KR20160099910A - Evaluation method of biodegradation - Google Patents

Evaluation method of biodegradation Download PDF

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KR20160099910A
KR20160099910A KR1020150022193A KR20150022193A KR20160099910A KR 20160099910 A KR20160099910 A KR 20160099910A KR 1020150022193 A KR1020150022193 A KR 1020150022193A KR 20150022193 A KR20150022193 A KR 20150022193A KR 20160099910 A KR20160099910 A KR 20160099910A
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gas
surface area
sample
biodegradable polymer
biodegradation
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KR1020150022193A
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Korean (ko)
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김중래
문정헌
김미연
김창만
송영은
이재춘
김보미
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(주) 웹스
부산대학교 산학협력단
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    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12QMEASURING OR TESTING PROCESSES INVOLVING ENZYMES, NUCLEIC ACIDS OR MICROORGANISMS; COMPOSITIONS OR TEST PAPERS THEREFOR; PROCESSES OF PREPARING SUCH COMPOSITIONS; CONDITION-RESPONSIVE CONTROL IN MICROBIOLOGICAL OR ENZYMOLOGICAL PROCESSES
    • C12Q1/00Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions
    • C12Q1/02Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions involving viable microorganisms
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004Gaseous mixtures, e.g. polluted air
    • G01N33/0009General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0062General constructional details of gas analysers, e.g. portable test equipment concerning the measuring method, e.g. intermittent, or the display, e.g. digital
    • G01N33/0067General constructional details of gas analysers, e.g. portable test equipment concerning the measuring method, e.g. intermittent, or the display, e.g. digital by measuring the rate of variation of the concentration

Abstract

The present invention relates to a method for evaluating biodegradation and, more specifically, relates to a method for evaluating biodegradation, which evaluates the biodegradation of a biodegradable polymer substance in a rapid and accurate manner. According to the present invention, the method for evaluating biodegradation comprises the steps of: manufacturing an analysis sample using a crusher and a biodegradable polymer sample; inserting the analysis sample, a microorganism culturing medium, and anaerobic sludge in a sealed-type flask; culturing the flask in a stirrer at a constant temperature after sealing the same; measuring an amount of gas generation produced by analyzing an atmospheric composition; calculating a speed of gas generation per specific surface area; and evaluating the biodegradation.

Description

{Evaluation method of biodegradation}

The present invention relates to a method for evaluating biodegradability, and more particularly, to a method for evaluating biodegradability of a biodegradable polymer particle, granule, film, sheet, etc. using microorganisms contained in sewage sludge To a biodegradability evaluation method for rapidly and accurately evaluating the biodegradability of a biodegradable polymer substance in a short period of time within a few days.

Recently, the consumption of various plastic materials has increased rapidly due to population growth and industrial scale expansion, and plastic products based on existing petrochemical raw materials are being replaced by biodegradable products using biomass resources as raw materials.

There is no net increase in atmospheric carbon dioxide, and various regulations and regulations are being strengthened for the production and dissemination of biodegradable plastics and polymer composites based on eco-friendly materials.

Establishment of quantitative biodegradability (analysis) method of biodegradable polymers in the natural world is an essential element for producing tailor-made products for biomedical polymers and expanding the market of environmentally friendly plastics.

However, since most of the biodegradation test period is carried out over a period of several weeks and several months, improvement of products using the result of biodegradability and production of customized products suited to consumer needs are obstacles.

Conventional conventional biodegradation analysis methods are simply measuring physico-chemical hydrolysis rate, loss rate analysis by measuring viscosity change rate, and analysis of reduction rate by weight measurement.

In addition, since the experimental conditions are tested at 80 to 102 ° C using an organic solvent, it is difficult to survive the microorganisms as the final decomposer of the biodegradation under these conditions, so that biodegradation I can not say.

The definition of 'biodegradable' means that the polymer substance is completely mineralized by the action of microorganisms such as bacteria, fungi, and green algae that exist in nature, such as carbon dioxide and methane.

Therefore, the existing biodegradation evaluation method does not satisfy the requirement of biodegradability and merely evaluates desorption or hydrolysis rate of the polymer substance which is a pre-stage of biodegradation.

Korean Patent Publication No. 10-2014-0048405

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to provide an analysis method suitable for the definition of biodegradability by carrying out an analysis based on degradability of a polymer material of a microorganism.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are not restrictive of the invention as set forth in the accompanying drawings. It will be possible.

The method for evaluating biodegradability according to the present invention comprises measuring the surface area of a biodegradable polymer sample, measuring the rate of gas evolution after biodegrading the biodegradable polymer sample into microorganisms, measuring the rate of gas evolution of the biodegradable polymer sample And the gas generation rate per unit area of the polymer sample is calculated using the surface area and the gas generation rate.

The gas generation rate is a gas generation rate of carbon dioxide in an aerobic condition and a gas generation rate of methane in an anaerobic condition.

Also, there is provided a method for producing a biodegradable polymer, comprising the steps of: preparing a biodegradable polymer sample by using a pulverizer; A second step of introducing the analytical sample into a closed flask, feeding the microorganism culture medium and the anaerobic sludge into the closed flask; A third step in which the flask is closed and incubated in a constant temperature stirrer; A fourth step of collecting the gas in the flask with a gas sample syringe, analyzing the composition of the gas phase, and measuring the amount of gas produced; A fifth step of calculating a gas generation rate per specific surface area using the specific surface area of the analytical sample and the amount of generated gas; And a sixth step of evaluating the degree of biodegradation using the gas generation rate per non-surface area.

The method further includes the step of removing oxygen by filling with nitrogen in the anaerobic condition in the third step.

In the third step, the culture is performed at 20 to 50 ° C at a rotation speed of 100 to 200 rpm.

According to the solution of the above-mentioned problems, the biodegradability evaluation method of the present invention has an effect of providing a more accurate evaluation method of biodegradability by carrying out an analysis based on the degradability of a polymer material of a microorganism.

In addition, since the carbon dioxide and methane produced as the final decomposition products are calculated as an index, mathematical modeling can predict the time required for complete decomposition according to the amount of actual waste.

In addition, it is possible to develop a quantitative index comparable to the speed at which the soil is degraded by weight measurement in parallel with the actual soil experiment, and various biodegradable polymer materials or polymer complexes It is possible to predict the decomposition speed.

1 is a flowchart showing the flow of the method for evaluating biodegradability according to the present invention.
FIG. 2 is a graph showing the amount of generated carbon dioxide over time in the analysis of the gas production rate per unit area of the biodegradable polymer according to the particle size.
FIG. 3 is a graph showing the amount of methane generated over time in the analysis of gas production rate per unit area of biodegradable polymer by particle size.
FIG. 4 is a graph showing the amount of generated carbon dioxide over time in an experiment for analyzing the gas generation rate per specific surface area by the input amount of the biodegradable polymer having the same particle size.
FIG. 5 is a graph showing the amount of methane generated over time in an experiment for analyzing the gas generation rate per specific surface area by the input amount of the biodegradable polymer having the same particle size.
FIG. 6 is a graph showing the amount of methane generated over time in the analysis of gas velocity at specific surface area according to polymer samples having different biodegradability.

The above and other objects, features and advantages of the present invention will be more apparent from the following detailed description taken in conjunction with the accompanying drawings, in which: FIG. BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention and the manner of achieving them will become apparent by reference to an embodiment which will be described in detail below with reference to the accompanying drawings.

The present invention relates to a method for evaluating the biodegradability of biodegradable polymers, and relates to a method for evaluating the biodegradability of biodegradable polymers by using a sewage sludge containing various microorganisms or a pure microorganism and measuring the production rate of carbon dioxide (CO 2 ) or methane (CH 4 ) It is a method to quantitatively analyze and evaluate biodegradability.

In the present invention, the gas generation rate of a gas generated after biodegradation of a biodegradable polymer sample through microorganisms is measured, and the gas generation rate per unit area of the biodegradable polymer sample with respect to the surface area of the biodegradable polymer sample is calculated And a method for evaluating biodegradability is provided.

The polymer sample may be prepared by pulverizing a biodegradable polymer material in a pulverizer and separating the polymer material according to the particle size, cutting the polymer film to a predetermined size, or molding polymer particles (granules) of various sizes by molding the particles according to particle size using a polymer template. Can be used.

The gas is preferably methane (CH 4) is produced in case of end-minute gas generated in accordance with the sea, and if aerobic conditions to carbon dioxide (C0 2) is produced as the final degradation products, anaerobic conditions, the final degradation products Do.

The gas generation rate per unit area of the surface of the biodegradable polymer sample indexed by the biodegradability evaluation method is defined by the following equation (1).

Figure pat00001

The biodegradability evaluation method described above will be described in detail below with reference to the drawings.

≪ Evaluation method of biodegradability &

1 is a flowchart showing the flow of the method for evaluating biodegradability according to the present invention.

First, in a first step (S110), a biodegradable polymer sample is prepared by using a crusher. Specifically, a biodegradable polymer sample to be measured is crushed with a crusher to prepare an analytical sample.

The particle size of the biodegradable polymer sample may be variously changed according to the characteristics, strength and degree of crushing of the sample to be analyzed, but it is preferable to uniformly standardize the biodegradable polymer sample to easily obtain the specific surface area of the biodegradable polymer sample .

Also, according to the hardness of the pellets of the biodegradable polymer, various crushers and crushers and crushing conditions can be used. In order to minimize melting due to heat generation during crushing, dry ice can be used.

Next, in the second step (S120), the analytical sample is introduced into a closed flask, and the microbial culture medium and the anaerobic sludge are introduced into the closed flask. Specifically, the crushed analytical sample is introduced into a closed flask, and the prepared microorganism culture medium and anaerobic sludge are introduced.

The microorganism culture medium contains ammonium chloride (NH 4 Cl), sodium monophosphate (NaH 2 PO 4 .H 2 O), sodium hydrogen phosphate (Na 2 HPO 4 ) , potassium chloride (KCl), vitamins and minerals in distilled water , The acetate is added to the initial microorganism growth substrate and the pH is titrated to neutral (pH 7.0) suitable for microbial growth.

The chemical composition of the microorganism culture medium can be adjusted depending on the inoculum, and the pH can be adjusted to a pH of 6.5 to 7.5 suitable for general microbial growth and metabolism.

In addition, the anaerobic sludge uses sludge that has been filtered by removing impurities from sewage sludge. The anaerobic sludge is used as a microorganism inoculation source containing various microorganisms at a high concentration and can be replaced with a mixed microorganism including pure microorganisms or anaerobic sludge.

The amount of the microorganism culture medium and anaerobic sludge is adjusted according to the amount of the analytical sample.

Next, in a third step (S130), the flask is closed and incubated in a constant temperature stirrer. Specifically, the flask containing the above-mentioned analytical sample, microorganism culture medium, and anaerobic sludge is sealed and fixed by a constant temperature stirrer.

The microorganisms of the microorganism culture medium and the anaerobic sludge are adhered to the surface of the biodegradable polymer and then cultured in a microorganism culture condition using a constant temperature stirrer.

The stirrer may be replaced with a magnetic stirrer or a constant temperature water chamber.

The culturing conditions are incubated at a temperature of 20 to 50 DEG C and a rotation speed of 100 to 200 rpm, which is suitable for microbial growth. Optimal culture conditions using the above-mentioned constant temperature stirrer are most preferably incubated at a rotation speed of 160 rpm at 37 캜.

Through the above cultivation, microorganisms adhere to the surface of the biodegradable polymer to initiate a decomposition activity, and metabolic activities such as hydrolysis of the polymer, production of organic acid, and final gas production are performed through the metabolism of the microorganism.

In the third step S 130, the anaerobic condition is filled with nitrogen (N 2 ) to remove oxygen. Specifically, when analysis is performed under anaerobic conditions, the flask containing the analytical sample, the microbial culture medium, and the anaerobic sludge is purged with nitrogen (N 2 ) to remove oxygen, and the stopper is closed and sealed in a thermostatic stirrer Start culturing.

Next, in a fourth step (S140), the gas in the flask is sampled with a gas sample syringe, and the amount of produced gas is measured by analyzing the composition of the gas phase. Specifically, after the gas in the flask is sampled with a gas sample syringe while being cultured under the above conditions, the gas phase composition is analyzed by gas chromatography or the like to analyze carbon dioxide (CO 2 ) or methane (CH 4 ) produced in the gas phase Measure production.

The gas is the final degradation products are carbon dioxide (C0 2) of the polymer through the mineralization in the final decomposition products carbon dioxide (C0 2) or measure the methane (CH 4), aerobic conditions in which oxygen is abundant supply of biodegradable polymer , And it is preferable to measure it on the basis of methane (CH 4 ) under oxygen-poor anaerobic conditions.

The gas chromatography can be replaced with various analytical instruments capable of detecting the gas components of the carbon dioxide (CO 2 ) and methane (CH 4 ), such as the gas detector and the detector for measuring the final decomposition products of the biodegradable polymer.

Next, in a fifth step (S150), the specific surface area of the analytical sample and the gas generation rate are used to calculate the gas generation rate per specific surface area. Specifically, the rate of gas generation per non-surface area is calculated in consideration of the specific surface area and the time according to the analytical sample.

The specific surface area of the analytical sample can be calculated assuming that the shape of the particle is spherical. However, by calculating the exact surface area of the sample per unit weight with an analyzer such as a surface area analyzer (BET) or a particle size analyzer, The amount of gas generated per area can be calculated.

Next, in the sixth step (S160), the degree of biodegradation is evaluated using the gas generation rate per non-surface area. Specifically, the calculated rate of gas generation per surface area is indexed to evaluate the degree of biodegradation.

Next, the biodegradability evaluation method described above will be described in more detail using experiments and examples.

A. Of biodegradable polymers by particle size Non-surface area  Gas production rate analysis

The following experiment is an experiment for analyzing the gas production rate per unit area of the biodegradable polymer according to the particle size, and is shown in Examples 1 to 3.

First, polylactic acid (PLA) as a biodegradable polymer sample was placed in a pulverizer (PMF-600 Miller, QS Machinery) to set the differentiator blade interval to 0.9 mm and to crush 300 kg per hour at 10000 rpm. .

The crushed analytical samples are classified into 20-40 mesh, 60-80 mesh, and 100-120 mesh according to particle size to prepare Examples 1, 2, and 3.

[Example 1]

In Example 1, the particle size of the analytical sample was pulverized to 20 to 40 mesh based on the analysis conditions of the biodegradability evaluation method of the present invention.

[Example 2]

In Example 2, the particle size of the analytical sample was pulverized to 60 to 80 mesh based on the analysis conditions of the biodegradability evaluation method of the present invention.

[Example 3]

In Example 3, the particle size of the analytical sample was ground to 100 to 120 mesh based on the analysis conditions of the biodegradability evaluation method of the present invention.

Next, 20 g of each of the above Examples 1 to 3 was placed in a 250 ml-closed flask, and 100 ml of the prepared microorganism culture medium and 10 ml of the anaerobic sludge were introduced.

The microbial culture medium contained 0.31 g of ammonium chloride (NH 4 Cl), 2.69 g of sodium phosphate monobasic (NaH 2 PO 4 .H 2 O), 4.33 g of sodium hydrogenphosphate (Na 2 HPO 4 ) , potassium chloride ), 12.5 ml of vitamins and 12.5 ml of minerals, and 0-40 mM of acetate was added to the initial microorganism growth substrate. The pH was adjusted to neutral (pH 7.0) suitable for microbial growth.

The anaerobic sludge used as the microorganism inoculation source was collected from a second anaerobic tank of a swimming sewage treatment plant and sieved with a 10 mesh sieve to remove impurities and used filtered sludge.

Next, the flask containing each of the above Examples 1 to 3 was purged with 100% nitrogen (N 2 ) for 5 minutes to remove oxygen. After closing the cap and sealing, the culture was started by fixing on a constant temperature stirrer. Culturing conditions were generally incubated at 37 ° C and a rotation speed of 160 rpm, which is suitable for microbial growth.

Next, while the culture was being carried out, the gas in the flask was collected by a gas lock syringe (Hamilton, USA), and the gas was analyzed by gas chromatography (Young Lin 6500, Young Lin) (CO 2 ) and methane (CH 4 ) produced in the gas phase were measured.

Next, the gas velocity per specific surface area was calculated in consideration of the specific surface area and time of the charged carbon dioxide (CO 2 ) and methane (CH 4 ) gas in the above-mentioned Examples 1 to 3.

The specific surface area is calculated assuming that the particles of Examples 1 to 3 are spherical, and the formula for calculating the surface area per volume of the sphere is as follows.

Figure pat00002

Figure pat00003

Figure pat00004

Table 1 below is a table showing the specific surface area per unit weight according to the particle size in consideration of the density (PLA 1.25 g / cm 3 ) of Examples 1 to 3 above.

Sample Particle Size Specific Surface area Example 1: 20-40 mesh 0.00753 m 2 / g Example 2: 60-80 mesh 0.02233 m 2 / g Example 3: 100-120 mesh 0.03491 m 2 / g

1) The above carbon dioxide ( C0 2 ) As a reference Non-surface area  The gas generation rate is as follows.

Table 2 below shows the amount of carbon dioxide (CO 2 ) generated in the analytical samples of Examples 1 to 3 over time.

Time (days) Example 1 (ml) Example 2 (ml) Example 3 (ml) 0 0 0 0 3 2.10 5.3 7.5 6 5.16 11.2 14.377 10 6.3 16.55 21.25 13 7.44 20.28 26.84

Table 1 and Table 2, specific surface area and carbon dioxide derived by using the formula 1 (C0 2) production rate are given in Table 3.

CO 2 Example 1 Example 2 Example 3 Non-surface area
Gas production rate (ml / daym 2 )

0.380

0.349

0.296

FIG. 2 is a graph showing carbon dioxide (CO 2 ) production over time in an analysis of gas production rate per unit area of a biodegradable polymer by particle size.

As shown in Table 3 and Table 2, the values of the specific surface area gas production rates of Examples 1 to 3 are similar to each other as shown in Table 3, and the amount of generated carbon dioxide (CO 2 ) .

2) The above methane (CH 4 ) As measured on the basis of Non-surface area  The gas generation rate is as follows.

Table 4 below shows the amounts of methane (CH4) generated in the analytical samples of Examples 1 to 3 over time.

Time (days) Example 1 Example 2 Example 3 0 0 0 0 3 2.9 5.0 7.3 6 8.12 18.3 28.1 10 17.2 30.21 61.0 13 20.47 54.19 86.63

The rate of methane (CH 4 ) formation per specific surface area derived from Table 1, Table 4 and Formula 1 is shown in Table 5.

CH 4 Example 1 Example 2 Example 3 Non-surface area
Gas production rate (ml / daym 2 )

1.04

0.93

0.95

FIG. 3 is a graph showing the amount of methane (CH 4 ) generated over time in an experiment for analyzing the gas production rate per unit area of the biodegradable polymer according to the particle size.

As shown in Table 5 and FIG. 3, the values of the specific surface area gas production rates of Examples 1 to 3 are similar to each other as shown in Table 5, and the amount of methane (CH 4 ) .

That is, the particle size of the biodegradable polymer does not affect the rate of gas evolution per non-surface area, and the rate of gas evolution per non-surface area of the biodegradable polymer depends on the particle size It can be seen that it is constant without.

Therefore, it can be confirmed that the rate of gas generation per surface area can be used as a criterion for evaluating biodegradability of biodegradable polymer as an indicator.

N. By the amount of biodegradable polymer of the same particle size Non-surface area  Gas generation rate analysis

The following experiment is an experiment for analyzing the gas generation rate per unit area of the biodegradable polymer with the same particle size and shown in Examples 4 to 7.

First, Example 4, Example 5, Example 6, and Example 6 were prepared by classifying PLA (Poly Lactic Acid) pellets as 5 g, 10 g, 15 g, and 20 g, respectively, as biodegradable polymer samples. .

[Example 4]

In Example 4, 5 g of polylactic acid (PLA) pellet (5) was used as an analytical sample based on the analysis conditions of the biodegradability evaluation method of the present invention.

[Example 5]

In Example 5, based on the analysis conditions of the biodegradability evaluation method of the present invention, 10 g of polylactic acid (PLA) pellet (mesh size: 5) was used as an analytical sample.

[Example 6]

In Example 6, 15 g of polylactic acid (PLA) pellets (mesh size: 5) was used as an analytical sample based on the analysis conditions of the biodegradability evaluation method of the present invention.

[Example 7]

In Example 7, 20 g of polylactic acid (PLA) pellet (mesh size: 5) was used as an analytical sample based on the analysis conditions of the biodegradability evaluation method of the present invention.

Next, the above Examples 4 to 7 are put into a 250 ml-closed flask, and 100 ml of the prepared microorganism culture medium and 10 ml of the anaerobic sludge are introduced.

The microbial culture medium contained 0.31 g of ammonium chloride (NH 4 Cl), 2.69 g of sodium phosphate monobasic (NaH 2 PO 4 .H 2 O), 4.33 g of sodium hydrogenphosphate (Na 2 HPO 4 ) , potassium chloride ), 12.5 ml of vitamins and 12.5 ml of minerals, and 0-40 mM of acetate was added to the initial microorganism growth substrate. The pH was adjusted to neutral (pH 7.0) suitable for microbial growth.

The anaerobic sludge used as the microorganism inoculation source was collected from an anaerobic digestion tank of a swimming sewage treatment plant and sieved with a 10 mesh sieve to remove impurities and use filtered sludge.

Next, the flasks containing each of Examples 4 to 7 were purged with 100% nitrogen (N 2 ) for 5 minutes to remove oxygen, and the caps were closed and sealed, and then fixed on a constant-temperature stirrer to start culturing. The culture conditions were generally incubated at 37 ° C and a rotation speed of 160 rpm suitable for microbial growth.

Next, while the culture was being carried out, the gas in the flask was collected by a gas lock syringe (Hamilton, USA), and the gas was analyzed by gas chromatography (Young Lin 6500, Young Lin) (CO 2 ) and methane (CH 4 ) produced in the gas phase were measured.

Next, the gas velocity per specific surface area was calculated in consideration of specific surface area and time according to the amounts of the above-described Examples 4 to 7, in which the measured amounts of carbon dioxide (CO 2 ) and methane (CH 4 ) were generated.

Table 6 below is a table showing the total surface area according to the amount of sample input considering the density (PLA 1.25 g / cm 3 ) of Examples 4 to 7.

Sample name Sample input Specific surface area per unit weight Overall surface area Example 4 5g 0.0012 m 2 / g 0.006 ㎡ Example 5 10g 0.0012 m 2 / g 0.012 ㎡ Example 6 15g 0.0012 m 2 / g 0.018 ㎡ Example 7 20g 0.0012 m 2 / g 0.024 ㎡

Table 7 is a table showing a carbon dioxide (C0 2) and methane (CH 4) generation of Examples 4 to 7.

CO 2 production by polymer weight CH 4 production by polymer weight Decomposition time (h) Example 4 (5 g) Example 5 (10 g) Example 6 (15 g) Example 7 (20 g) Decomposition time (h) Example 4 (5 g) Example 5 (10 g) Example 6 (15 g) Example 7 (20 g) 0 0.000 0.000 0.000 0.000 0 0.000 0.000 0.000 0.000 24 0.014 0.042 0.056 0.076 24 0.081 0.123 0.184 0.269 48 0.028 0.057 0.093 0.114 48 0.161 0.161 0.242 0.323 72 0.041 0.085 0.154 0.174 72 0.196 0.323 0.623 0.645 96 0.057 0.114 0.187 0.227 96 0.245 0.489 0.636 0.897 120 0.067 0.134 0.234 0.264 120 0.318 0.516 0.769 0.290 144 0.087 0.188 0.297 0.378 144 0.341 0.669 0.968 0.347 168 0.094 0.213 0.343 0.423 168 0.379 0.716 0.161 0.517 192 0.114 0.227 0.373 0.455 192 0.419 0.846 0.271 0.798 216 0.137 0.278 0.444 0.546 216 0.516 0.997 0.570 0.164 240 0.149 0.321 0.560 0.682 240 0.549 0.016 0.648 0.222

1) The above carbon dioxide ( C0 2 ) As a reference Non-surface area  The gas generation rate is as follows.

Table 6 and Table 7 and a specific surface area of carbon dioxide production rate formula derived using a 1 (C0 2) are given in Table 8.

CO 2 Example 4 Example 5 Example 6 Example 7 Non-surface area
Gas production rate (ml / daym 2 )

2.48

2.68

3.11

2.84

4 is a graph showing the amount of generated carbon dioxide (CO 2 ) over time in the analysis of the gas generation rate per unit area of the biodegradable polymer with the same particle size.

As shown in Table 8 and Table 4, as shown in Table 8, the values of gas production rates per unit area of Examples 4 to 7 are similar, and as shown in FIG. 4, the amount of generated carbon dioxide (CO 2 ) .

2) The above methane ( CH 4 ) As measured on the basis of Non-surface area  The gas generation rate is as follows.

The rate of methane (CH 4 ) formation per specific surface area derived from Table 6, Table 7, and Formula 1 is shown in Table 9.

CH 4 Example 4 Example 5 Example 6 Example 7 Non-surface area
Gas production rate (ml / daym 2 )

9.15

8.47

9.16

9.26

In addition, Figure 5 is a graph showing the methane (CH 4) in accordance with the amount of time in the same particle size by specific surface area biodegradable input gas generating rate assay of the polymer.

As shown in Table 9 and Table 5, the values of the specific surface area gas production rates of Examples 4 to 7 are similar to each other as shown in Table 9, and the amount of methane (CH 4 ) .

That is, the amount of biodegradable polymer added does not affect the rate of gas evolution per unit area, and the rate of gas evolution per non-surface area of the biodegradable polymer is biodegradable by the amount of biodegradable polymer Regardless of the input amount of the polymer.

Therefore, it can be confirmed that the rate of gas generation per surface area can be used as a criterion for evaluating biodegradability of biodegradable polymer as an indicator.

C. Biodegradability  Based on other polymer samples Non-surface area  Gas generation rate analysis

The above experiment was conducted to analyze the rate of gas generation per unit area according to polymer samples having different degrees of biodegradation. Examples 8 to 11 are the analytical samples, and four analytical samples (5 g, 10g, 15g, and 20g).

[Example 8]

In Example 8, 5 g, 10 g, 15 g and 20 g of polyethylene pellets were used as analytical samples based on the biodegradability evaluation method of the present invention.

[Example 9]

In Example 9, 5 g, 10 g, 15 g, and 20 g of polyethylene terephthalate pellets were used as analytical samples based on the biodegradability evaluation method of the present invention.

[Example 10]

In Example 10, 5 g, 10 g, 15 g and 20 g of polycaprolactone (PCL) pellets were used as analytical samples based on the biodegradability evaluation method of the present invention.

[Example 11]

In Example 11, 5 g, 10 g, 15 g and 20 g of polylactic acid (PLA) pellets were used as analytical samples based on the biodegradability evaluation method of the present invention.

6 is a graph illustrating the biodegradability of the methane (CH 4) amount with time of the specific surface area the gas generating rate assay in accordance with another polymer sample.

As shown in FIG. 6, the rate of formation of methane (CH 4 ) per specific surface area is very similar to that of the polymer sample, and the rate of methane (CH 4 ) formation per unit area of the polymer sample having different biodegradability is considerably different .

That is, it can be seen that the calculated rate of gas evolution per unit area is used as a quantitative value for analyzing the degree of biodegradation, and it can be utilized as a biodegradability assessment method for evaluating the biodegradability of each polymer by indexing and comparing them.

As described above, it is to be understood that the technical structure of the present invention can be embodied in other specific forms without departing from the spirit and essential characteristics of the present invention.

Therefore, it should be understood that the above-described embodiments are to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than the foregoing description, All changes or modifications that come within the scope of the equivalent concept are to be construed as being included within the scope of the present invention.

S110. The first step of preparing the biodegradable polymer sample by using the crusher
S120. A second step of introducing the analytical sample into a closed flask and feeding the microbial culture medium and the anaerobic sludge into the closed flask
S130. A third step of incubating the flask in a sealed incubator,
S140. A fourth step of measuring the amount of gas produced by analyzing the gas phase composition after collecting the gas in the flask with a gas sample syringe,
S150. A fifth step of calculating a gas generation rate per non-surface area using the specific surface area of the analytical sample and the amount of the generated gas
S160. The sixth step of evaluating the degree of biodegradation using the gas generation rate per non-surface area

Claims (6)

Measuring the surface area of the biodegradable polymer sample, measuring the rate of gas evolution after biodegradation of the biodegradable polymer sample into microorganisms,
Wherein the gas generating rate per unit area of the polymer sample is calculated using the measured surface area of the biodegradable polymer sample and the gas generation rate,
The method according to claim 1,
Wherein the gas generation rate is a gas generation rate of carbon dioxide (CO 2 ) in an aerobic condition and a gas generation rate of methane (CH 4 ) in an anaerobic condition.
A first step of preparing a biodegradable polymer sample by using a crusher;
A second step of introducing the analytical sample into a closed flask, feeding the microorganism culture medium and the anaerobic sludge into the closed flask;
A third step in which the flask is closed and incubated in a constant temperature stirrer;
A fourth step of collecting the gas in the flask with a gas sample syringe, analyzing the composition of the gas phase, and measuring the amount of gas produced;
A fifth step of calculating a gas generation rate per specific surface area using the specific surface area of the analytical sample and the amount of generated gas;
And a sixth step of evaluating the degree of biodegradation using the gas generation rate per non-surface area.
The method of claim 3,
Characterized in that the particle size is uniformly standardized at the time of preparing the analytical sample in the first step
The method of claim 3,
Wherein the culturing is carried out at 20 to 50 ° C at a rotation speed of 100 to 200 rpm in the third step,
The method of claim 3,
Further comprising the step of removing oxygen by filling with nitrogen (N 2 ) in the anaerobic condition in the third step
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