KR20150068642A - Preparation method of cellulose solution from urochorda and cellulose fiber from urochorda - Google Patents

Abstract

The present invention relates to a method for manufacturing a cellulose solution originated from urochorda marine life shells and a cellulose fiber originated from urochorda marine life shells. More specifically, the present invention relates to a method for preparing a cellulose solution originated from urochorda marine life shells, the invention comprising the steps of: (1) preprocessing urochorda marine life shells wherein the washed and dried urochorda marine life shells are alkali treated, thereafter, acid treated and bleached; (2) pulverizing the preprocessed shells by a pin milling method to 10 to 200 mesh and producing into a powder; and (3) dissolving the shell powder in a cellulose solution and homogenizing. The present invention also relates to a cellulose fiber originated from urochorda marine life shells wherein the cellulose fiber can be obtained by extruding and spinning a cellulose solution, which is prepared from urochorda marine life shells, through a spinneret and thereafter by coagulating the spun fiber. According to the present invention, it is possible to prepare a cellulose solution from urochorda marine life shells by economically dissolving cellulose and thereafter, a regenerated cellulose fiber can be manufactured therefrom. Accordingly, it is possible to enhance a utilization rate and create an added value of urochorda marine life shells which are almost entirely discarded.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a cellulose fiber from a sea cucumber marine organism shell and a method for producing the cellulose fiber from a sea cucumber marine organism shell,

The present invention relates to a method for producing a cellulose solution derived from a crayfish and a marine biological shell, and a cellulose fiber derived from a crayfish and a marine biological shell.

Cream-colored marine organisms belong to the crustacean animal, the off-white animal animal, including midduk and urchin. These off-white marine organisms are marine organisms with the characteristics of plants, and the keratin skin is covered with hard cellulose. In particular, it is a creature found throughout Korea. It is a typical animal in the larval stage and has a distinct skeletal structure. However, when attached to a proper site, skin keratin forms β-1,4 bonds similar to vegetable celluloses have. It has been reported that in the case of sea weed, the cellulose content is 50-60% based on the dry skin and the degree of polymerization is 900-3500, which is higher than the degree of polymerization (DPw = 700-1000) of pulp cellulose for regenerated fibers.

On the other hand, cellulose is the main constituent of plant cell wall together with lignin, and it is made by the earth plants in 10 ¹¹ ~ 10 ¹² ton every year. It is generally present in relatively pure form in cotton but it is mostly present as lignocellulose in association with lignin or in association with hemicellulose.

Cellulose as a raw material of polymer has been used for a long time by mankind in the form of cotton, flax and paper, and it is still changing its chemical form to make fiber, membrane, film, Or in a variety of products for home use. Cellulose has a property that glucose, which is a monomer, forms a supramolecular structure which is strongly connected through hydrogen bonding, and therefore, is not dissolved in general organic solvents or water at all. The study of cellulosic treatments, which began early in the mid-19th century, was commercialized on a large scale with the development of the viscose process used as raw materials for rayon and cellophane in the early 20th century. However, due to environmental pollution such as toxic carbon disulfide (CS ₂ ) as a solvent, many related companies have abandoned the viscose process, and various new solvents are being developed. The method using the NMMO / H ₂ O solvent system has been widely used as a solvent for the production of regenerated cellulose fibers and films due to the recently developed excellent solubility and low toxicity. Since NMMO is highly hydrophilic due to strong polar NO bonding, its solubility in water is very high and it can be completely mixed and tends to have a high hydrogen bonding tendency. The NO bond acts as a strong oxidizing agent, releasing large energy, is thermally unstable, and is sensitive to various catalysts. Since the polarity of the NO bond is large, the hydrogen bonding ability is great and the NO bond is weak. Therefore, it is widely used as a solvent of cellulose today.

The manufacturing process of the cellulose fiber using the NMMO solvent is widely used in the manufacturing process of the cellulose material because the produced fiber and the film have high mechanical strength in that they are a pollution-free process due to the total recovery and reuse of the solvent Many of these methods have been proposed starting from US Pat. No. 3,447,935. In U.S. Patent Nos. 4,142,913, 4,144,080, 4,196,282 and 4,246,221, NMMO aqueous solution containing not more than 50% water is subjected to vacuum distillation of water from NMMO aqueous solution containing cellulose swelling and swelling cellulose, And then extruded to make fibers. However, these methods require a long time from dissolution to radiation, which may result in degradation of physical properties due to thermal decomposition. Also, the amount of energy consumed is large, which causes a rise in manufacturing cost.

In view of the fact that a large amount of cellulose is contained in the skin of the off-marine marine organism, the present invention is capable of enhancing the cellulose dissolution efficiency by preparing the powder by pretreatment and crushing the skin of the off-marine marine organism, And a method for producing a cellulose solution derived from an off-white marine biological shell by effectively dissolving it in a cellulose dissolution solution.

It is another object of the present invention to provide a cellulose fiber derived from an off-white marine biological shell obtained by using a cellulose solution derived from the above-mentioned off-white marine biological shell.

According to an aspect of the present invention,

(1) Pretreatment of off-shore marine biological shells by alkaline treatment of off-shore marine organisms prepared by washing with water and drying, followed by acid treatment and bleaching;

(2) pulverizing the pretreated shell into 10 to 200 mesh by a pin milling method and pulverizing the pretreated shell; And

(3) dissolving the shell powder in a cellulose solution, and homogenizing the shell powder. The present invention also relates to a method for producing a cellulose solution derived from an off-white marine biological shell.

Preferably, the off-marine marine life is characterized by being bumpy or throbbing.

Preferably, the step (1)

An alkaline treatment step in which the off-shore marine hulls prepared by washing with water and naturally dried are mixed with NaOH aqueous solution, heated and treated with strong alkali, and washed several times;

Mixing the alkali-treated skin with the acidic solution, heating the acidic solution, washing with water several times, and neutralizing the skin; And

Bleaching the neutrally diluted shell and then drying it.

Preferably, the step (2)

The pretreated shells were first crushed to 10-100 mesh by a pin milling method,

Secondarily pulverizing the primary crushed shell powder into 100 to 200 mesh; And

And a third step of pulverizing the secondary crushed shell powder to 100 to 200 mesh.

Preferably, the cellulose solution of step (3) is a mixture of [Amim] Cl (1-allyl-3-methylimidazolium chloride) or [Amim] Cl / NMMO (N-methylmorpholine N-oxide) And is a solvent.

According to another aspect of the present invention,

There is provided a cellulose fiber derived from a cryogenic marine biological shell, which is obtained by extrusion-spinning a cellulose solution derived from a cryogenic marine biological shell through a spinneret, and then solidifying the spinning fiber according to the above method.

According to the method of the present invention, the impurities of the off-white marine biological shell are removed by pretreatment, and the tough fibrous structure of the shell is effectively pulverized by the pin milling method to facilitate the dissolution of the cellulose, It is possible to more effectively dissolve cellulose from the above-mentioned off-white marine biological shell powder by using a mixed liquid of a gaseous liquid or an ionic liquid and NMMO.

In addition, according to the present invention, a cellulose solution can be economically produced from a cryogenic marine biological shell which is discarded and discarded, and a regenerated cellulose fiber can be obtained from the cellulose fiber. Thus, It is possible to increase the utilization and the added value.

FIG. 1 shows a process for producing a cellulose solution derived from a crayfish-related marine biological shell according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

The present invention relates to a method for producing a cellulose solution derived from an unfiltered marine biological shell by dissolving it in an environmentally friendly cellulose solution so as to increase the cellulose dissolution efficiency by preparing a powder by pretreatment and pulverization of a cryogenic marine biological hull.

Specifically, according to one aspect of the present invention,

(1) Pretreatment of off-shore marine biological shells by alkaline treatment of off-shore marine organisms prepared by washing with water and drying, followed by acid treatment and bleaching;

(2) pulverizing the pretreated shell into 10 to 200 mesh by a pin milling method and pulverizing the pretreated shell; And

(3) a step of dissolving the shell powder in a cellulose solution and homogenizing the shell powder; and (3) dissolving the shell powder in a cellulose solution and homogenizing the shell powder.

In the present invention, the step (1) of the present invention is a step of pretreatment of a cropland-like marine biological shell, which comprises washing and drying and then alkali-treating the prepared off-marine biological shell to remove impurities such as ash and protein contained in the shell , Acid treatment, neutralization, bleaching and purification.

Preferably, the step (1) includes an alkaline treatment step of mixing a marine biological shell prepared by washing with water and naturally dried, a marine biological shell prepared by mixing with an aqueous NaOH solution, heating the mixture to strong alkali treatment, and washing the water with water several times; Mixing the alkali-treated skin with the acidic solution, heating the acidic solution, washing with water several times, and neutralizing the skin; And bleaching the neutrally diluted shell and drying. At this time, the bleaching may be either an oxidation bleaching method or a chlorine bleaching method. However, in consideration of the convenience of the method and industrial production, an oxidation bleaching method of bleaching with an aqueous hydrogen peroxide solution is more preferable.

In one embodiment of the present invention, in the present invention, impurities such as proteins are removed from the skin of the axilla by heating the sea squirt and 10% aqueous NaOH solution in a bath ratio of 1:30 at 100 to 120 ° C for 3 hours, and washed with water once and then diluted with a strongly alkaline with potassium yakyal castle, heating again for 2 hours at 100 ℃ to a 5% H ₂ SO ₄ aqueous solution bath ratio 1:30 by acid treatment, the water was neutral using pH paper Lt; / RTI > After the alkali treatment and the acid treatment, 10% hydrogen peroxide solution was added and the mixture was heated at 95 to 100 ° C. for about 1 hour, and then washed with water to bleach and purify the skin of the sea urchin, and the mixture was dried at 100 to 140 ° C. .

In the present invention, the step (2) is a step of pulverizing the pretreated shell, and the dissolution of the cellulose contained in the off-white marine biological shell is easily performed according to the degree of pulverization in the step (2) It is important to select the optimum grinding method in consideration of the shape, size, amount of moisture, physical strength and elongation of the shell for dissolving cellulose. Therefore, in order to crush the tough fiber structure of the off-white marine biological shell in the crushing in the step (2), the off-marine marine biological shell pretreated and dried in the step (1) , And is preferably pulverized by a pin milling method in which the blade is cut and ruptured by a blade on the blade. In this case, the powder is pulverized into 10 to 200 mesh. More preferably, in the step (2), the pretreated shell is first pulverized by 10 to 100 mesh by a pin milling method, and then the first pulverized shell powder is secondarily pulverized by 100 to 200 mesh; And a third step of pulverizing the secondary crushed shell powder with 100 to 200 mesh. At least a third pulverization step is carried out to finely pulverize the off-white marine biological shell, so that the cellulose can be dissolved well Let's do it.

In one embodiment of the present invention, the pretreated jackal skin is first pulverized to 30 mesh, then the pulverized squid powder is pulverized again to 120 mesh, and the pulverized third mesh is pulverized to 120 mesh to obtain finer pulverized powder , The equipment was overheated at the time of crushing, so the crushing was carried out with a certain period of cooling.

In the present invention, the step (3) is a step of dissolving the unseasoned marine biological shell powder in a cellulose solution and homogenizing the cellulose. The cellulose forms a supramolecular structure in which glucose as a monomer is strongly bonded through hydrogen bonding It is very important that the cellulose solution is selected in the above step (3) because it has characteristics that it is not soluble in general organic solvents or water at all.

Therefore, preferably, the cellulose solution is a mixture of [Amim] Cl (1-allyl-3-methylimidazolium chloride) or [Amim] Cl / NMMO (N-methylmorpholine N-oxide) do.

Since the ionic liquid is composed of ions only, it is composed of a large cation containing nitrogen and a small anion, so that the lattice energy of the crystal structure is reduced, and as a result, the ionic liquid has a low melting point and can be used as various solvents and catalysts As a result, when the ionic liquid is used, the cellulose can be more completely dissolved. Further, when the NMMO solvent and the mixed solvent used as the solvent of the conventional cellulosic solvent are used when the cellulose is dissolved using the ionic liquid as a solvent, when the cellulose is dissolved by using the NMMO solvent alone, ), It is possible to oxidize the sample by dissolving the sample. By mixing the [Amim] Cl ionic liquid and using it as a catalyst, the sample can be dissolved at a lower temperature to obtain better solubility and physical properties.

According to one embodiment of the present invention, in the dissolution method using the ionic liquid, due to the high viscosity property of the [Amim] Cl ionic liquid, the ionic liquid is dissolved in the reaction vessel through the impeller at 70 to 80 ° C for 20 minutes or more It was confirmed that the dissolution of cellulose could be performed well.

According to another aspect of the present invention, a cellulose solution derived from a crayfish-derived marine biological shell produced by the above method is capable of producing a cellulose fiber by spinning. According to another aspect of the present invention, there is provided a method for producing a cellulosic solution Is extruded and spun through a spinneret, and then the coagulated fiber is obtained by coagulation, thereby providing a cellulose fiber derived from a cryogenic marine biological shell.

According to one embodiment of the present invention, after the pretreatment and crushing of the skimney shell powder is dissolved in the [Amim] Cl ionic liquid through the impeller, the impurities and the undissolved powder are filtered and then injected into a radiator The cellulose fiber was prepared by being immersed in a coagulation bath by spinning through a spinneret.

As described above, the cellulose solution prepared by dissolving the fine powder of the off-white marine biological shell obtained by the pretreatment and pulverization into the cellulose solution is spun by extrusion spinning, coagulated, washed with water and dried to obtain cellulose fibers do. In this case, the cellulose fiber derived from the above-mentioned off-shore marine biological shell can be controlled in properties such as tensile strength or strength by optimizing the extrusion conditions such as the extrusion pressure and the extrusion temperature during the extrusion spinning.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

≪ Example 1 > Pretreatment of acorn skin

1-1 Alkali and Acid Treatment

In this embodiment, crude wastes containing a large amount of impurities collected in the process of removing the bark to sell the contents to the market were used after being washed in a simple manner and naturally dried in the field.

Next, it was rinsed with water three times to remove salts and impurities contained in the prepared axel bark. Taking into account that the process of obtaining α-cellulose in the skull skin will be similar to the process of producing wood pulp, the Kraft process using NaOH as in pulp manufacturing process was utilized to obtain a large amount of α-cellulose material. Specifically, the sea squirt was treated with a 10% NaOH aqueous solution at a bath ratio of 1:30 at 100 ° C for 2 hours to remove impurities such as ash and protein in the shell, and was diluted with water 2-3 times to dilute the strong alkalinity .

Next, a 5% aqueous H ₂ SO ₄ solution was treated at 100 ° C for 2 hours in a 1:30 bath ratio for neutralization. The acid-treated samples were washed with neutral pH paper using pH paper.

1-2 bleaching of axel skin

In order to bleach the pretreated silkworm shell, firstly, it was put into a 5-10% aqueous hydrogen peroxide solution by oxidation bleaching method and treated at a temperature of 95-100 ° C for 1 hour in a weak basic solution of pH 9.5-10.0 at a bathing ratio of 1:30 And then rinsed with water. The bleached skins were removed from the dehydrator with excess water, placed in a drier and dried by hot air at 140 ° C.

Example 2: Pretreatment of the skeleton of crustacea

Pin milling is a method of inserting a sample into a pin roller and cutting and breaking the blade by a blade on the blade by friction and pressing force. In order to minimize the moisture content of the frog skin, It was confirmed that it was broken by inserting it into the pin roller. The shredded skins were first filtered through a sieve of 30 mesh, then the skinshell powder was replaced with a second 120 mesh sieve, filtered, and finally pulverized with 120 mesh to obtain a fine powder, Powder of fine particles was prepared.

As mentioned above, the morphological structure of the venom shell, due to its tough fibrous structure, should be taken into consideration in selecting the pulverization method for pulverization, such as the shape, size, amount of moisture, physical strength and elongation of the object. It can be confirmed that it can be effectively crushed by a pin milling method in which it is inserted into a roller and is cut and broken by a blade on the blade by friction and pressing force.

Example 3 Cellulose dissolution

(1) NMMO solvent

The NMMO solvent was evaporated from the 50% (wt) liquid supplied by Hyosung Corporation to 87% (wt) and used. The cellulose / NMMO solution used n-propyl gallate as 0.5% (wt) (per wt. Cellulose) as an antioxidant to prevent the molecular weight decrease due to high heat generated during the dissolution process.

Specifically, the rhizome skin powder was weighed 3% (wt) by weight with respect to the solvent NMMO / H ₂ O, and 0.5% (wt) of n-propyl gallate as an antioxidant was added thereto. The mixture was put into a reactor equipped with a thermostat, a mechanical stirrer and a condenser, and was completely dissolved by being heated at 110 ° C for 1 hour while gradually raising the temperature.

(2) Ionic liquid solvent

An ionic liquid is a liquid composed of ions, usually composed of a large cation containing nitrogen and a smaller anion. By this structure, the lattice energy of the crystal structure is decreased, resulting in a low melting point, and it is used as a clean solvent and catalyst in various organic chemical reactions.

In this example, 1-Allyl-3-metylimidazolium Chloride ([Amim] Cl) was used in various ionic liquids.

[Amim] Cl The ionic liquid itself is a honey-like formulation with a very high viscosity. If the solution of venomous shell cellulose is dissolved in this solution, the viscosity of the solution becomes higher. [Amim] Cl was carried out in the following manner so as to dissolve the skimmed cellulose in the ionic liquid.

Specifically, in the reaction tank, the skinshell cellulose was dissolved in an impeller at 80 ° C for 1 hour by adding [Amim] Cl ionic liquid at a concentration of 3 wt%, respectively. When it was dissolved for the first time, the ionic liquid and the skinshell cellulose were respectively shaken at room temperature and stirred while being slowly heated to 80 ° C. As a result, the melting was very good through the rotating impeller, but there was a loose part.

To reduce this, a sample was blown into an ionic liquid, mixed well with the glass membrane, and stirred while heating to 80 ° C., so that a lot of bubbles were formed and the impeller rises. This phenomenon became worse as the concentration increased.

To solve this problem, the viscosity of the ionic liquid was lowered beforehand at 80 ° C, and then the sample was added and stirred. The sample was immediately stirred, and a bundle was formed. The viscosity of the ionic liquid was lowered beforehand at 80 ° C., the sample was added, and the sample was uniformly dispersed in the glass membrane, followed by dissolving at 80 ° C. for 1 hour. The solution was filtered, cast on a glass plate, and immersed in methanol. Dissolving through the impeller required the reaction to occur quickly and evenly, shortening the dissolution time.

Thus, the viscosity of the ionic liquid was lowered beforehand at 80 ° C, the sample was added, and the mixture was uniformly dispersed in the glass membrane, followed by stirring at 80 ° C for 25 minutes. The solution was rapidly filtered, cast on a glass plate, immersed in methanol, and the shape was preserved in a hydrogel state.

Therefore, as a result of this example, it was judged that the dissolution of cellulose could be performed well by dissolving the sea urchin shell cellulose in the [Amim] Cl ionic liquid through the impeller in the reactor at 80 ° C for 25 minutes.

When an NMMO solvent and a mixed solvent, which are conventionally used as a solvent of a cellulose solvent, are used when dissolving cellulose using the ionic liquid as a solvent, an NMMO solvent dissolving at a high temperature of 110 to 120 ° C and a solvent of 70 to 80 ° C It can be dissolved at a temperature lower than 110 ° C by the mixing of [Amim] Cl ionic liquid which dissolves at a relatively low temperature of about 80 ° C. In this case, when cellulose is solely used as an NMMO solvent, there is a possibility of oxidation due to the dissolution of the sample at a high temperature (110 ° C.). When [Amim] Cl ionic liquid is mixed and used as a catalyst, It is expected that better dissolution and physical properties will be obtained by dissolving the sample.

Example 4 Production of Cellulose Fibers

In order to utilize cellulase derived from the skeleton shells as a different type of biomaterial, we carried out the experiment of spinach lysis solution. In the above example, the strength of the film prepared from the sea tangle skin solution with the concentration of 3 wt% was not suitable enough to maintain the shape of the yarn, so that the sea tangle shell powder corresponding to 5 wt% was used.

[Amim] Cl ionic liquid was selected in the same manner as in Example 3, and dissolved at a temperature of 80 ° C for 2 hours. The finished skimmed cellulosic solution was filtered to remove impurities and undissolved powder, transferred to a self-made spinner and spun through a spinnerette. The spun fibers were immersed in a solidified water bath of methanol having a columnar shape and did not exhibit high tensile strength or strength, but it was found that by optimizing the extrusion conditions such as extruding pressure and temperature of the radiator, It is considered that the physical properties can be controlled.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (6)

(1) Pretreatment of off-shore marine biological shells by alkaline treatment of off-shore marine organisms prepared by washing with water and drying, followed by acid treatment and bleaching;
(2) pulverizing the pretreated shell into 10 to 200 mesh by a pin milling method and pulverizing the pretreated shell; And
(3) dissolving the shell powder in a cellulose solution, and homogenizing the cellulose powder; and (3) dissolving the shell powder in a cellulose solution and homogenizing the shell powder. The method according to claim 1,
Wherein the off-marine marine life is a sea bream or a sea bream. ≪ RTI ID = 0.0 > 15. < / RTI > The method according to claim 1,
The step (1)
An alkaline treatment step in which the off-shore marine hulls prepared by washing with water and naturally dried are mixed with NaOH aqueous solution, heated and treated with strong alkali, and washed several times;
Mixing the alkali-treated skin with the acidic solution, heating the acidic solution, washing with water several times, and neutralizing the skin; And
Bleaching the neutrally diluted shell, and drying the neutralized shell. The method according to claim 1,
The step (2)
The pretreated shells were first crushed to 10-100 mesh by a pin milling method,
Secondarily pulverizing the primary crushed shell powder into 100 to 200 mesh; And
The method according to any one of claims 1 to 3, further comprising a third step of pulverizing the secondary crushed shell powder to 100 to 200 mesh. The method according to claim 1,
The cellulose solution in the step (3) is characterized by being a mixed solvent of [Amim] Cl (1-allyl-3-methylimidazolium chloride) or [Amim] Cl / NMMO (N-methylmorpholine N-oxide) Wherein the cellulosic material is a cellulose fiber. A method for producing a cellulose-free marine biological shell-derived, non-cryo-derived marine biological shell-derived cellulose fiber obtained by extrusion-spinning a cellulose solution prepared from a cryogenic marine biological shell by a method according to any one of claims 1 to 5, Cellulose fiber.

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