5) Other This adsorbent can be used as a detergent for hand washing, especially after handling oils, and by roasting food using pellets made from waste mushroom beds and vegetable oils such as coconut oil or olive oil, essential oils such as terpenes, or animal fats, it can be used to flavor or scent food.Furthermore, if various volatile oils are contained in fungal propagation materials, they evaporate very slowly, so they can be used as a base material for air fresheners. The use of the above-mentioned fungal bed-based adsorbent can be applied to fungal propagation materials artificially produced by cultivation in addition to waste fungal beds, as already mentioned.

[0054] [Example] Examples of the present invention will be explained below with reference to the drawings. Figures 1 and 2 compare the oil adsorption state of the adsorbent of the present invention with that of a conventional commercially available mineral-derived adsorbent. In both cases, 50 ml of ordinary engine oil was poured and spread onto an aluminum tray. Figure (A) shows the adsorbent produced using the ash fungal bed of the present invention, while Figures (B) and (C) show 100 ml of commercially available mineral-derived adsorbents from different manufacturers, each evenly sprinkled with oil adsorption, and then the oil-adsorbed adsorbents were pushed to one side.

[0055] Figures 2(B-1) and (C-1) are enlarged photographs of parts of Figures 1(B) and (C). Both are based on the scenario of oil spilled on a flat surface such as a road surface being sprayed with absorbent material to absorb and recover the oil.

[0056] According to this experiment, in the case of Figure 1(A), most of the oil was absorbed by the adsorbent itself, and it was removed to the extent that almost no oil remained on the bottom of the tray, whereas in the case of Figure 1(B) and Figure 2(B-1), the adsorbent itself was not able to absorb all of the oil, and streaks of oil remained along with the adsorbent.Furthermore, in Figure 1(C) and Figure 2(C-1), the adsorbent was also not able to absorb all of the oil, and a thick oil film remained in a flowing state on the bottom of the tray.

[0057] Figures 3(A) to (C) show an enameled tray filled with enough water to cover the entire surface, with (A) showing the state in which 30 ml of waste cooking oil has been dripped onto it, (B) showing the state in which an adsorbent made from the waste mushroom bed of the present invention has been sprayed on top of that, and (C) showing the state after the adsorbent has been recovered and removed after adsorbing the oil in (B). This photo shows that almost all of the oil was recovered by absorbing the absorbent material.

[0058] Figures 4(A) to (C) are photographs taken in separate trays of the state of three types of adsorbents that had adsorbed oil using the method shown in Figure 3. In this example, Figure 4(A) shows an adsorbent made from waste mushroom beds, Figure 4(B) shows a commercially available oil-added cellulose fiber adsorbent, and Figure 4(C) shows a commercially available polypropylene fiber adsorbent.

[0059] In this example, to recover 30 ml of waste cooking oil, approximately 45 ml of adsorbent (A) made from the waste mushroom bed of the present invention was sufficient, whereas in the examples of (B) and (C) in the same figure, 100 to 150 ml of adsorbent was required, which was found to be approximately 2 to 6.7 times the volume of (A). Furthermore, as in the example of Figure 1, it was also possible to visually confirm that the waste mushroom bed was superior in terms of whether it was able to fully absorb the oil (oil absorbency).

[0060] Figure 6 shows a test in which the particle size diameter of the pulverized adsorbent of the present invention, which uses waste mushroom beds, was classified into four levels, from less than 1 mm to 4 mm or more, and the oil adsorption capacity and sinking ability in water for each particle size were compared against oil floating on the water surface. It has been confirmed that particles less than 1 mm have low oil adsorption capacity, generate dust, and are prone to sinking in water. Furthermore, particles less than 1 mm can cause water-soluble components to elute from the waste mushroom beds, causing the water to turn brown. For this reason, it is desirable to avoid particle sizes less than 1 mm.

[0061] Figure 7 shows a photograph of the waste mushroom bed adsorbent that has adsorbed waste cooking oil and been made into pellets. It was revealed that these pellets have 1.3 to 1.5 times the calorific value of regular wood pellets and are also highly water-resistant during storage. Incidentally, it is difficult to pelletize regular sawdust that has absorbed oil as is, but it was confirmed that it is possible to pelletize the mushroom bed-based adsorbent.

Claims

1. An oil absorbent material made by drying a culture medium in which fungal hyphae have propagated and grown.

2. 2. The oil adsorbent according to claim 1, wherein the culture medium is a waste mushroom bed used for mushroom cultivation.

3. 2. The oil adsorbent according to claim 1, which comprises a culture medium based on a chemical polymer, plant fiber, wood substrate or porous solid material.

4. 3. A fuel in the form of pellets of the oil adsorbent according to claim 1 or 2, which has adsorbed oil and been pulverized.

5. 3. A compost fermentation aid comprising the oil adsorbent according to claim 1 or 2, which has adsorbed vegetable oil or animal oil and has been pulverized.

6. A livestock feed comprising the adsorbent according to any one of claims 1 to 5 which has adsorbed vegetable oil and has been pulverized.

7. A method for producing an oil adsorbent, comprising the steps of inoculating fungi into a medium containing a fiber aggregate made of chemical polymers, plant fibers, or wood substrates, or a substrate made of a porous solid material, to which nutrients necessary for mycelial growth have been added, cultivating the fungi, and then drying the fungi.

8. This is a method for manufacturing an oil adsorbent by crushing waste mushroom beds used in mushroom cultivation to a specified particle size, re-cultivating the fungi in the crushed culture medium base material, and then drying the medium.

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