KR20120127354A - Chitosan-Biomass composite and Preparation method thereof - Google Patents

Abstract

PURPOSE: A chitosan-biomass complex in which a bacterial biomass is supported in chitosan is provided to improve adsorption performance. CONSTITUTION: A chitosan-biomass complex contains amine group-containing cationic polymers crosslinked on the surface. The bacterial biomass is a solid waste. An amine group-containing cationic polymer is conjugated with a functional group existing in bacterial biomass. The amine group-containing cationic polymer is polyethylene imine, amine-terminated polyethylene oxide, amine-terminated polyethylene/propylene oxide, dimethyl amino ethyl methacrylate polymer, a copolymer of dimethyl amino ethyl methacrylate and vinyl pyrrolidone; a linear polymer of epichlorohydrin and dimethyl amine, polydialryldimethyl ammonium chloride, polyethanol amine/methyl chloride, or modified polyethylene. [Reference numerals] (AA) Anionic contaminant; (BB) Attractive force; (CC) Repulsive power; (DD) Biomass

Description

Chitosan-Biomass Composite and Preparation Method

The present invention relates to a chitosan-biomass complex and a method for preparing the same, and more particularly, to a chitosan-biomass complex having a bacterial biomass supported on a binder, chitosan, and a method for producing the same.

Wastewater containing heavy metals or dyes such as lead, mercury and cadmium is generated in various industrial sites such as dyeing plants. Since such heavy metal or dye-containing wastewater enters the water system, it causes serious pollution, destroys the aquatic ecosystem, and has a harmful effect on humans by bioconcentration.

As a method for removing contaminants such as dyes and heavy metals in industrial wastewater, chemical treatment methods, physicochemical treatment methods and biological treatment methods are used. Chemical treatment methods include chlorine-based oxidation, Fenton's reagent method, ozone method and the like. However, this chemical treatment has the disadvantage of generating chemical sludge, generating harmful intermediates, and expensive operating costs.

Biological treatment method is generally used the activated sludge process to adsorb or decompose organic matter by the activated aerobic microorganisms, but this has the disadvantage that the amount of sludge generated and the solid-liquid separation in the sedimentation tank is not good. In addition, the dyes in the dyeing waste water are mostly made of a material that is difficult to biologically decompose and can produce toxic substances even if degraded, resulting in poor treatment efficiency. Physical treatment methods of industrial wastewater include precipitation, ion exchange resin, adsorption, electrophoresis and membrane removal, but these methods have problems such as high sludge generation, non-selectivity, excessive initial facility cost and high operating cost. Therefore, there is a need for a biological method that is environmentally friendly and has high selectivity and efficiency for hardly decomposable substances such as dyes and heavy metals. If such hardly decomposable substances are removed by biological methods, they can be selectively removed. As economics and efficiency are expected to be higher than those of conventional processes, interest in biosorption technology is increasing. Therefore, there is a need for the development of biomass capable of effectively treating hardly degradable contaminants such as dyes and heavy metals.

On the other hand, valuable metals (platinum group, gold, etc.) are used in various industries due to their unique chemical, electrical and physical properties. Particularly, catalysts of valuable metals generate waste materials containing valuable metals after producing reactants. The treatment of waste liquids containing these valuable metals is not only environmental preservation, but these valuable metals are very expensive and do not have any residual amount in Korea, and most of them depend on imports. very important. The smelting process, which recovers valuable metals from mineral resources and secondary resources (scrap and waste from manufacturing processes, waste products discarded after use, spent catalysts, etc.), consists of metal concentration, extraction, separation and refining processes. . Separation and purification of metals is very closely related to solution chemistry, and widely used separation and purification methods include chemical precipitation and crystallization, solvent extraction and ion exchange, oxidation distillation, and electrolytic refining. Separation and purification of the metal is mainly made of chemical precipitation or solvent extraction. However, with the recent stricter regulations on human risks of environmental regulations and working conditions, the development of new separation technologies that can guarantee more environmentally friendly and safe operation is urgently needed.

The present invention is to provide a biosorbent having excellent adsorption capacity and easy to apply to the actual process.

The present invention provides a chitosan-biomass complex that can be used as a biosorbent.

One aspect of the present invention relates to a chitosan-biomass complex carrying a bacterial biomass in a binder of chitosan.

Chitosan-biomass composites of the present invention comprise an amine group-containing cationic polymer crosslinked on its surface.

Another aspect of the invention is a step of stirring a mixture comprising bacterial biomass, chitosan and acidic solution; It relates to a method for producing a chitosan-biomass complex comprising the step of spinning the base solution and the mixture into the spinning machine.

The present invention comprises the steps of adding the chitosan-biomass complex to the amine group-containing cationic polymer solution to react; And a step of reacting the chitosan-biomass fibers with the amine group-containing cationic polymer solution by adding a crosslinking agent to the chitosan-biomass fibers.

Another aspect of the present invention is to mix and react the slurry bacterial biomass and amine group-containing cationic polymer solution, and to remove the supernatant; Stirring the mixture of chitosan and an acid solvent added to the reactant; Inserting the base solution and the mixture into a spinning machine and spinning; Reacting the spun fiber by adding the amine group-containing cationic polymer solution; And adding a crosslinking agent to the fiber and the amine group-containing cationic polymer solution to react the chitosan-biomass composite.

In another aspect, the present invention relates to a biosorbent composition comprising 10-50% (w / v) of bacterial biomass, 1-10% (w / v) of chitosan and 1-10% (v / v) of acid solvent. do.

The present invention relates to a chitosan-bacterial biomass complex formed by dropping the composition and curing with a base solution.

Chitosan-biomass fibers according to the present invention can be used directly in the biomass in the form of a slurry, so that the drying step of the biomass can be omitted and economical. In addition, the present invention provides a chitosan-biomass composite in the form of beads or fibers, which is difficult to apply to the actual process due to the small size of the biomass itself, particularly difficult to obtain a smooth flow rate due to high head (pressure). Solved it.

Chitosan-biomass fibers or composites according to the present invention further improved the adsorption performance.

1 is a schematic diagram showing the structure of a main functional group when bacterial biomass is present in an aqueous solution.
Figure 2 shows chitosan fibers (a), chitosan-biomass complexes (b), chitosan-biomass complexes (c) and amine group-containing cations coated with an amine group-containing cationic polymer without using a crosslinking agent. SEM image of composite (d) crosslinked with a polymer.
Figure 3 shows a chitosan-biomass complex (d) crosslinked with bacterial biomass (a), chitosan powder (b), chitosan fiber (c), chitosan-biomass complex (d), and amine group-containing cationic polymer Fourier transform infrared spectroscopy (FTIR) spectra are shown.
Figure 4 is a nitric acid containing ruthenium biomass of chitosan-biomass composites (corresponding to Examples 1-7) and Comparative Preparation Examples 1, 2 (corresponding to Comparative Examples 1, 2) obtained in Preparation Examples 1-7 It shows the result of carrying out ruthenium adsorption experiment in the waste liquid.
5 is an isothermal adsorption using the Langmuir model and Freundlich model by selecting Preparation Example 1 (Comparative Example 8), Comparative Production Example 1 (Comparative Example 3), Comparative Production Example 3 (Comparative Example 4) as the adsorption material It is a graph which performed the experiment and showed the result.
Figure 6 shows the ruthenium adsorption performance over time when the initial concentration of ruthenium is 61.6 mg / L.
Figure 7 shows the ruthenium adsorption performance over time when the initial concentration of ruthenium is 1822.9 mg / L.

Hereinafter, the present invention will be described in more detail.

One embodiment of the present invention relates to a chitosan-biomass complex in which bacterial biomass is supported on a binder of chitosan.

As used herein, the term "biomass" refers to a living or dead biological material that can be used for industrial production. In particular, the bacterial biomass of the present invention is killed by E. coli or Corynebacterium. It means a biomass consisting of the bacterial cells.

Bacteria such as Escherichia coli and Corynebacterium are widely used as strains producing substances such as antibiotics, anticancer agents, amino acids and nucleic acids. They are killed after being used and discarded as solid fermentation waste.

Figure 1 is a schematic diagram showing the structure of the main functional group when the solid waste bacterial biomass is present in the aqueous solution. Referring to FIG. 1, the bacterial biomass is rich in anionic functional groups (carboxyl or phosphate groups) and cationic functional groups (amine groups).

Chitin is a type of viscous polysaccharide in which N-acetyl-D-glucosamine is β-1,4-glycoside-bound, and is a chemical structural formula in which the hydroxyl group of C-2 in the glucose residue of cellulose is substituted with acetylamino group, and chitosan is present in chitin. It has a structural formula from which an acetyl group has been removed. Chitosa is obtained by deacetylation with strong alkali of chitin. However, deacetylation is not complete and chitosan is generally a polymer in which chitin and deacetylated chitin are mixed. The primary amine at the C-2 site of the glucosamine residue plays an important role in the reactivity and dissolution metastasis of chitosan. Chitosan is generally characterized by deacetylation and is insoluble in water, but is soluble in most acidic media up to about pH 6.5 (which may range from about pH 6.2 to pH 6.5, depending on the amine content of chitosan).

The chitosan which can be used in the method of the present invention is not particularly limited. For example, modified chitosan derivatives are included, as well as chitosan dissolved in dilute acid as described above. These chitosans also include N-acyl chitosan derivatives prepared by homogeneous deacetylation of chitin and dissolved in deionized water and N-acyl chitosan derivatives prepared by N-acylation, or N-carboxyalkyl chitosan derivatives having a carboxyalkyl group introduced therein. do. Chitosan that can be used in the process of the invention, preferably The degree of deacetylation is 40% to 100%, and the chitosan has a molecular weight of 13,000 to 1,000,000.

Figure 2 shows chitosan fibers (a), chitosan-biomass complexes (b), chitosan-biomass complexes (c) and amine group-containing cations coated with an amine group-containing cationic polymer without using a crosslinking agent. SEM image of composite (d) crosslinked with a polymer. Referring to (a), the chitosan fiber shows a smooth and wrinkled surface, and referring to (b), the chitosan-biomass composite shows an uneven and rough shape. In addition, referring to (c), the amine group-containing cationic polymer on the surface shows a rough and irregular shape, but when coated with a crosslinking agent as shown in (d) it can be seen that the surface is uniform.

Comparing Fig. 2 (a) and (b), (c), (d), it can be seen that the bacterial biomass particles are supported inside the chitosan. That is, in the complex of the present invention, chitosan is used as a support or a matrix, and bacterial biomass is supported on chitosan, preferably inside chitosan. More specifically, as the chitosan is cured, the biomass may be incorporated into the chitosan and embedded and fixed or supported. In one embodiment of the present invention, the mixture containing the bacterial biomass, chitosan and acidic solution is stirred to dissolve the chitosan in the acidic solution and simultaneously disperse the bacterial biomass in the chitosan solution. In one embodiment of the present invention, the mixture of the bacterial biomass and chitosan solution blended as above is cured chitosan into fibrous or bead phase using a basic solution, and as a result, the bacterial biomass particles are supported on the cured chitosan and granulated. Can be mad. Here, granulation means that the powder form of the biomass particles is supported on the chitosan support and becomes visible in the form of agglomerates.

FIG. 3 shows the four-ier transform of FTIR of bacterial biomass (a), chitosan powder (b), chitosan fiber (c), chitosan-biomass complex (d), and amine group-containing cationic polymer crosslinked (e) Infrared spectroscopy spectra. Referring to FIG. 2, the spectrum of the chitosan-biomass complex (d) shows the spectral characteristics of specific functional groups of the bacterial biomass (a) and the chitosan (b), confirming that the chitosan and the biomass are well mixed. Can be. In addition, in the spectrum of the complex (e) in which the amine group-containing cationic polymer is crosslinked, the amine group of the large amount of cationic polymer is coated to smooth the spectrum of the ami group, and the characteristics of the spectrum of the newly generated imine group by crosslinking the polymer by the crosslinking agent. This indicates that the amine group-containing cationic polymer is well coated on the surface of the chitosan-biomass composite.

The weight ratio of chitosan and bacterial biomass constituting the complex may be 1: 1-20, preferably 1: 1: 1.

The size of the bacterial biomass may be 1 ~ 20㎛, preferably 1 ~ 10㎛.

When the composite is in the form of a fiber, the diameter may be 50 to 1000 μm, preferably 50 to 200 μm.

The bacterial biomass may comprise an amine group-containing cationic polymer crosslinked on its surface, and may also be cured using a mixture comprising bacterial biomass, chitosan, amine group-containing cationic polymer and acidic solution. A complex of bacterial biomass, chitosan and amine group-containing cationic polymer can be formed.

The chitosan-biomass complex may comprise an amine group-containing cationic polymer crosslinked on its surface. The chitosan had a property of dissolving in acid and had a limit as an adsorbent. In the present invention, in order to solve this problem, the amine group-containing cationic polymer is bonded to the chitosan surface, and then a crosslinking agent is added to consolidate the binding thereof. In more detail, the amine group-containing cationic polymer reacts with a functional group present on the surface of the biomass and a functional group present in the chitosan, and when a crosslinking agent is added thereto, the biomass and amine group-containing cationic supported on the chitosan are added. It is possible to consolidate chemical bonds between polymers.

The complex in which the amine group-containing cationic polymer was crosslinked solved the problem that chitosan was dissolved in acid, and the physical strength of the composite was increased.

As used herein, the term “amine group-containing cationic polymer” refers to a polymer having an amine group in the main chain or side chain and having a totally positive charge. The amine group-containing cationic polymer of the present invention is one or more cations. It can be prepared by polymerizing a monomer, or by polymerizing one or more nonionic monomers and one or more cationic monomers.

The method of crosslinking the amine group-containing cationic polymer to the complex is not particularly limited, but preferably, the amine group-containing cationic polymer is crosslinked to the bacterial biomass surface to the chitosan surface by an amine group or a hydroxy group. It is desirable to have.

In the present invention, bacterial biomass is Corynebacterium sp.), Escherichia sp . ), Bacillus sp . ) And Serratia sp . ) And one or more bacterial cells selected from the group consisting of.

Non-limiting examples of the bacteria that make up such bacterial biomass include Corynebacterium ammoniagenes, Corynebacterium glutamicum, Escherichia coli, and Bacillus megate. Bacteria such as Bacillus megatherium and Serratia marcescens and Brevibacterium ammoniagenes.

In addition to the above-mentioned bacteria, Corynebacterium betae, Corynebacterium beticola, Corynebacterium bovis, Corynebacterium callunae, Corynebacterium Corybacterium fascians, Corynebacterium flak, Corynebacterium diphtheriae, Corynebacterium equi, Corynebacterium fascians flaccumfaci, Corynebacterium flavescens, Corynebacterium hoagii, Corynebacterium ilicis, Corynebacterium insidiosum, Corynebacterio insidium bacterio Bacteria, such as Neybacterium kutscheri and Corynebacterium lilium, It may include.

Examples of the amine group-containing cationic polymer usable in the present invention include polyethyleneimine, amine-terminated polyethylene oxide, amine-terminated polyethylene / propylene oxide, polymer of dimethyl amino ethyl methacrylate and dimethyl aminoethyl meta It can be selected from the group consisting of copolymers of acrylate and vinylpyrrolidone, linear polymers of epichlorohydrin and dimethylamine, polydiallyldimethylammonium chloride, polyethanolamine / methylchloride and modified polyethyleneimines. . More preferred are polymers having primary amines among polymers having primary, secondary and tertiary amines.

The amine group-containing cationic polymer may be a polyethyleneimine homopolymer of Formula 1 or a modified polyethyleneimine.

In the formula, n is 10 to 500.

The amine group-containing cationic polymer may have a cationic charge of 70 mol% or more, and the molecular weight of the amine group-containing cationic polymer is not particularly limited, but may be, for example, in the range of 1000 to 200,000.

The amine group-containing cationic polymer is a polyethyleneimine homopolymer and the biomass may be a biomass of Corynebacterium glutamicum.

In an embodiment of the bacterial biomass to the complex of the present invention, anionic functional groups on the surface may be further blocked to increase the adsorption capacity of the anionic contaminants.

In another aspect the present invention relates to a method for preparing a chitosan-bacterial biomass complex. When preparing the chitosan-bacterial biomass complex according to the present invention, the mixture containing the bacterial biomass, chitosan and acidic solution is stirred, and then, the base solution and the mixture are added to the spinning machine, and then spin-cured.

Hereinafter, each step of the present invention will be described in more detail.

Mixture Stirring  step

The step is stirring the mixture containing the bacterial biomass, chitosan and acid solution.

In the step, the above-described bacterial biomass and chitosan are mixed in an acidic solution to dissolve the chitosan in the acidic solution, and the bacterial biomass is dispersed in the chitosan solution.

10 to 50% (w / v) of the bacterial biomass and 1 to 10% (w / v) of the chitosan may be added to the acidic solution. It is preferable that the pH of the acid solution is 1 to 3, and the content thereof is not particularly limited, but may preferably include 1 to 10% (v / v).

The acidic solution is acetic acid, tartaric acid, salicylic acid, citric acid, hydroxyacetic acid, ringoic acid, propionic acid, lactic acid, glycerin acid, L-ascorbic acid, xenoic acid, sulfonic acid and formic acid, and organic acids of hydrochloric acid, sulfuric acid and phosphoric acid. It may be selected from the group consisting of. The bacterial biomass may be a bacterial biomass in a slurry state. Slurry biomass generally refers to a state in which water is contained as dead cell waste. The slurry may also be heated to remove some moisture by heating the biomass in the slurry state.

On the other hand, the present invention may use a wet (wet) biomass in which the supernatant is removed after centrifugation of the slurry biomass. The wet state indicates that some of the water in the slurry state has been removed. For example, the slurry biomass may have a water content of 80 to 90%, and the wet biomass may have some water removed, and thus the content may be 60 to 70%.

In the present invention, since the biomass in the slurry state can be used directly, it is economical without undergoing a separate drying process.

The method may further add an amine group-containing cationic polymer solution to the mixture. Since the amine group-containing cationic polymer solution has been described above, a description thereof will be omitted.

The amine group-containing cationic polymer solution may include one or more selected from the group consisting of water, alcohol, chloroform and pyridine as a solvent.

The mixture may be formed comprising bacterial biomass, chitosan, acidic solution and amine group-containing cationic polymer solution. There is no restriction on the composition ratio, but preferably 10 to 50% (w / v) of the bacterial biomass, 1 to 10% (w / v) of the chitosan, and 1 to 10% (w / v) of the amine group-containing cationic polymer. v) and 1-10% (v / v) of acidic solution can be used.

The mixture may be formed comprising bacterial biomass, chitosan, acidic solution, amine group-containing cationic polymer solution and crosslinking agent. There is no restriction on the composition ratio, but preferably 10 to 50% (w / v), the chitosan 1 to 10% (w / v), the amine group-containing cationic polymer 1 to 10% (w / v) and acidic Solutions 1-10% (v / v) and crosslinking agents 0.1-10% (v / v) can be used.

Curing step

The step is to add a base solution to the mixture to cure the mixture. The mixture of the bacterial biomass and chitosan solution blended by the above step is used to cure the chitosan using a basic solution, and as a result, the bacterial biomass particles may be supported on the chitosan.

The curing step may include spinning the base solution and the mixture into a spinning machine. According to the present invention, when the base solution and the mixture are put into a spinning machine and spun, the polymer chitosan is cured in a fiber form, and the biomass blended with chitosan is supported on the chitosan fiber. As a result, a fibrous chitosan-biomass composite can be produced.

Meanwhile, in the curing step, the mixture may be dropped and cured with a base solution. In this case, a bead-type chitosan-biomass complex may be prepared.

As the base solution, an aqueous sodium hydroxide solution, an aqueous ammonium hydroxide solution, or the like can be used.

Neutralization stage

The present invention may further comprise the step of neutralizing the chitosan-biomass complex after the curing step. In this step, the complex wetted with the base solution can be neutralized using an acid solution (for example sulfuric acid) or distilled water in which chitosan is not dissolved. The approximate pH range for neutralization is pH 5-9.

An amine group -contain Cationic Polymer  Crosslinking stage

This step is a step of adding a chitosan-biomass complex to the amine group-containing cationic polymer solution to react. By this step the chitosan-biomass complex may comprise an amine group-containing cationic polymer crosslinked on its surface.

Since the amine group-containing cationic polymer has been described above, a description thereof will be omitted. As one example, the amine group-containing cationic polymer has a cationic charge of at least 70 mol%, the molecular weight is preferably in the range of 1000 to 200,000.

The method of the present invention may further comprise the step of minimizing functional groups exhibiting repulsive force against anionic contaminants by blocking the anionic functional groups on the surface of the chitosan-biomass complex.

In this step, the chitosan-biomass complex is preferably dispersed in a sufficient amount of the amine group-containing cationic polymer, for example, the ratio of the chitosan-biomass complex and the amine group-containing cationic polymer is 1: 0.01. ˜1 (w: w), preferably 1: 0.01 to 0.1 (w: w) is preferably mixed.

The temperature for reacting the complex with the amine group-containing cationic polymer is not particularly limited, but for example, the complex may be reacted at a temperature of about 20 ° C. to 150 ° C. to increase the reaction efficiency.

By the above reaction, the amine group-containing cationic polymer reacts with the amine group or the hydroxyl group present on the surface of the chitosan-biomass and is bonded.

Cross-linking agent  Processing steps

When the amine group-containing cationic polymer is crosslinked on the surface of the chitosan-biomass complex, a crosslinking agent is treated to solidify the chemical bond between the complex and the amine group-containing cationic polymer. In this case, at least one selected from the group consisting of glutaraldehyde, isocyanide derivatives, and bisdiazobibenzidine may be used as the crosslinking agent.

In the case of treating the crosslinking agent, the crosslinking agent may be mixed in a solution state at 0.01 to 10% (v / v) with respect to the mixed solution of the complex and the amine group-containing cationic polymer, preferably 0.01 to 1% (v / v) is better to mix.

As the solvent, one or more selected from the group consisting of alcohols such as water, methanol, chloroform, pyridine, ethanol and butanol can be used.

In the present invention, the amine group-containing cationic polymer may be bonded (bonded) to the surface of the composite, and then a crosslinking agent may be added to solidify the bond with them.

Cleaning and Drying Steps

When the crosslinker treatment is complete, the composite is washed and dried. The washing and drying method is not particularly limited. In one example, the composite may be lyophilized or dried for a period of time in a hot oven. The drying temperature and drying time can be arbitrarily adjusted according to the water content of the composite and the like.

In another aspect, the present invention comprises the steps of mixing the slurry bacterial biomass and the amine group-containing cationic polymer solution to react, and removing the supernatant; Stirring the mixture of chitosan and an acid solvent added to the reactant; Inserting the base solution and the mixture into a spinning machine and spinning; Reacting the spun fiber by adding the amine group-containing cationic polymer solution; And reacting the fiber with an amine group-containing cationic polymer solution by adding a crosslinking agent.

The method first reacts the amine group-containing cationic polymer on the biomass, followed by the addition of chitosan and an acid solvent. The reaction conditions of the biomass and the amine group-containing cationic polymer are the same as the reaction conditions of the chitosan-biomass complex and the amine group-containing cationic polymer described above.

The method further comprises adding a crosslinking agent to the mixing reaction step of the slurry bacterial biomass and the amine group-containing cationic polymer solution to mix and react.

Specific details of the manufacturing method may refer to the above-described contents.

Hereinafter, the present invention will be described in more detail with reference to examples, but these are merely to illustrate preferred embodiments of the present invention, and the examples do not limit the scope of the present invention.

Example  One

Corynebacterium glutamicum biomass ( C. glutamicum) , a fermentation waste obtained in the form of slurry from the fermentation process 300 mL of biomass (target Gunsan Plant, Gunsan, Jeonbuk) (water content 85%) was added to 21 g of 7% (w / v) chitosan and 15 mL of 5% (v / v) acetic acid to prepare a mixture and stirred. The above mixture was placed in a spinning machine and dropped into 2M NaOH solution to obtain chitosan-biomass fibers. After stirring for curing the chitosan-biomass fibers, the supernatant was removed and 1M sulfuric acid was added to neutralize the chitosan-biomass fibers. Subsequently, after washing with distilled water, 300 mL of distilled water was added in a volume ratio of 1: 1 to the chitosan-biomass fiber, and 9 g of 3% (w / v) polyethyleneimide (weight average molecular weight 2500 g / L) was stirred at room temperature for about 24 hours. It was. After the reaction, 0.6% (v / v) glutaraldehyde (1.8 mL) was added thereto, followed by stirring at room temperature. After the reaction was completed, washed with deionized water and lyophilized to obtain a surface-modified biomass.

Example  2

Corynebacterium glutamicum biomass ( C. glutamicum) , a fermentation waste obtained in the form of slurry from the fermentation process biomass) (Daesan Gunsan Plant, Gunsan, Jeonbuk) (Water content 85%) 300 mL of 7% (w / v) chitosan 21 g, 5% (v / v) acetic acid 15 mL, 3% (w / v) polyethylene 9 g of mead (weight average molecular weight 25000 g / l) was added to prepare a mixture, which was stirred. Since the process was carried out in the same manner as in Example 1.

Example  3

Corynebacterium glutamicum biomass ( C. glutamicum) , a fermentation waste obtained in the form of slurry from the fermentation process biomass) (Daesan Gunsan Plant, Gunsan, Jeonbuk) (Water content 85%) 300 mL of 7% (w / v) chitosan 21 g, 5% (v / v) acetic acid 15 mL, 3% (w / v) polyethylene 9 g of mid (weight average molecular weight 25000 g / l) and 0.6% (V / V) glutaraldehyde were added to 1.8 mL of a mixture to prepare a mixture, which was stirred. Since the process was carried out in the same manner as in Example 1.

Example  4

Corynebacterium glutamicum biomass ( C. glutamicum) , a fermentation waste obtained in the form of slurry from the fermentation process biomass) (subject, Gunsan Plant, Gunsan, Jeonbuk) (moisture content 85%) after centrifugation to remove the supernatant to obtain a wet biomass. 40 g of wet biomass (65% water content) was added to 20 g of 6% (w / v) chitosan solution to prepare a mixture, which was stirred. Since the process was carried out in the same manner as in Example 1.

Example  5

Corynebacterium glutamicum biomass ( C. glutamicum) , a fermentation waste obtained in the form of slurry from the fermentation process 300 mL of biomass (target Gunsan Plant, Gunsan, Jeonbuk) (water content 85%) was added to 9 g of 3% (w / v) polyethyleneimide (weight average molecular weight 25000 g / l) and the supernatant was removed. Here 40g of the reaction was taken and mixed with 20g of 6% (w / v) chitosan and stirred. Since the process was carried out in the same manner as in Example 1.

Example  6

Corynebacterium glutamicum biomass ( C. glutamicum) , a fermentation waste obtained in the form of slurry from the fermentation process biomass) (Daesan Gunsan Plant, Gunsan, Jeonbuk) (water content 85%) 300 mL of 3% (w / v) polyethyleneimide (weight average molecular weight 25000 g / l) 9 g, 0.6% (V / V) glutar The reaction was added to 1.8 mL of aldehyde (glutaraldehyde) and the supernatant was removed. Here 40g of the reaction was taken and mixed with 20g of 6% (w / v) chitosan and stirred. Since the process was carried out in the same manner as in Example 1.

Example  7

Corynebacterium glutamicum biomass ( C. glutamicum) , a fermentation waste obtained in the form of slurry from the fermentation process biomass) (subject, Gunsan Plant, Gunbuk, Jeonbuk) (water content 85%) was centrifuged and the supernatant was removed to obtain wet biomass and dried. 40 g of dried biomass (0% water content) was added to 40 g of 6% (w / v) chitosan solution to prepare a mixture, which was stirred. Since the process was carried out in the same manner as in Example 1.

Comparative example  One

The fermentation waste Corynebacterium glutamicum biomass was obtained by centrifugation to remove the supernatant and drying the wet biomass.

Comparative example  2

2 g of Corynebacterium glutamicum, a fermented waste dried without pretreatment, was added to 500 ml distilled water of 3% (w / v) polyethyleneimide (weight average molecular weight 25000 g / l) and stirred at room temperature for 2 hours. It was. Subsequently, a 3 mL solution of 0.6% (V / V) glutaraldehyde was added to a mixed solution containing biomass and stirred. After completion of the reaction, washed with deionized water and lyophilized to obtain PEI-surface modified biomass.

Experiment 1

The chitosan-biomass complex obtained in Example 1-7 and the biomass in Comparative Examples 1 and 2 were placed in an acetic acid waste solution containing ruthenium and subjected to isothermal adsorption experiments for ruthenium adsorption. The results are shown in FIG. 4. .

Referring to FIG. 4, Examples 1 to 7 show higher ruthenium adsorption amounts than Comparative Examples 1 and 2. FIG. Referring to Examples 1 to 7, it can be seen that the adsorption material having excellent performance can be produced even by using the biomass in the sludge state. In Example 1, since the biomass slurry is directly used and the PEI and GA treatments are performed only once, the manufacturing cost is low, but there is an advantage of never falling in terms of adsorption performance.

Comparative example  3

In Comparative Example 3, an ion exchange resin (Bayer Lewatit MONOPLUS ^™ M600) was used as an adsorption material.

Experiment 2

Example 1, Comparative Example 1 and Comparative Example 3 were selected as the adsorption material in order to evaluate the ruthenium maximum adsorption amount was carried out isothermal adsorption experiment using the Langmuir model and Freundlich model, the results are shown in Figure 5 .

5, it can be seen that the Langmuir model fits all three adsorption materials. From the Langmuir model, the maximum adsorption amount of ruthenium of Example 1 was 110.5 mg / g, about 6.2 times higher than the maximum adsorption amount of Comparative Example 3, 17.7 mg / g, and about 16.5 times higher than the maximum adsorption amount of Comparative Example 4, 6.7 mg / g. It can be seen that it shows a large amount of adsorption.

Experiment 3

The ruthenium adsorption performance of Example 1 and Comparative Example 3 was evaluated under the conditions of flow rate 1.2 mL / min and bed volume 25 mL in the column process. The column experiment was performed by dividing the acetate wastewater containing low concentration of ruthenium (61.6 mg / L) and the acetate wastewater containing high concentration of ruthenium (1822.9 mg / L) and shown in FIGS. 6 and 7.

Figure 6 shows the ruthenium adsorption performance over time when the initial concentration of ruthenium is 61.6 mg / L. The breakthrough point was set to the point where 10% of the ruthenium initial concentration was released. 6, in Comparative Example 3, the breakthrough point was about 0.22 hours, and the ruthenium treatment time was very short. In contrast, the breakthrough point of Example 1 was found to adsorb a large amount of ruthenium at 42.32 hours and to be able to process for considerably longer time than Comparative Example 3.

Figure 7 shows the ruthenium adsorption performance over time when the initial concentration of ruthenium is 1822.9 mg / L. In this experiment, the temperatures were evaluated at 20, 40, and 60 degrees. Referring to FIG. 7, it can be seen that Example 1 has a much longer breakthrough point than Comparative Example 3. In addition, it can be seen that the time to reach the breakthrough point increases as the temperature increases in the column operation.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Those skilled in the art will readily appreciate that various changes, modifications, and variations may be made without departing from the spirit and scope of the present invention, as defined by the following claims and accompanying drawings.

Claims (19)

A chitosan-biomass complex supported on chitosan, wherein the bacterial biomass is a binder, the complex comprising an amine group-containing cationic polymer crosslinked on its surface;
The bacterial biomass is dead solid waste,
The complex is formed by the mixed bacterial biomass supported on chitosan during the curing of chitosan,
The amine group-containing cationic polymer is combined with functional groups present in chitosan and bacterial biomass, and the amine group-containing cationic polymer is polyethyleneimine, amine-terminated polyethylene oxide, amine-terminated polyethylene / propylene Oxide, polymer of dimethyl amino ethyl methacrylate and copolymer of dimethyl aminoethyl methacrylate and vinylpyrrolidone, linear polymer of epichlorohydrin and dimethylamine, polydiallyldimethylammonium chloride, polyethanolamine / methyl Chitosan-biomass composites, characterized in that at least one selected from the group of chlorides and modified polyethyleneimines. The method of claim 1, wherein the bacterium is Corynebacterium ammoniagenes to Ness (Corynebacterium ammoniagenes), Corynebacterium glutamicum (Corynebacterium glutamicum ), Escherichia coli , Bacillus megatherium and Serratia marsense marcescens and Brevibacterium Ammonia genes ) chitosan-biomass complex, characterized in that the bacteria selected from the group consisting of. The chitosan-biomass complex according to claim 1, wherein the weight ratio of the chitosan to the bacterial biomass is 1: 1 to 20. The chitosan-biomass composite according to claim 1, wherein the complex has a size of 50 to 1000 µm. Stirring the mixture comprising bacterial biomass, chitosan and acid solution;
Adding a base solution to the mixture to cure the mixture; And
Adding the complex obtained by the curing step to an amine group-containing cationic polymer solution to react,
The bacterial biomass is dead solid waste,
The complex is formed by supporting the bacterial biomass incorporated into the chitosan during the curing of the chitosan,
The amine group-containing cationic polymers include polyethyleneimine, amine-terminated polyethylene oxide, amine-terminated polyethylene / propylene oxide, polymers of dimethyl amino ethyl methacrylate and dimethyl aminoethyl methacrylate and vinylpyrrolidone. Of the chitosan-biomass complex, characterized in that at least one selected from the group consisting of: copolymers of epichlorohydrin and dimethylamine, polydiallyldimethylammonium chloride, polyethanolamine / methylchloride and modified polyethyleneimine Manufacturing method. The method of claim 5, wherein the method
And adding a amine group-containing cationic polymer solution to the complex to react the crosslinking agent, and then reacting the chitosan-biomass complex. 6. The method of claim 5, wherein the curing step comprises inserting the mixture into a spinning machine and spinning in a base solution. The method of claim 5, wherein the curing step comprises dropping the mixture and curing with a base solution. 6. The method according to claim 5, wherein the method further comprises neutralizing the chitosan-biomass complex formed by curing. The method of claim 5, wherein the method further comprises the step of washing and drying the chitosan-biomass complex. The method of claim 5, wherein the method uses a slurry of biomass in the form of a chitosan-biomass composite. 6. The method of claim 5, wherein the method further adds an amine group-containing cationic polymer solution to the mixture. The method of claim 5, wherein the method further comprises adding an amine group-containing cationic polymer solution and a crosslinking agent to the mixture. [Claim 6] The chitosan-biomass composite according to claim 5, wherein the wet mass biomass is removed from the supernatant after centrifugation of the slurry biomass. Mixing the slurry bacterial biomass with the amine group-containing cationic polymer solution to react, and removing the supernatant;
Stirring the mixture of chitosan and an acid solution added to the reactant;
Inserting the base solution and the mixture into a spinning machine and spinning;
Reacting the spun fiber by adding the amine group-containing cationic polymer solution; And
Reacting the fiber with an amine group-containing cationic polymer solution by adding a crosslinking agent,
The bacterial biomass is dead solid waste,
The fiber is formed by supporting the bacterial biomass incorporated into the chitosan during the curing of the chitosan,
The amine group-containing cationic polymers include polyethyleneimine, amine-terminated polyethylene oxide, amine-terminated polyethylene / propylene oxide, polymers of dimethyl amino ethyl methacrylate and dimethyl aminoethyl methacrylate and vinylpyrrolidone. Of the chitosan-biomass complex, characterized in that at least one selected from the group consisting of: copolymers of epichlorohydrin and dimethylamine, polydiallyldimethylammonium chloride, polyethanolamine / methylchloride and modified polyethyleneimine Manufacturing method. The method of claim 15, wherein the method comprises the step of mixing and reacting by adding a crosslinking agent to the mixing reaction step of the slurry bacterial biomass and the amine group-containing cationic polymer solution, the chitosan-biomass composite Way. [Claim 16] The chitosan-biomass complex according to claim 5 or 15, wherein the method adds 10-50% (w / v) of the bacterial biomass and 1-10% (w / v) of the chitosan. Manufacturing method. The method of claim 5 or 15, wherein the acid solution is acetic acid, tartaric acid, salicylic acid, citric acid, hydroxy acetic acid, ringoic acid, propionic acid, lactic acid, glycerin acid, L- ascorbic acid, xenoic acid, sulfonic acid and formic acid Method for producing a chitosan-biomass complex, characterized in that selected from the group consisting of organic acids and inorganic acids of hydrochloric acid, sulfuric acid and phosphoric acid. 16. The chitosan-bio according to claim 5 or 15, wherein the crosslinking agent is at least one selected from the group consisting of glutaraldehyde, isocyanide derivatives and bisdiazobibenzidine. Method for producing mass composite.

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