KR20130057508A

KR20130057508A - Maunfacturing method of high purity chitosan and chitosanoligosaccarid

Info

Publication number: KR20130057508A
Application number: KR1020110123247A
Authority: KR
Inventors: 박형준
Original assignee: 박형준
Priority date: 2011-11-24
Filing date: 2011-11-24
Publication date: 2013-06-03

Abstract

PURPOSE: A manufacturing method of purifying decontaminant using chitosan and chitosan oligosaccharide polymer is provided to improve water purification by destroying specific microorganism (Gram-negative bacteria and Gram-positive bacteria) according to molecular weight and enhance water purification by combining and absorbing toxic material and heavy metal through space structure of chitosan. CONSTITUTION: A manufacturing method of purifying decontaminant comprises the following steps. A step of dissolving 2.0~7.0% of Chitosan which has over 90% of the degree of distillation and 10~23 cps of viscosity to 0.5~5.0% of acetic acid solution; and a step of producing low molecular Chitosan oligosaccharide having less than 5000 of molecular weight by adding 0.5~5.5 unit/kg of citizens to react for 10~16 hours at pH 4.0~6.5, and 30~55°C. Moreover the manufacturing method of purifying decontaminant comprises the following steps. A step of dissolving 1.0~3.0% of Chitosan which has over 80% of the degree of distillation and 200~400 cps of viscosity to 0.5~5.0% of acetic acid solution, and a step of generating high molecular Chitosan oligosaccharide having less than 300,000 of molecular weight by adding 0.5~5.5 unit / kg of citizens to react for 8~12hours at pH 4.0~6.5 and 30~55°C. [Reference numerals] (AA) Ammonium; (BB) Ammonium sulfate; (CC) Supernatant; (DD) CENTRIFUGE; (EE) Ultra filtration

Description

Water Purification Method Using Chitosan and Chitosan Oligosaccharide Polymers {MAUNFACTURING METHOD OF HIGH PURITY CHITOSAN AND CHITOSANOLIGOSACCARID}

The present invention relates to a method of seeding a water purification agent using chitosan and chitosan oligosaccharide polymers, and more particularly, to hydrolyze chitosan and chitosan oligosaccharides, which are mainly used in existing food additives or pharmaceuticals, by using an acid hydrolysis method. The present invention relates to a method for preparing a water purification agent using chitosan and chitosan oligosaccharide polymers which can obtain eco-friendly biologics by purifying chitooxidation or chitosan oligosaccharides at an appropriate size using an excellent enzyme.

In general, chitosan is composed of poly-β-glucosamine (2-amido-2-deoxy-β-D-glucose) and chitin (poly-β-D-acetylglucosamine; Poly -β-D-acetylglucosamine) is a biodegradable and non-toxic natural polymer made of amino group by removing acetyl group among acetamide groups located at C-2 position.

In recent years, chitosan has attracted attention due to various advantages in the treatment of wastewater. Chitosan and chitosan derivatives as environmental pollution and hardly degradable materials have been researched as adsorption remover of metal ions since 1990s. This is because chitosan is not only economically rich and naturally rich, but also has excellent adsorption property.

Therefore, chitosan as an adsorbent shows high efficiency for the following reasons.

Preliminary experiments with chitosan and agar biopolymers resulted from the measurement of dissolved oxygen (DO) and chemical oxygen demand (COD). A case has been reported that concludes that COD, a chemical oxygen demand as an indicator, can effectively prevent water pollution.

Since the 1970s, in Japan, chitosan and chitosan oligosaccharides used for water purification and water purification have been removed by adsorption and sedimentation and removal of pollutants related to water pollution such as CODcr, BODs, TN, TP, and SS by means of constellation analysis and microbial activity analysis. Membrane used has been developed and commercialized.

Conventionally, water purification is performed by adding a water-soluble metal salt to form a pH using caustic soda or slaked lime and adding a polymer flocculant to generate a hydroxide of metal, which is then floated or precipitated to be sludged and removed. It is used.

In the case of nitrogen, phosphorus and organics, Biological Oxdation Technigues and activated carbon adsorption are mainly adopted. This water treatment technology uses excessive amounts of chemicals, which increases the amount of sludge produced and often requires secondary wastewater treatment.

Complementing this problem is chitosan, a cationic eco-friendly polymer material, which is an environmentally friendly material, and the main characteristics of chitosan are firstly, a hydroxy group having chitosan having a hydrophilic and chelating effect. This is because the amine group exhibits a cation in acidity, and forms an electron double layer to bond with the cationic metal. Wastewater and hospital wastewater treatment methods have been researched and treated in various ways such as chemical precipitation, chemical oxidation, biological treatment, electrolysis, and ozone treatment.

Among them, the adsorption of harmful metals, organic substances, and E.coil dissolved in wastewater using biological resources is valuable in terms of reducing environmental pollution.

Chitin / chitosan, xanthate, zeolite, clay, algae / alginate and the like have been reported as such bioresorbents. Chitosan and its derivatives are known as non-toxic biodegradable polymers, and the high reactivity of chitosan to organic adsorption is due to the chelating effect and the ability to specifically bind cationic and solid phases to hydroxy and amino groups. This is because there are many groups. In other words, in the former Soviet Union, uranium and plutonium can be adsorbed with chitosan, which has the ability to adsorb toxic substances to heavy metals and chitosan conformation (tertiary structure) to chitosan ano groups (NH2).

It can be seen that chitosan demonstrates its excellent ability to adsorb and release harmful heavy metals. However, among the trace metals, calcium, magnesium, and the like are not bonded at all. It is also reported to adsorb substances such as dioxins, which are environmental hormones. Since dioxins are hydrophobic substances, chitosan is hydrophobic and dislikes water even in the helix structure, which is a twisted structure. Therefore, it combines with and adsorbs hydrophobic materials such as dioxins.

Patent Registration No. 10-0939634 Patent Publication No. 1998-0033476

Accordingly, in the preparation of chitosan and chitosan oligosaccharides used for water purification, chitosan production process is carried out by simultaneously decomposing the acid hydrolysis and using a specific enzyme (Endo type enzyme derived from Bacillus species) and decomposing it into an appropriate size for water purification. The present invention provides a method for preparing a water purification agent using chitosan and chitosan oligosaccharide polymers, which can achieve both purification and stabilization of water quality and aquatic ecosystems.

Another object of the present invention is to suppress the aerobic microorganisms and improve the activity of basic microorganisms in water purification by using the properties of chitosan and chitosan oligosaccharides to control BOD, COD, cationic chitosan and chitosan oligosaccharides, and It stabilizes and aggregates fine particles, clays, and calcareous substances in water by using high molecular weight chitosan with a molecular weight of 50,000 to 300,000, and low molecular weight chitosan and chitosan oligosaccharides inhibit aerobic microorganisms in the water ecosystem. At the same time to maximize the activity of the basic microorganisms to provide a water purification agent using a chitosan and chitosan oligosaccharide polymer that can achieve the balance of the ecosystem.

The present invention for achieving the above object is deacetylation degree of 90% or more viscosity 10cps ~ 23cps, chitosan 2.0 to 7.0% dissolved in 0.5% to 5.0% solution of acetic acid and pH 4.0 ~ pH6.5, temperature 30 ℃ ~ 55 It provides a method for producing a water purification agent using a chitosan and chitosan oligosaccharide polymer, characterized in that by producing a low molecular weight chitosan oligosaccharide having a molecular weight of 5000 or less by adding a chitosanase 0.5 ~ 5.5 units / kg and reacted for 10 to 16 hours.

The present invention for achieving the above object, deacetylation degree of 80% or more viscosity 200cps ~ 400cps, chitosan dissolved in 0.5% to 5.0% solution of acetic acid to 1.0 to 3.0% and pH 4.0 ~ pH6.5, temperature 30 ℃ ~ It provides a water purification agent using a chitosan and chitosan oligosaccharide polymer, characterized in that to produce a high molecular weight chitosan oligosaccharide having a molecular weight of 300,000 or less by adding a chitosanase 0.5 ~ 5.5 units / kg at 55 ℃, 8-12 hours.

As described above, the present invention can improve the water purification and stabilization of the water ecosystem by concentration treatment of BOD, COD, TN, TP, etc., and specific microorganisms (Gram-negative bacteria and Water purification can be improved by killing gram-positive bacteria). In addition, by combining and adsorbing toxic substances and heavy metals through the three-dimensional structure (third structure) of chitosan, there is an effect that can improve the water purification.

1 is a process chart of a method for separating chitosan and chitosan oligosaccharides by molecular weight according to the present invention,
Figure 2 is a table and graph showing the results of the antimicrobial activity test (MIC test) according to the molecular weight of the present invention,
Figure 3 is a photograph of the sample form for the antimicrobial activity test according to the molecular weight of the present invention.

Hereinafter, a method for preparing a water purification agent using the chitosan and chitosan oligosaccharide polymer of the present invention will be described in detail with reference to the accompanying drawings.

First of all, the main raw material of the water purification agent according to the present invention is to remove the acetyl group from the acetamide group in the C-2 position of chitosan to make the water purification by the biological treatment method to make an amino group using a biodegradable and nontoxic natural polymer material It inhibits and kills water purification, wastewater treatment, and pathogenic bacteria, while adsorbing organic matter and giving hydrophilic and chelating effects.

In addition, the present invention can stabilize both the water purification and the aquatic ecosystem as an eco-friendly formulation according to the stable water purification using chitosan and chitosan oligosaccharides, which are environmentally friendly materials that do not affect the water quality and the aquatic ecosystem.

In the present invention, chitosan oligosaccharides are prepared for two kinds of low molecular weight chitosan and high molecular weight chitosan, respectively.

1 is a process chart of a method for separating molecular weight chitosan and chitosan oligosaccharides according to the present invention. As shown in Figure 1, the low-molecular chitosan according to the present invention, the deacetylation degree 90% or more viscosity 10cps ~ 23cps, chitosan dissolved in 0.5% to 5.0% solution of acetic acid to 2.0 to 7.0% pH 4.0 ~ Chitosan oligosaccharides having a molecular weight of 5,000 or less are produced by adding a pH 6.5, a temperature of 30 ° C to 55 ° C, and 0.5 to 5.5 units / kg of chitosanase and reacting for 10 to 16 hours.

It will be preferable here that the low molecular weight molecular weight is 2000-5000.

On the other hand, the chitosan for polymers according to the present invention is dissolved in 0.5% to 5.0% acetic acid so that the deacetylation degree of the viscosity is 200 cps to 400 cps and the chitosan is 1.0 to 3.0%. Chitosan oligosaccharides having a molecular weight of 300,000 or less are produced by adding a chitosanase at 0.5 to 5.5 units / kg and reacting for 8 to 12 hours.

It is preferable that the polymer molecular weight is 100,000 to 300,000 here.

And the molecular weight 2000-5000 low molecular weight chitosan and chitosan oligosaccharide, and molecular weight 100.000-300,000 high molecular weight chitosan and chitosan oligosaccharides are mixed, and a water purification agent is completed.

The antimicrobial activity test results according to the molecular weight of the chitosan oligosaccharide manufacturing method are shown in the table and graph of FIG.

Using the prepared chitosan mixture plays a more stable role in the process of organic matter, such as inflow of pollutants, which is one of the difficulties of water purification and seasonal nitrogen nitrate and dissolved oxygen.

Generally, toxic substances that cause water pollution are divided into heavy metals and organochlorine compounds. Heavy metals such as mercury, copper, lead, cadmium, cobalt, manganese, and zinc are toxic to the human body in small amounts. Cause problems. In particular, among these heavy metals, copper, cobalt, zinc, cadmium, etc. are widely used, which is a material of great concern for secondary environmental pollution. Therefore, in order to remove such toxic metal ions, the chitosan and chitosan oligosaccharides for the polymer prepared by the preparation method are allowed to settle by adsorbing heavy metals and fine molecules.

The chitosan and chitosan oligosaccharides produced by the above two production methods have different roles, that is, the chitosan and chitosan oligosaccharides for the polymer react with and adsorb and precipitate with micromolecules and heavy metals in the water, and the low molecular weight chitosan is a pathogenic microorganism or organic compound. To stabilize aquatic ecosystems and cut plants.

That is, the two chitosans and chitosan oligosaccharides are chitosans partially deacetylated from chitin, which is abundant in nature, and have excellent alkali resistance, easy hydrophilization and hydrophobicity, and excellent adsorption to transition metals. Selective formation of chelates have affinity, which is very effective in removing heavy metals from wastewater.

As described above, the present invention is the adsorption and precipitation of water pollutants and organic compounds having high molecular weight and high molecular weight adsorption of the primary polymer chitosan and chitosan oligosaccharides, and the secondary low-molecular chitosan and chitosan oligosaccharides are active in aquatic microorganisms and water ecosystem To maximize the development of environmentally friendly water purification.

The natural high molecular weight chitosan and chitosan oligosaccharides are cationic natural polymer polymers used as flocculants to effectively agglomerate high turbidity raw water. Therefore, they are mixed with low molecular weight chitosan and high molecular weight chitosan. As a result, both water purification and aquatic ecosystems can stabilize.

Claims

Deacetylation degree 90% or more Viscosity 10cps ~ 23cps, chitosan 2.0 ~ 7.0% dissolved in 0.5% ~ 5.0% acetic acid solution, pH4.0 ~ pH6.5, temperature 30 ℃ ~ 55 ℃, chitosanase 0.5 ~ 5.5unit / A method of preparing a water purification agent using chitosan and chitosan oligosaccharide polymers, which comprises adding kg and reacting for 10 to 16 hours to produce low molecular weight chitosan oligosaccharides having a molecular weight of 5000 or less.

Deacetylation degree 80% or more Viscosity 200cps ~ 400cps, Chitosan dissolved in 0.5% ~ 5.0% acetic acid solution to 1.0 ~ 3.0%, pH4.0 ~ pH6.5, temperature 30 ℃ ~ 55 ℃, chitosanase 0.5 ~ 5.5unit / A method of preparing a water purification agent using chitosan and chitosan oligosaccharide polymers, which comprises adding kg and reacting for 8 to 12 hours to produce high molecular weight chitosan oligosaccharides having a molecular weight of 300,000 or less.

3. The method according to claim 1 or 2,
Method for producing a water purification agent using a chitosan and chitosan oligosaccharide polymer, characterized in that the molecular weight 2000 ~ 5000 low molecular chitosan and chitosan oligosaccharide and molecular weight 100.000 ~ 300,000 polymer chitosan and chitosan oligosaccharide.