KR20060030380A - Biosorbent prepared from waste biomass of corynebacterium sp. and its application method - Google Patents

Abstract

The present invention relates to a dye adsorbent using microbial cells of Corynebacterium sp. Fermentation wastes, and to a method for preparing and using the same, to prepare a biosorbent by drying the Corynebacterium cells after acid treatment. The adsorbent may be applied to the dye wastewater to adsorb and remove the dye which is a color causing agent in the dye wastewater. The adsorbent according to the present invention effectively adsorbs reactive dyes under acidic conditions, basic dyes under neutral to alkaline conditions, and can be easily desorbed and regenerated, and can be used again. It is possible to provide an excellent low cost adsorbent that can replace the exchange resin.

Biosorbent, Fermentation Waste, Corynebacterium, Cells, Dyeing Wastewater

Description

Color adsorption agent for color removal in dyeing wastewater using fermentation waste and method of using the same [Biosorbent Prepared from Waste Biomass of Corynebacterium sp. and Its Application Method}

1 is a chemical structure of each reactive dye used in the present invention.

Figure 2 is a graph showing the removal rate of the dye when changing the equilibrium pH in removing the dye by applying the bioadsorbent according to the invention to various dye wastewater.

Figure 3 is an isothermal adsorption curve showing the relationship between the final dye concentration and the amount of adsorption in removing the dye by applying the bioadsorbent according to the present invention to various dye wastewater.

The present invention relates to an adsorbent using fermentation waste and a method of using the same, and particularly, to remove dyes produced by using microbial cells ( Corynebacterium sp. It relates to a biosorbent for. In addition, the present invention relates to a method of adsorbing and removing dyes in dyeing wastewater by using the biosorbent according to the present invention, and desorbing the adsorbed dye to regenerate and reuse the biosorbent repeatedly.

Dyes are widely used in industries such as dyeing factories, paper mills and textile dyeing. Dyeing wastewater generated in such industrial sites is inevitably generated after the dyeing process, and its components are complicated and difficult to decompose, causing water pollution. In particular, when the dye is discharged to the river is very high diffusivity, there is a great risk of increasing the pollution of the water system by disturbing the ecosystem by absorbing sunlight and inhibit the activity of photosynthetic organisms.

On the other hand, chemical, physical, chemical, and biological treatment methods have been proposed for removing dyes in dyeing wastewater.

Typical chemical treatment methods (oxidation methods) include chlorine-based oxidation methods, Fenton's reagent methods, and ozone methods. The chlorine-based oxidation method is inexpensive and simple to maintain, but has a disadvantage in that it cannot be decolorized unless used in large quantities. The Fenton's reagent method shows an effective discoloration of water-soluble and insoluble dyes, but has a disadvantage of generating sludge. In addition, the ozone method has a strong oxidizing power and does not generate sludge but has a short half life of about 20 minutes to use a lot of electricity. (Korean Patent Publication Nos. 2004-0065770, 2004-0034750, 2004-0013369) No. 2001-0045515, Domestic Journal of Advanced Environmental Technology, Nov. 1996, p. 13, "Methods and Problems of Bleaching Technology")

The biological treatment method is generally used the activated sludge process that adsorbs or decomposes organic matter by activated aerobic microorganisms, but has the disadvantage of high sludge generation and poor liquid-liquid separation in the sedimentation tank. 1998-0048018, 1998-0048016, 1997-0043028, Advanced Environmental Technology of the Korean Journal, November 1996, p. 6, "Current removal technology of dyeing wastewater and its countermeasures")

On the other hand, physical and chemical treatment methods include agglomeration, ion exchange resin, membrane separation, and adsorption. In the flocculation method, a flocculant is used. The flocculant includes an inorganic type and a polymer crab, and mainly an inorganic type. Polymeric coagulants are expensive and limited in scope, but inorganic coagulants are inexpensive and can aggregate many colored materials. However, there is a problem that the decolorization effect is changed according to the type of dye, the combination of the flocculant, the pH and the amount of flocculant added, and a large amount of sludge is generated. (Korean Patent Publication Nos. 2003-0082644, 2003-0023270, 2000- 0018060, Domestic Journal of Advanced Environmental Technology, Nov. 1996, pp. 13 ~ 15, "Method and Problem of Bleaching Technology")

The ion exchange resin method has excellent dye removal ability, but the ion exchange resin has a limitation in application to dye wastewater treatment because of its high price and high adsorption power for some dyes. The membrane separation method removes irrespective of the type of dye, but has a disadvantage of generating concentrated sludge. (Korean Patent Publication No. 2003-0070317)

On the other hand, the adsorption method is known to be the most feasible method compared to other methods because the treatment process is simple and the dye removal ability is excellent. However, activated carbon, which is generally used in adsorption, has the disadvantage of being expensive and mostly non-recyclable. (Remediation of dyes in textile effluent: a critical review on current treatment technologies, International Journal of Bioresourse Technology, 2001, pp. 77-247. with a proposed alternative ")

To solve this drawback, a new concept of dye adsorbent is urgently needed, and in particular, cells of a living organism can be used as a low-cost adsorbent. Adsorbents made from living organisms are termed biosorbents, which are very cheap ($ 0.1 to $ 14 / kg), unlike activated carbon ($ 1 to $ 2 / kg) and ion exchange resins ($ 7 to $ 14 / kg). /kg).(Foreign Books, Biosorption of Heany Metals, by B. Volesky, CRC Publisher CRC Press, Boca Raton, Florida, 1990)

The biosorbents researched and developed so far are as follows.

Korean Laid-Open Patent Publication No. 2003-0038964 relates to a cellulose-based adsorbent having a cationic functional group and a method for regenerating the same. An adsorbent obtained by crosslinking a compound containing a selected functional group and then reacting with a quaternary ammonium compound is disclosed.

Korean Laid-Open Patent Publication No. 2003-0045502 relates to an adsorbent for wastewater treatment using sawdust, which is prepared by introducing a nitrogen-containing cationic adsorption group after crosslinking sawdust with a compound containing a crosslinking functional group or a thermosetting resin. Is disclosed.

Korean Laid-Open Patent Publication No. 2003-0047633 relates to the manufacture of high concentration wastewater and waste liquid adsorbent using waste paper, and discloses a waste water adsorbent using high concentration wastewater or waste liquid in industrial wastewater by grinding the waste paper into soft powder.

However, such biosorbents have their own characteristics and advantages, but due to difficulties in the manufacturing process, cost problems, or their efficacy, they are still difficult to apply in practice.

In addition, the solid waste (corynebacterium cells) generated in the amino acid fermentation plant used in the present invention has not been studied as a raw material of the biosorbent so far, but only under alkaline conditions in Korean Patent Publication No. 2003-0074019 Microbial Corynebacterium YT-14 with TPA degrading capacity and methods for biologically treating wastewater containing TPA are described. The microbial Corynebacterium YT-14 used here is characterized in that TPA is decomposed by the metabolic process of microorganisms in a live state, but the cells of the genus Corynebacterium used in the present invention are used for amino acid production in an amino acid fermentation plant. The present invention relates to a biosorbent prepared from raw solid wastes that have been killed and then removed from the dyeing wastewater using the same. That is, the present invention utilizes the electrostatic attraction between functional groups and dye substances present in the cell, irrespective of the metabolic process of microorganisms, and thus the principle of eliminating raw materials, materials to be treated, and contaminants is completely different.

Solid wastes (Corinebacterium cells) are currently processed by ocean dumping, so if they are made of biosorbents, they can reduce the cost of waste disposal and generate profit from the waste.

On the other hand, the inventors of the present invention to focus on the following points to prepare a biosorbent using Corynebacterium cells. In other words, Corynebacterium cells genetically engineered to produce excessive amounts of amino acids contain a large amount of amino acids and proteins, and thus are rich in anionic functional groups (carboxyl groups) and cationic functional groups (amine groups). Considering that it will be able to adsorb reactive dyes effectively, while studying the technology of producing biosorbents using Corynebacterium cells as raw materials, biosorbents prepared through simple pretreatment were applied to dyeing wastewater. The present invention has been made by discovering that chromaticity can be effectively removed.

The present invention has been made in accordance with the idea as described above, using a fermentation waste dye adsorbent excellent in color absorption material (dye) in the dyeing wastewater, inexpensive, can be regenerated and repeatedly used The purpose is to provide.

In addition, the present invention is to provide a method for recycling the fermentation waste being dumped in the ocean as a biosorbent to reduce the environmental burden of the fermentation industry, and ultimately reduce the marine dumping to induce the effect of preventing marine pollution have.

In order to achieve the above object, the color adsorbent for removing color in the dyeing wastewater using the fermentation waste according to the present invention is applied to the dyeing wastewater in the dye adsorbent to adsorb and remove the dye causing the color, the adsorbent fermentation The cells in the corynebacterium waste are acidified and hydrogenated, and the hydrogenated cells are washed with water and dried.

In addition, in the method of using a biosorbent for applying the biosorbent according to the present invention to the dye wastewater by absorbing the dye which is a color causing material, the process of adsorption and removal of the anionic reactive dye with the biosorbent is acidic, cation The process of adsorbing the basic basic dye is characterized in that it is carried out in neutral to alkaline conditions.

In addition, after applying the bioadsorbent to the dye wastewater to adsorb the dye, it is characterized in that it further comprises the step of desorbing the adsorbed dye by adjusting the pH to regenerate the adsorbent.

Hereinafter, with reference to the accompanying drawings, a biosorbent using a fermentation waste according to the present invention will be described in detail.

The dye adsorbent according to the present invention is prepared by hydrogenating and drying Corynebacterium cells, which is a kind of fermentation waste, and the biosorbent is used to adsorb dyes from dyeing wastewater.

In order to use fermented waste Corynebacterium cells as dye adsorbents, dye adsorbents should be prepared using Corynebacterium cells first.

To prepare the dye adsorbent, first, the Corynebacterium cells are separated or concentrated from the slurry state. A strong acid solution (1M HNO ₃ ) is added to the isolated or concentrated cells, followed by stirring to substitute various ions in the cells with hydrogen ions to hydrogenate the functional groups. At this time, the stirring is performed at room temperature for about 12 hours at about 120 rpm. The hydrogenated cells are washed several times with water and dried in an oven at about 60 ° C. for about 24 hours.

By the above process, a color adsorbent for color removal using a fermented waste corynebacterium cell according to the present invention is prepared.

On the other hand, summarized the requirements that the fermentation waste as a biological adsorption material is as follows.

First, it should have high affinity and maximum adsorption amount (q _max ) for chromatic inducing substances.

Second, it must be recyclable at low cost.

Third, the repeated reuse of adsorption and desorption should be possible.

Fourth, the effects of the characteristics of the dyeing wastewater (such as salt concentration) should be less.

Fifth, it should be able to be used for various color inducing substances.

The adsorbent prepared by the present invention has all of the above conditions as a biosorbent material, and its performance has been proved through the following examples, and since the fermentation waste is used as a raw material, it is economical and environmentally friendly. It is expected to be valuable as a low-cost biosorbent material that can replace ion exchange resins.

The inventors carried out the following experiment to determine the adsorption characteristics of the dye of the biosorbent using the Corynebacterium cells according to the present invention.

In order to examine the efficacy of the present invention, a biosorbent was prepared from the Corynebacterium Glutamicum cells, which are fermentation wastes generated in the amino acid fermentation process, and used for the experiment. Reactive Orange 16 (RO16), Reactive Yellow 2 (RY2) and two cationic basic dyes (Methylene Blue (MB) and Basic Blue 3 (Basic Blue 3, BB3)) Used. The chemical structure of the dye used is shown in FIG. General properties of the dye are shown in Table 1 below. The dyes were purchased from Sigma-Aldrich Chemical Company, USA.

Kinds Dye Molecular formula Molecular Weight Color Index (＃) Dye Content (%) Maximum light absorption wavelength λ _max (nm) Anionic reactive dyes RO16 C ₂₀ H ₁₇ N ₃ O ₁₁ S ₃ 2Na 617.54 17757 50 494 RY2 C ₂₅ H ₁₅ Cl ₃ N ₉ O ₁₀ S ₃ 3Na 872.97 18972 60-70 404 Cationic basic dyes MB C ₁₆ H ₁₈ ClN ₃ SxH ₂ O 319.9 52015 85 661 BB3 C ₂₀ H ₂₇ ClN ₃ O 360.9 51004 25 654

Example 1

The effect of pH of the dye solution on the adsorption performance was examined.

First, a dye solution in 500 mg / L was prepared by dissolving the dye in deionized distilled water.

After putting 40 mg of the synthetic synthetic wastewater of 500 mg / L prepared as described above into a flask, and adding 0.4 g of the biosorbent prepared, the pH of the synthetic wastewater containing the biosorbent was adjusted from 1 to 12 with 1M NaOH and 1M. Adjusted with HNO ₃ . Thereafter, the flask was placed in a stirrer and stirred at 150 rpm at room temperature for 24 hours. Thereafter, in order to separate the solid biosorbent and the liquid synthetic wastewater, the centrifugal separator was centrifuged at 8000 rpm for 5 minutes, and the maximum light absorption wavelength of each dye was measured using a spectrophotometer (UV-mini-1240 Spectrophotometer). _max ) was analyzed for the remaining dye concentration in the synthetic wastewater.

The results for the removal rate of the dye at each pH are shown in FIG. Referring to Figure 2, the anionic reactive dye showed a removal rate of more than 99% in acidic conditions, neutral to alkaline conditions for the cationic basic dyes.

Example 2

Biosorption Isotherms were determined from initial reactive dye concentrations ranging from 50 to 5000 mg / l in acidic conditions (pH 1) to determine the maximum adsorption performance of the prepared biosorbent dye.

Bioadsorption isotherm means a line drawn between the dye adsorption rate (q = mg dye / g adsorbent) and the dye concentration (C _f = mg dye / L solution) remaining in the solution.

Figure 3 shows the isothermal adsorption curve obtained by the experiment, the maximum adsorption amount of each dye using the Langmuir equation (q = q _max K _a C _e / (1 + K _a C _e ) 137 ~ 464mg The maximum adsorption amount was considerably higher when compared to several other adsorbents (see Table 2), and considering that the biosorbents produced are very inexpensive, activated carbon, other biosorbents, It is believed that it will be able to replace existing adsorbents such as ion exchange resins.

Dys Sorbent Maximum sorption capacities (g / kg) RR 222 Remazol Black B BR 22 MB RR 222 Chitosan (non-cross-linked) Fungus Activated carbon, fuller's earth C. glutamicum biosorbent Chitosan (non-cross-linked) 1026-1106 286-588 460-520 378 299-380 RB 2 BB 69 AB 158 Activated sludge Peat Chitin 250 184-233 216 BB3 C. glutamicum  biosorbent 210 RY2 RO16 AB 25 RY 145 RO 16 Telon Blue Astrazone Blue C. glutamicum biosorbent C. glutamicum biosorbent Chitin Chitosan (non-cross-linked) S6326a, strong basic anion exchanger Activated carbon Maize cob 199 189 183 117-179 167-160 160 RB 2 RO 16 RY 2 RO 16 Rice husk OC1066, polystyrene, unfunctionalized Bacteria MP62, weak basic anion exchanger 130 129 52-124 123 RR 222 AB 25 RB 222 BB 29 Mordant Yellow 5 RR 222 Disperse Red 1 Erionyl Red Direct Red 84 Astrazone Blue MO, MB, RB Acid Violet 17 CR, MV, AB AB 29 AB 25 Congo Red Acid Orange 10 Acid Brilliant Blue Chitin Carbon, peat, alumina Chitosan (non-cross-linked) Peat, fly ash Chitin Activated carbon Peat, bentonite, slag, fly ash Maize cob Chitin Silica Banana and orange peel Orange peel Banana and orange peel Peat, fly ash Peat Activated carbon (coir pith) Activated carbon Banana pith -100 83-99 54-87 54-46 52 -50 23-50 48 44 -25 14-21 20 6-18 14-15 5-9 7 2-6 4-5

That is, as shown in Figure 3, the biosorbent prepared in the present invention has a large maximum adsorption amount (q _max ) for a variety of dyes, in particular, has a high affinity (K _a ) at low concentrations, causing chromaticity in the dye wastewater The removal performance was excellent for the dye, which is a substance.

Kinds dyes q _max (mg / g) K _a (ℓ / mg) R ² Anionic reactive dyes RO16 188.77 1.3 × 10 ^-2 0.987 RY2 198.66 7.8 × 10 ^-3 0.887 Cationic basic dyes MB 378.37 7.9 × 10 ^-3 0.749 BB3 210.02 9.8 × 10 ^-3 0.807

Example 3

Next, an experiment was performed to determine the desorption performance of the dye adsorbed on the biosorbent according to the present invention.

For the desorption experiment, the bioadsorbent with the reactive dye adsorbed at pH 7 and the biosorbent with the basic dye adsorbed at pH 2 were stirred at 150 rpm for 24 hours.

Table 4 shows the results of the desorption test for each dye.

Kinds dyes Desorption pH Desorption rate (%) Anionic reactive dyes RO16 7 100 RY2 7 100 Cationic basic dyes MB 2 50-70 BB3 2 40-50

As a result, the desorption rate was 100% for the anionic reactive dyes RO16 and RY2, and up to 90% for the cationic basic dyes MB and BB3.

Therefore, after adsorbing the dye in the present invention, the bioadsorbent can desorb the dye again only by adjusting the pH.

Example 4

Experiments were conducted to evaluate the repeatability of the prepared biosorbents. Specifically, RY16, an anionic reactive dye, was adsorbed at pH 1 and desorbed at pH 7, and the adsorption / desorption process was performed up to 8 times. MB and BB3, which are cationic basic dyes, were adsorbed at pH 2 and desorption at pH 10, and the adsorption / desorption process was performed up to four times. The results are summarized in Table 5.

Kinds dyes Number of adsorption / desorption One 2 3 4 5 6 7 8 Adsorption rate (%) Desorption rate (%) Adsorption rate (%) Desorption rate (%) Adsorption rate (%) Desorption rate (%) Adsorption rate (%) Desorption rate (%) Adsorption rate (%) Desorption rate (%) Adsorption rate (%) Desorption rate (%) Adsorption rate (%) Desorption rate (%) Adsorption rate (%) Desorption rate (%) Anionic reactive dyes RO16 100 87.3 90.7 98.5 92.8 84.0 99.7 80.4 99.9 78.7 99.1 76.9 100 85.8 100 88.8 RY2 100 100 100 100 100 100 100 100 100 100 Cationic basic dyes MB 100 66.5 100 56.8 100 55.6 100 54.5 BB3 100 48.7 100 44.5 100 42.1 100 43.3

As a result of the desorption experiment, it can be seen that the cells can be regenerated and used repeatedly by repeating adsorption-desorption.

This shows that the bioadsorbent according to the present invention is easy to be desorbed and reused as compared with the difficulty of desorbing ion exchange resins or activated carbon, which are commercially widely used adsorbents.

In addition, the adsorption and desorption processes are economical because they are made only by changing the pH.

Example 5

In the dyeing process, since a large amount of salt (NaCl or Na ₂ CO ₃ ) is used to effectively dye, the dyeing wastewater generally contains an excessive amount of salt. Therefore, an experiment was conducted to determine the effect of salt concentration on the adsorption performance when the dye is adsorbed by the biosorbent according to the present invention. In this experiment, two dyes (RO16, RR4) were treated with synthetic dye wastewater containing various NaCl concentrations using a biosorbent roll according to the present invention. The results are summarized in Table 6.

Kinds dyes Initial dye concentration (mg / ℓ) Amount of NaCl (M) 0 0.05 0.10 0.15 0.20 0.25 0.30 Anionic reactive dyes RO16 Adsorption amount (mg / g) 200 18.3 18.1 18.1 18.0 17.3 17.2 17.5 1000 90.0 86.3 87.2 84.7 85.0 82.8 81.9 3000 168.5 166.0 169.8 165.0 157.2 149.5 151.6 RR4 Adsorption amount (mg / g) 500 49.0 50.0 49.2 50.4 49.6 49.6 49.7

In view of the results of such a salt effect, the bioadsorbent according to the present invention is negligible the effect on the salt.

This is to remove the chromaticity in the dyeing wastewater, when applying the biosorbent according to the present invention, there is no deterioration of the adsorption performance by the dye contained in the dyeing wastewater has the advantage that it can effectively treat the actual wastewater.

By using the biosorbent prepared from the fermentation waste according to the present invention as described above, it is possible to provide a dye adsorbent having excellent adsorption performance, economical, repeatable regeneration, and not affected by salinity in dyeing wastewater. There is an effect.                     

In addition, since the present invention is a waste recycling method, it is eco-friendly, and is easy to manufacture and use, so that it can be easily applied for practical use. It can be effective.

As described above, the present invention is to provide a biosorbent capable of adsorbing and removing dye-causing dyes in the dyeing wastewater by using the fermentation waste Corynebacterium cells, to provide an adsorbent of excellent performance, Many modifications and variations are possible without departing from the spirit of the invention.

Claims (3)

In the dye adsorbent that is applied to the dyeing wastewater to remove the dye causing the color, The adsorbent is to remove the color in the dyeing wastewater using the fermentation waste, characterized in that the fermentation waste was produced by the acid treatment of the cells in the Corynebacterium sp. Biosorbent. In the method of using a biosorbent to apply the biosorbent of claim 1 to the dyeing waste water to absorb and remove the dye is a color-causing material, The process of adsorbing and removing the anionic reactive dye with the dye adsorbent is performed under acidic conditions, and the process of adsorbing cationic basic dye is performed under neutral to alkaline conditions. How to use. The dyeing wastewater according to claim 2, further comprising: applying the biosorbent to the dyeing wastewater to adsorb the dye, and then adjusting the pH to desorb the adsorbed dye to regenerate the adsorbent. A method of using a biosorbent for removing chromaticity in water.

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