TWI705173B - Method for making paper with discarded oyster shells and its finished products - Google Patents

Abstract

The present invention relates to a method for making paper from discarded oyster shells and its finished products. It includes the following steps: (a) enzymes to remove the rotten flesh of oyster shells; (b) grinding oyster shells into powder, and taking a part of the oyster shell powder Do high-temperature sintering to obtain sintered oyster shell powder; (c) prepare a binder mixed solution: take the sintered oyster shell powder, fucoidan, konjac glucomannan and glycerin and mix with water to prepare a binder mixed solution (D) Take another part of the ground but unsintered oyster shell powder and the above-mentioned binder mixture solution to uniformly mix into oyster shell paper material; (e) molded oyster shell paper: pour the oyster shell paper material Put it into a mold, heat and dry, and get oyster shell paper after demolding.

Description

Method for making paper from discarded oyster shells and its finished products

The present invention relates to a method for making paper from discarded oyster shells and its finished products, in particular to a method of using discarded oyster shells through pineapple enzyme aqueous solution to remove the rotten flesh on the oyster shells, and then crushing the oyster shells from which the rotten flesh has been removed after drying After being broken into pieces, they are sequentially ground and processed into waste oyster shell powder. A part of the waste oyster shell powder is sintered at a high temperature to form the sintered oyster shell powder. Then another part of the unsintered waste oyster shell powder is mixed with fucoidan, konjac glucomannan, sintered oyster shell powder, glycerin and water mixed binder to make oyster shell paper by casting method Technology.

According to the current survey data, it takes about four metric tons of wood to produce one metric ton of paper pulp, which is equivalent to cutting 23 trees. Due to the current industrial and commercial economy, the demand for pulp has increased greatly, and humans have cut down a large number of trees in the forest, which has gradually reduced the forest area in various places. A large number of deforestation not only seriously affects the balance of the natural ecological environment, but also leads to one of the culprits of global warming. In addition, the traditional pulp and paper method must use a large amount of water and chemicals to bleach the wood pulp, which causes the pollution of precious water resources such as rivers and oceans. Therefore, all countries in the world expand the area of artificial forestation on the one hand, and actively on the other hand. Develop alternatives to pulp.

In view of the serious natural ecological and environmental protection problems caused by cutting wood for papermaking Question, many researchers and industry have invested in the research, development and manufacture of green paper. The so-called green paper is generally called stone paper in Taiwan, and it is a viable product to replace paper made from pulp. It is currently known that the conventional preparation method of green paper is made by mixing inorganic ore powder and resin as materials through a specific process. Since the green paper can be decayed and ashed and returned to the soil after being used in the sun, it will not cause secondary pollution to the environment. The recycled paper is burned in an incinerator and will not produce black smoke and poisonous gas. The remaining inorganic ore powder can return to the earth again.

Taiwan Invention Announcement No. 581791 "High-gloss calcium carbonate coating composition and coated paper and cardboard made therefrom" patent case, which contains the blending of first and second discontinuous aragonite precipitated calcium carbonate (PCC) particles Match. The average particle size (APS) of the first type of calcium carbonate (PCC) particles is about 0.4 microns, the average particle size (APS) of the second type of calcium carbonate (PCC) particles is about 0.5 microns, and the first 0.4-micron particles are The weight ratio of the two 0.5 micron particles is from about 50:50 to about 80:20. Although the paperboard produced in this patent case meets the requirements of environmental protection, recycling and recycling, it still has the following shortcomings: 1. It needs to use a specific stone and be ground by a special machine to make the first and second particle deposits. The average particle size (APS) of calcium carbonate is 0.4 and 0.5 microns, respectively. The cost of machinery and equipment is high, and the manufacturing cost is relatively increased. The cost of the paper is relatively high, and the economic value is not high. Therefore, it cannot be effectively mass-produced and popularized.

Taiwan Invention Publication No. 31024501 "Stone Paper Manufacturing Technology" is a mixture of PE and nano-calcium carbonate. The filling amount of PE plastic material is 3~90%. Nano-calcium carbonate is made of granules. Nanometer calcium carbonate particles with diameters ranging from 30 to 100 nm are formed by agglomerating structure, and the filling amount of nano calcium carbonate can account for 10-97% in the stone paper. It is added with polymer materials such as polypropylene (PP) and polyethylene (PE), which makes the paper texture relatively softer than the Taiwan Invention Patent No. 581791 It is soft, but it still has the following shortcomings: 1. The average particle size of the nano-calcium carbonate in this patent is between 30 and 100 nanometers. The particle size is small, and a special grinding process is required to make the particle size reach the nanometer level. , The high cost of machinery and equipment has caused a relatively large increase in manufacturing costs. Because the cost price is higher than that of ordinary paper, the economic value of this customary product is not high, so it cannot be effectively mass-produced and popularized.

Furthermore, according to the statistics of the Council of Agriculture of the Executive Yuan, Taiwan is rich in oysters. It is conservatively estimated that the oyster shells produced each year weigh as much as 160,000 metric tons, which has always been difficult to handle. In the past, most of the oyster shells were discarded arbitrarily, not only occupying space, but also prone to breeding mosquitoes and flies, as well as foul odors due to high temperature and sunlight, causing serious environmental pollution. The main ingredient of oyster shell is calcium carbonate, with other ingredients such as phosphorus, zinc, magnesium, aluminosilicate and iron oxide. In recent years, the government has promoted the reuse of oyster shells and increased their added value. For example, cooked oyster shells are used in agriculture and animal husbandry, as feed for chickens and ducks, as materials and fertilizers for soil improvement and soil pollution improvement. Used in water quality improvement, as a water quality buffer, water quality pollution indicator and circulating water filter material. Used in medicine, it extracts nacre peptides that can be used as beauty care products, calcium supplements that are easily absorbed by the body, and natural bacteriostatic agents. Materialized applications include cement, cement, aggregates for concrete, etc. In order to assist the government in solving and digesting a large amount of discarded oyster shells, the inventors of the present invention actively invest in research. The inventor is aware of the technology of environmentally friendly paper and the concept of environmental protection. The waste oyster shell ingredients should be used as environmentally friendly paper. The inventor invests in research on the ingredients of discarded oyster shells, how to prepare discarded oyster shell paper materials, and make waste oyster shell paper with environmental protection effects. After continuous experiment and trial production, the results of the present invention are finally obtained. It is believed that when it is effectively used for commercial and full use in the future, it will be able to more effectively solve the odor and environmental problems derived from discarded oyster shells, thereby enhancing the added value of the reuse of discarded oyster shell resources.

The first object of the present invention is to provide a method for making oyster shell paper that has environmental protection properties and can be biodegraded. The technical means to achieve this goal include the following steps: (a) Removal of oyster shell rot with enzymes: pineapple enzyme to remove scum of discarded oyster shells; (b) Preparation of oyster shell powder required for papermaking: pulverization of discarded oyster shells Take a part of the oyster shell powder for high-temperature sintering to obtain waste oyster shell powder after sintering; (c) Prepare an environmentally friendly binder mixed solution: take the sintered waste oyster shell powder, fucoidan and konjac glucomannan , Glycerin and water to prepare a binder mixed solution; (d) Prepare oyster shell paper materials: take another part of the waste oyster shell powder and the above binder mixed solution and mix it into oyster shell paper materials. (E) Molded oyster shell paper: pour the oyster shell paper material into a mold, heat and dry, and then release the oyster shell paper.

The second object of the present invention is to provide an environmentally friendly oyster shell paper that can be biodegraded. It uses the method of the first objective in the previous paragraph to prepare oyster shell paper. The oyster shell paper is mixed with unsintered oyster shell powder, sintered oyster shell powder, fucoidan, konjac glucomannan and glycerin, which is environmentally friendly The effect of being biodegradable.

The third object of the present invention is to provide a product using the oyster shell paper of the present invention that can be biodegraded with environmental protection properties. The product can be disposable wrapping paper, anti-fungal and antibacterial insoles, straws curled into tubes, and disposables. Decomposable dinner plate or lunch box.

(a)‧‧‧Enzyme to remove oyster shell carrion

(b)‧‧‧Oyster shell powder required for papermaking

(c)‧‧‧Preparation of environmentally friendly adhesive mixed solution

(d)‧‧‧Mixed oyster shell paper materials

(e)‧‧‧Molded oyster shell paper

10‧‧‧Oyster Shell

20‧‧‧Oyster Shell Powder

21‧‧‧Sintered oyster shell powder

30‧‧‧Environmental protection adhesive

40‧‧‧Oyster shell paper material

50‧‧‧Mould

60‧‧‧Spreader

Figure 1 is a schematic diagram of the manufacturing process of oyster shell paper of the present invention; Figure 2 is a schematic diagram of the oyster shell paper molding process of the present invention; Figure 3 is a schematic diagram of the oyster shell paper of the present invention; Figure 4 is a physical photo of the oyster shell paper of the present invention; Figure 5 is the oyster shell of the present invention during different stages of processing and sintering The schematic photo after completion.

In order for your reviewer to further understand the overall technical features of the present invention and the technical means to achieve the purpose of the present invention, specific examples and drawings are used to describe in detail as follows.

Please refer to Figures 1 to 3 for the method of making paper from discarded oyster shells to achieve the first objective of the present invention. The specific embodiment includes the following steps: (a) Enzymes to remove oyster shell rotten flesh: Pineapple enzymes to remove discarded oysters Rotten flesh of the shell; (b) Preparation of oyster shell powder 20 required for papermaking: grind waste oyster shells into powder to obtain waste oyster shell powder 20, take a part of oyster shell powder 20 and sinter at high temperature to obtain sintered oyster shell Powder 21; (c) Prepare an environmentally friendly adhesive mixed solution: Take the sintered waste oyster shell powder 21, fucoidan, konjac glucomannan and glycerin and mix with water to prepare a adhesive mixed solution; (d) Prepare oyster shells Paper-making material 40: Take another part of the unsintered waste oyster shell powder 20 and the above-mentioned binder mixture solution and mix uniformly to form an oyster shell paper material 40; (e) Molded oyster shell paper: Pour the oyster shell paper material 40 The oyster shell paper 10 can be obtained after being put into a mold 50, heated and dried, and demolded. The oyster shell paper 10 includes unsintered waste oyster shell powder 20 and an environmentally friendly adhesive 30, and the environmentally friendly adhesive 30 includes sintered waste oyster shell powder 21, fucoidan, konjac glucomannan, glycerin and water.

In a preferred embodiment of the present invention, in step (a), the pineapple enzyme aqueous solution is prepared with water and pineapple enzyme to prepare an pineapple enzyme aqueous solution containing 0.05 to 0.3% of pineapple enzyme, and oyster shells are soaked in the pineapple enzyme aqueous solution 6 -12 hours, then rinse the oyster shells soaked in the pineapple enzyme aqueous solution with a high-pressure water column to remove the sediment and rotten flesh on the surface of the oyster shells.

In a preferred embodiment of the present invention, in step (b), the sintering temperature and time are 800 to 1000° C. and 1 to 3 hours, respectively. The heating rate is set at 5°C per minute. Figure 5 shows the situation of the oyster shells of the present invention during different stages of processing and after sintering. In Figure 5, A refers to the state where the oyster shell is crushed by a corner cutter; B refers to the oyster shell after rough grinding with a vertical grinder, and its average diameter is about 20-30um; C refers to The place is the oyster shell powder after the oyster shell is finely ground by the air-flow grinder. The average diameter of the oyster shell powder is about 5-10um; the point D refers to the oyster shell after the sintered oyster shell has been heat-treated in a high-temperature sintering furnace at 900℃ for 2 hours. Oyster shell powder.

In a preferred embodiment of the present invention, in step (c), the binder mixture solution is 95-99 parts by weight of distilled water, 0.1-0.5 parts by weight of sintered oyster shell powder, and 0.1-0.5 parts by weight of brown algae Polysaccharides, 0.1 to 0.5 parts by weight of konjac glucomannan, and 0.1 to 0.5 parts by weight of glycerin are mixed with each other to prepare the binder mixed solution. After completing step (c), in step (d), 75 to 95 parts by weight of unsintered oyster shell powder and 5 to 25 parts by weight of the binder mixed solution are uniformly mixed to form an oyster shell paper material. After completing step (d), in step (e), pour the oyster shell paper material into the mold and cast.

In a preferred embodiment of the present invention, in step (c), glycerin is added to distilled water and stirred, then fucoidan is added and stirred, then konjac glucomannan is added, stirred and frozen, and then the sintered oyster is added The shell powder is stirred to obtain a uniform mixed solution of the binder.

In a preferred embodiment of the present invention, in step (e), the drying temperature and time are 40~80°C and 8~12 hours respectively.

The embodiment to achieve the second objective of the present invention is to prepare the oyster shell paper 10 (as shown in Figures 2 and 3) by the method of the present invention described above, and the oyster shell paper 10 is mixed with oyster shell powder 20 and an environmentally friendly adhesive 30 , The environmentally friendly binder 30 includes fucoidan, konjac glucomannan, glycerin and water. That is, the oyster shell paper 10 prepared by the present invention contains unsintered oyster shell powder 20, sintered oyster shell powder 21, fucoidan, konjac glucomannan, glycerin and water. Specifically, the composition of oyster shell paper includes 7.5 to 9.5 parts by weight of unsintered oyster shell powder, 0.1 to 0.5 parts by weight of sintered oyster shell powder, 0.1 to 0.5 parts by weight of fucoidan, and konjac glucomannan It accounts for 0.1 to 0.5 parts by weight, and glycerin accounts for 0.1 to 0.5 parts by weight.

The third objective of the invention is achieved by using the environmentally friendly oyster shell paper made by the invention that can be biodegraded, and the oyster shell paper is made into various products. The products can be disposable wrapping paper, mildew-proof and antibacterial insoles , Straws curled into tubes, disposable decomposable dinner plates or lunch boxes. Making these products biodegradable, not only has environmental protection functions, but also greatly increases the reuse value of discarded oyster shells.

In the experimental example of the present invention, the disposal method of discarded oyster shells is to first prepare 20L of 0.1% pineapple enzyme aqueous solution: take a 20 liter container, pour 20 liters of tap water, add 20g pineapple enzyme, and stir for 3 minutes to completely dissolve the pineapple enzyme. The pineapple enzyme aqueous solution is obtained. Take 3Kg of discarded oyster shell and soak it in the pineapple enzyme aqueous solution and let it stand for 6 hours. Wash the discarded oyster shells soaked in the pineapple enzyme aqueous solution with a high-pressure water column to remove the sediment and rotten flesh on the surface of the discarded oyster shells. After cleaning, the discarded oyster shells without mud, sand and rotten flesh are layered and placed in a stainless steel dryer for drying. The stainless steel dryer has a temperature of 85°C and a drying time of 30 minutes. will After drying, the waste oyster shells are crushed by an angle cutter to form fragments, and then coarsely ground with a vertical mill, and finally finely ground with a jet mill to obtain waste oyster shell powder.

Sintering of waste oyster shell powder in the present invention. Weigh a portion of the finely ground waste oyster shell powder, place it in a crucible and place it in a high-temperature sintering furnace for heat treatment at 900°C for 2 hours, and set the heating rate to 5°C/min. Then, it is cooled to room temperature by furnace cooling and taken out to obtain the waste oyster shell powder after sintering. The waste oyster shell powder after sintering is sealed and stored in a dry box.

As shown in Figures 2, 3 and 4, the preparation of the oyster shell paper of the present invention. The preparation process of oyster shell paper is to first mold the waste oyster shell powder after washing, drying, fine grinding and sintering with a non-petrochemical binder. The preparation of the binder mixed solution of the present invention is mixed with fucoidan, konjac glucomannan, sintered waste oyster shell powder, glycerin and water. Among them, about 95 to 99 parts by weight of distilled water, about 0.1 to 0.5 parts by weight of sintered waste oyster shell powder, about 0.1 to 0.5 parts by weight of fucoidan, and about 0.1 to 0.5 parts by weight Konjac glucomannan and 0.1 to 0.5 parts by weight of glycerin. First add 0.1-0.5 parts by weight of glycerin to 95-99 parts by weight of distilled water, stir evenly, then add 0.1-0.5 parts by weight of fucoidan, and after evenly stirring, add 0.1-0.5 parts by weight of konjac glucomannan, and stir evenly Afterwards, freeze the mixed solution for one hour, and then add 0.1-0.5 parts by weight of the sintered waste oyster shell powder to the mixed solution. After stirring for a period of time, a uniform binder mixed solution can be obtained. Pour 75~95 parts by weight of the unsintered waste oyster shell powder and 5~25 parts by weight of the above-mentioned homogeneous binder mixed solution into the mold 50 for casting, and use the flat plate 60 (shown in Figure 2) to make appropriate Smooth it and dry for 8-12 hours in the temperature range of 40-80℃. After demolding, you can get oyster shell paper 10, as shown in Figures 2, 3 and 4.

The above are only feasible embodiments of the present invention, and are not intended to limit the patent scope of the present invention. Any equivalent implementation of other changes based on the content, characteristics and spirit of the following claims shall be It is included in the scope of the patent of the present invention. The structural features of the invention specifically defined in the claim are not found in similar articles, and are practical and progressive, and have already met the requirements of an invention patent. The application is filed in accordance with the law. I would like to request the Bureau of Jun to approve the patent in order to protect this The legitimate rights and interests of the applicant.

(a)‧‧‧Enzyme to remove oyster shell carrion

(b)‧‧‧Oyster shell powder required for papermaking

(c)‧‧‧Preparation of environmentally friendly adhesive mixed solution

(d)‧‧‧Mixed oyster shell paper materials

(e)‧‧‧Molded oyster shell paper

Claims (9)

A method for making paper from discarded oyster shells, which includes the following steps: (a) Enzyme removal of oyster shells: removing oyster shells with an aqueous solution of pineapple enzyme; (b) preparing oyster shell powder required for papermaking: grinding oyster shells into Oyster shell powder is obtained in powder form, and a part of oyster shell powder is sintered at high temperature to obtain sintered oyster shell powder; (c) To prepare an environmentally friendly binder mixed solution: take the sintered oyster shell powder, fucoidan, and konjac Glucomannan and glycerin are mixed with water to prepare a binder mixed solution; wherein the binder mixed solution is 95-99 parts by weight of distilled water, 0.1-0.5 parts by weight of sintered oyster shell powder, 0.1-0.5 parts by weight Parts by weight of fucoidan, 0.1-0.5 parts by weight of konjac glucomannan and 0.1-0.5 parts by weight of glycerin are mixed with each other to prepare the binder mixed solution; and (d) preparing oyster shell paper materials: take another A part of the unsintered oyster shell powder and the above-mentioned binder mixed solution are uniformly mixed to form an oyster shell paper material; and (e) molded oyster shell paper: pour the oyster shell paper material into a mold and heat it to dry , Oyster shell paper can be obtained after demoulding. The method according to claim 1, wherein, in step (a), the pineapple enzyme aqueous solution is prepared with water and pineapple enzyme to prepare an pineapple enzyme aqueous solution containing 0.05 to 0.3% of pineapple enzyme, and oyster shells are soaked in the pineapple enzyme aqueous solution , Then rinse the oyster shells soaked in the pineapple enzyme aqueous solution with a high-pressure water column to remove the sand and rotten flesh on the surface of the oyster shells. The method according to claim 1, wherein in step (b), the sintering temperature and time are respectively 800~1000°C and 1~3 hours; in step (e), the drying temperature and time are respectively 40~ 80℃ and 8-12 hours; the average diameter of the oyster shell powder is 5-10um. The method according to claim 1 or 3, wherein, in step (b), the sintering temperature is The temperature is increased at a rate of 5°C per minute. The method according to claim 1, wherein, in step (c), glycerin is added to distilled water and stirred, then fucoidan is added and stirred, then konjac glucomannan is added, stirred and frozen, and then sintered Stir the oyster shell powder to obtain a uniform binder mixed solution. The method according to claim 1, wherein step (c) is completed, and then in step (d), 75 to 95 parts by weight of unsintered oyster shell powder and 5 to 25 parts by weight of the binder mixed solution are uniformly mixed The oyster shell paper material is mixed. An oyster shell paper prepared by the method of claim 1, which contains unsintered oyster shell powder, sintered oyster shell powder, fucoidan, konjac glucomannan, glycerin and water. The oyster shell paper according to claim 7, wherein the unsintered oyster shell powder accounts for 7.5 to 9.5 parts by weight; the sintered oyster shell powder accounts for 0.1 to 0.5 parts by weight; the fucoidan accounts for 0.1 to 0.5 parts by weight The konjac glucomannan accounts for 0.1 to 0.5 parts by weight, and the glycerin accounts for 0.1 to 0.5 parts by weight; the average diameter of the oyster shell powder is 5-10um. A product using the oyster shell paper as described in claim 7, which product is a disposable wrapping paper, an anti-fungal and antibacterial insole, a straw curled into a tube, a disposable decomposable dinner plate or a lunch box.

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