KR100364508B1 - Bio-polymer amine and manufact uring method of same - Google Patents

Abstract

The present invention relates to an amine-based biopolymer and a preparation method thereof, and provides an amine-based biopolymer prepared by using starch on ammonia and urea. The amine-based biopolymer of the present invention can be used as a water treatment flocculant to not only adsorb and remove heavy metals such as iron, lead, aluminum, copper, and zinc in the wastewater, but also can be variously used for separation and purification of materials.

Description

Amine-based biopolymer and manufacturing method thereof {Bio-polymer amine and manufacturing method of same}

The present invention relates to an amine-based biopolymer and a method for producing the same, and more particularly, to an amine-based biopolymer and a method for producing the same that can be used as a flocculant for water treatment.

Today, the wastewater generated by economic development and the improvement of the standard of living of the people is showing qualitative diversification with quantitative increase. COD values of various industrial wastewater and domestic sewage are not only high, but also contain a large amount of hardly decomposable organic substances and harmful components, and thus limit the conventional chemical and biological treatments using inorganic coagulants. Therefore, in order to improve the removal efficiency of dissolved organic substances in the flocculation process, polyvinylamine-based, polyacrylamide-based, DMA-based (dimethylaminoethyl methacrylate), DAA-based (dimethylamineethyl acrylate), etc. Anionic and cationic polymer coagulants have been developed in various ways and used in various wastewater treatments, but they are expensive and most of them are imported from foreign countries. to be.

In particular, the flocculants for water treatment in common use are mostly due to chemical synthesis and can be divided into aluminum flocculants and iron salt flocculants. The aluminum flocculant includes aluminum sulfate and polyaluminum chloride, and the iron salt flocculant includes ferric chloride and ferric sulfate. The chemical synthetic water treatment flocculant is relatively inexpensive at the price of 60 to 140 won per kilogram, while the coagulation efficiency per gram is low, and the color and heavy metal removal efficiency is low.

In addition, most of the conventional technologies currently in use are related to chemical synthetic flocculants. Since chitin and chitosan, which use biopolymers for water treatment, are expensive, they are restricted in use. In the case of synthesizing various compounds such as cellulose, the synthesis method is complicated and synthetic. There is a problem such as a poor yield. In particular, synthetic biopolymers developed in foreign countries are not used as flocculants for water treatment because of high manufacturing and import costs.

Accordingly, an object of the present invention is to provide a biodegradable flocculant having a high efficiency of cohesion in a small amount.

It is another object of the present invention to provide a biodegradable flocculant which can be used for water treatment at low cost.

1 is a block diagram briefly illustrating a method for synthesizing an amine-based biopolymer of the present invention;

Figure 2 shows a schematic diagram of the cryogenic freezer used in the amine-based biopolymer production method of the present invention,

Figure 3 is a block diagram showing a method for separating or purifying the amine-based biopolymer of the present invention,

Figure 4 is a graph showing the detection time per molecular weight of the standard in order to convert the molecular weight of the synthetic polymer of the present invention,

5 is a graph showing a change in viscosity according to the concentration of the amine-based biopolymer of the present invention.

In order to achieve the above object, the present invention provides an amine-based biopolymer represented by the following formula (1).

[Formula 1]

N is from 3,170 to 3,200.

In addition, the present invention comprises the steps of (a) adding urea to ammonia water to dissolve at low temperatures, (b) swelling the starch by mixing starch in the melt of step (a), (c) drying the mixture at room temperature And evaporating ammonia again at 100 ° C., (d) adding nitrogen gas to the mixture to cause a polymer synthesis reaction, and (e) separating and purifying the synthesized amine-based biopolymer. It provides a method for producing an amine-based biopolymer, characterized in that.

Hereinafter, the present invention will be described in detail.

The present invention provides an amine-based biopolymer of Formula 1 prepared using starch.

[Formula 1]

N is preferably from 3,170 to 3,200, and has a molecular weight of about 1,200,000.

The amine-based biopolymer of the present invention has an apparent viscosity ([?? _a ]) of 123 to 1018 cp depending on the concentration.

In addition, the amine-based biopolymer of the present invention has the same removal efficiency of organic matter (COD) and suspended solids (SS) as the conventional synthetic polymer flocculant, and in particular, the conventional synthetic polymer flocculant has a cohesive efficiency of 25% to 65% for heavy metals. In contrast, the amine-based biopolymer of the present invention has a flocculation efficiency of 74% to 96%.

The amine-based biopolymer of the present invention can be used for municipal wastewater, sewage, industrial wastewater, especially papermaking wastewater treatment, and the like, and is not limited to the above.

The preparation method of the amine-based biopolymer of the present invention will be described in more detail.

In the amine-based biopolymer of the present invention, (a) adding urea to ammonia water to dissolve at low temperature, (b) swelling the starch by mixing starch in the lysate, and (c) drying the mixture at room temperature. Evaporating ammonia again at 100 ° C., (d) causing a synthesis reaction to the mixture, and (e) separating and purifying the amine-based synthetic biopolymer synthesized above.

In step (a), 10% by volume of urea is dissolved in ammonia water at -33 ° C and titrated at -35 ° C.

Starch mixed in the melt in step (b) is preferably 20 to 40% by weight, most preferably 30 to 35% by weight of the melt. In addition, the reaction temperature is preferably -35 ℃ and starch is preferably all starch, but most preferably corn starch containing amylose and amylopectin in a 1 to 4 ratio.

In the synthesis of step (d), it is preferable to charge nitrogen gas in a dryer and react at 135 ° C. for 4 hours.

In the step (e), the separation and purification of the amine synthetic biopolymer is characterized in that it is carried out by sized chromatography. The chromatography is preferably Sephadex CL-4B chromatography or FPLC.

Hereinafter, preferred examples are provided to aid in understanding the present invention. However, the following examples are provided only to more easily understand the present invention, and the present invention is not limited to the following examples.

Example 1

The starch used to synthesize the amine-based biopolymer was used corn starch that is commercially used. Corn starch contains amylose and amylopectin in a 1 to 4 ratio, and both amylose and amylopectin can be used for this synthesis. Ammonia water and urea to be used for the synthesis were used commercially.

(1) polymer synthesis

Synthesis method of the amine-based biopolymer is briefly shown in FIG. First, the ammonia water was added to the ultra-low temperature chamber of FIG. 2 where the stirrer was installed, and the temperature was adjusted to -33 ° C., and then urea was slowly dissolved while stirring at 100 rpm. After dissolving the solution at a temperature of -35 ° C., the starch was added at a weight ratio of 1/3 of the solution, and the starch was swollen while slowly stirring at 100 rpm. The swollen starch was dried at room temperature and then evaporated ammonia in a 100 ° C. dryer. After evaporating ammonia, the sample was filled with nitrogen gas and reacted at 135 ° C. for 4 hours to obtain an amine-based biopolymer composite.

(2) Purification of Synthetic Polymer

Purification of the synthetic polymer was carried out as briefly shown in FIG. First, gel chromatography was performed using Sephadex CL-4B resin purchased from Sigma, in order to verify the yield of the synthesized polymer. Sepadex SL 4 ratio resin swelled in Tris buffer solution (20 mM Tris-HCl, pH 7.0) was charged in a separation tube (2.5 × 100 cm), and 0.1 g of the synthesized polymer was dissolved in 100 ul and then placed on a column. The chromatography was performed at a column temperature of 40 ° C. at a flow rate of 1 ml / min. As a result, the synthesized polymer was separated by molecular weight depending on the presence or absence of synthesis. Figure 3 shows the absorbance according to the fraction separated by Sephadex CI 4 ratio, the highest molecular weight I peak eluted with a synthetic yield of 75%. In addition, to analyze the molecular weight of the peak I fraction, Sepadex CI 4 ratio chromatography was performed as a standard, and the elution time according to each molecular weight was measured. The results are shown in Table 1 below.

TABLE 1

sample Standard material Synthetic Polymer DEX 1 DEX 2 DEX 3 Molecular Weight (Da) 71,400 464,000 2,000,000 1,278,350 Detection time (min) 11.83 11.30 10.30 10.76

A graph of the detection time for each molecular weight of the standard of Table 1 was prepared as shown in FIG. 4 and converted into a graph prepared by detecting 10.76 minutes of the detection time of the synthetic polymer of the present invention (peak I in FIG. It was found that the synthetic polymer of the present invention has a molecular weight of approximately 1,278,350 Da.

It has a molecular weight of 10 which is commonly used as a coagulant.⁴To 10⁷In consideration of the Da range, it was determined that the synthetic polymer of the present invention could be used as a coagulant.

(3) structural analysis

In order to analyze the structure of the purified synthetic polymer, the purity of the synthetic polymer was investigated as FPLC. Synthesis of FPLC using a Superdex HR 10/30 resin at a flow rate of 0.6 ml / min in Tris buffer solution (20 mM Tris-HCl, pH 7.0) It was found that the polymer had a purity of 85%. However, it was difficult to accurately analyze the structure at 85% purity, and then FPLC was performed again to obtain a synthetic polymer having a purity of 96%. It was confirmed that the synthetic polymer of the present invention is an amine-based biopolymer of Chemical Formula 1 having a structure in which carbamate is bonded to a hydroxyl group at the carbon 6 position of glucose constituting starch.

[Formula 1]

Experimental Example

(1) property measurement

A rotary viscometer (DVII +, Brookfield, USA) was used to measure the physical properties of the amine-based biopolymers synthesized in the above example. After dissolving 0.1, 0.2 and 0.5% of the biopolymer in distilled water, the viscosity was measured at 25 ° C. Measured.

5 is a result of measuring the apparent viscosity according to the concentration of the amine-based biopolymer of the present invention, the apparent viscosity ([η _a ]) of 123 to 1018 cp when 0.1 to 0.5% of the amine-based biopolymer of the present invention is dissolved Could see.

(2) Measurement of cohesive efficiency

The actual flocculation efficiency of the amine-based biopolymer synthesized in the examples was evaluated. Jar-Test was performed on L and S plant wastewater using a 0.2% biopolymer solution, and the results are shown in Table 2 below.

TABLE 2

division 500 ppm injection of 0.2% biopolymer 500 ppm injection of 0.2% anionic synthetic polymer flocculant L factory S factory L factory S factory Alum injection amount (ppm) 800 1000 800 1000 % Removal COD 47.5 68.7 43.2 67.8 SS 95.7 98.4 96.7 94.7 Fe 93.2 92.8 45.4 37.5 Mn 79.4 84.6 57.2 48.9 Cr 86.3 79.1 41.3 28.7 Pb 83.0 74.9 63.5 64.6 Cu 97.5 96.8 73.9 64.2 CD 88.8 - 53.6 - As 95.3 - 24.8 -

As shown in Table 2, the amine-based biopolymer of the present invention shows a removal rate that is not significantly different from that of a synthetic polymer flocculant (0.2% solution) in terms of organic matter (COD) and suspended solids (SS) removal. On the other hand, heavy metals showed superior removal efficiencies compared to synthetic polymer flocculants.

As mentioned above, the amine-based biopolymer of the present invention is more efficient in removing heavy metals than the synthetic polymer flocculant used in the past, and is an inexpensive environmental friendly flocculant for water treatment.

In addition, the amine-based biopolymer of the present invention has a simple synthesis method compared to biopolymers or synthetic polymers developed to date, and can be easily separated at a low cost within a short time. It can be used industrially in resin for mass separation process.

Claims (7)

An amine biopolymer represented by the following Chemical Formula 1: [Formula 1] N is from 3,170 to 3,200. The amine-based biopolymer of claim 1, wherein the amine-based biopolymer is used as a flocculant. The amine-based biopolymer of claim 1 or 2, wherein the amine-based biopolymer is used as a flocculant for water treatment. (a) adding urea to ammonia water to dissolve at low temperature; (b) swelling the starch by mixing starch in the melt of step (a); (c) drying the mixture at room temperature and evaporating ammonia again at 100 ° C .; (d) adding nitrogen gas to the mixture to cause a polymer synthesis reaction; and (E) a method for producing an amine-based biopolymer comprising the step of separating and purifying the synthetic amine-based biopolymer synthesized above. The method of claim 4, wherein the starch of step (b) is mixed with the lysate at 20 wt% to 40 wt%. The method of claim 4, wherein the starch of step (b) is a conventional starch or corn starch containing amylose and amylopectin in a ratio of one to four. The method of claim 4, wherein the separation and purification of the step (e) is carried out by sized chromatography.