KR101877929B1 - manufacturing method of Biochar for removing heavy metal and biochar manufactured therefrom and absorbent comprising of the biochar for removing heavy metal - Google Patents

Abstract

The present invention relates to a method for manufacturing biochar for removing heavy metal, and specifically, to a method for manufacturing biochar for removing heavy metal, which comprises the following steps: washing and drying kelp and fusiformis; crushing the dried kelp and fusiformis to manufacture a kelp powder or a fusiformis powder having a particle size of 0.05 to 3.0 mm; and heating the kelp, fusiformis or a powder mixture thereof in an oxygen-free atmosphere at a rate of 3 to 10°C/min at the temperature of 400 to 700°C and pyrolyzing and cooling the same at the temperature of 400 to 700°C. The present invention solves the problem of disposal of abandoned algae by reusing the kelp and fusiformis, which are abandoned algae biomass in aquaculture and harvesting processes, as the biochar.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for producing a bio-tea for removing heavy metals, a bio-tea for removing heavy metals and an adsorbent for removing heavy metals,

More particularly, the present invention relates to a method for producing a bio-tea for removing heavy metals, and more particularly, to a method for producing a bio-tea comprising the steps of pyrolyzing a seaweed, a green tea or a mixture thereof to produce a bio- And more particularly, to a method for producing a bio-tea for removing heavy metals.

As industrial development accelerates and human industrial activities become more diverse, environmental pollution such as soil, air and water pollution caused by various pollutants is increasing. Particularly in the case of water pollution, iron, copper, nickel, Pollution problems by heavy metals containing wastewater containing zinc, lead, cadmium, and chromium are increasing.

Currently, ion exchange, activated carbon adsorption, membrane filtration, coagulation sedimentation, floatation, and electrochemical treatment methods are used to remove heavy metals from wastewater. As described in Korean Patent Laid-Open No. 10-2016-0114883, a method for modifying the surface of a carbon material with an iron oxide coating is currently under study, and effective adsorption of heavy metals and harmful chemical substances to be. However, in the case of the activated carbon adsorption method, it is difficult to supply raw materials such as palm, bamboo, and sawdust, and is produced through pyrolysis at a high temperature of 700 ° C. or more. Therefore, energy consumption is high and production cost is high. There is a limit.

Therefore, it is required to develop environmentally friendly alternative adsorbent materials and to develop technologies for treating refractory materials including heavy metals using the same.

Biochar, also known as biochar, is a carbon-rich solid material that is produced when biodegradable in an oxygen-free environment using biomass. It is used for carbon sequestration, renewable energy, waste management, Environmental restoration and other important functions have recently attracted a great deal of attention.

Furthermore, unlike woody biomass, algae biomass contains various minerals in seawater such as sodium, potassium, magnesium, calcium, phosphorus, etc. Thus, algae biochae produced from the algae biomass includes not only minerals but also algae minerals It may contain minerals that are 2 to 4 times more concentrated than the amount.

Unlike bio - tea derived from other land biomass, bio - tea containing various minerals in seawater is expected to be useful as a carrier for soil modifier and adsorbent.

However, seaweed biomass is expected to be useful in various fields.

Accordingly, the present invention provides a method for producing a bio-tea made of kelp, tar or mixtures thereof for removal of heavy metals using seaweed or seaweed, which is abandoned seaweed biomass during culturing and harvesting.

The present invention also provides a bio-tea for removing heavy metals, which is produced by the method for producing bio-tea.

It is another object of the present invention to provide an adsorbent for removing heavy metals, which comprises the bio-tea.

According to an aspect of the present invention,

Washing and drying the kelp and tar;

Crushing the dried kelp and tops, respectively, to prepare a tangle powder or a top powder having a particle size of 0.05 to 3.0 mm; And

Heating the kelp, chopped powder or a mixture thereof in an oxygen-free atmosphere at a rate of 3 to 10 ° C / min to 400 to 700 ° C, and then pyrolyzing and cooling the mixture at 400 to 700 ° C. And a method for producing a bio-tea for removing heavy metals.

According to another aspect of the present invention,

The present invention provides a biochip for removing heavy metals, which is produced according to the above production method.

According to another aspect of the present invention,

And an adsorbent for removing heavy metals.

The present invention can solve the above-mentioned problem of disposal of algae by reusing seaweeds or seaweed, which are abandoned algae biomass in the aquaculture and harvesting process, as bio-tea.

In addition, according to the present invention, the bio-tea produced by using kelp or tortoise can easily adsorb and remove heavy metals, and in particular, in the case of the tortobioc tea, it exhibits selective adsorption and removal efficiency against copper, And can be adsorbed and removed.

Thus, the bio-tea produced by using the kelp, the red pepper or the mixture thereof according to the present invention can be used as an adsorbent for eco-friendly heavy metal removal.

FIG. 1 is a graph showing the removal rates of heavy metals in the kelp bio-car (a) and the top-biocide (b) according to the temperature increasing rate according to an embodiment of the present invention.
FIG. 2 shows the amount of heavy metals adsorbed on the kelp bio-tea, the top-biocide, and the control group according to the pyrolysis temperature according to an embodiment of the present invention.
FIG. 3 is a graph illustrating the heavy metal adsorption capacity of kelp bio-tea and top-biocide according to initial concentration of heavy metals and thermal decomposition temperature according to an embodiment of the present invention.
FIG. 4 is a graph showing the pH values of kelp biochars, topchiocha, and a control group according to the pyrolysis temperature according to an embodiment of the present invention.
FIG. 5 is a graph illustrating the change in heavy metal concentration and the change in pH due to the tidal bio-tea and the top bio-tea according to an embodiment of the present invention.
FIG. 6 is a graph illustrating the adsorption efficiency of heavy metals in seawater bio-tea and top bio-tea according to an embodiment of the present invention.
FIG. 7 is a FT-IR analysis graph of a tuna biocha, a tobacco tea, and a pine sawdust bio-tea according to an embodiment of the present invention.
FIG. 8 is a photograph of a kelp base material, a kelp biochamel, a starch base material and a top biochannel according to an embodiment of the present invention.
9 is a SEM photograph of a kelp base material, a kelp bio-tea, a top-molding material and a top-bioc tea according to an embodiment of the present invention.
FIG. 10 is an analysis of the elements of kelp base material and kelp bio-tea according to an embodiment of the present invention.
FIG. 11 is a graph showing an analysis of the elements of the topsheet and the topsheet of the present invention according to an embodiment of the present invention.
FIG. 12 shows the yields of kelp biocham, top biocide, and control group according to the pyrolysis temperature according to an embodiment of the present invention.

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

According to an aspect of the present invention,

Washing and drying the kelp and tar;

Crushing the dried kelp and tops, respectively, to prepare a tangle powder or a top powder having a particle size of 0.05 to 3.0 mm; And

Heating the kelp, chopped powder or a mixture thereof in an oxygen-free atmosphere at a rate of 3 to 10 ° C / min to 400 to 700 ° C, and then pyrolyzing and cooling the mixture at 400 to 700 ° C. And a method for producing a bio-tea for removing heavy metals.

First, in the method for manufacturing heavy metal removal, the step of washing and drying the kelp and the tar is performed by washing and drying the kelp and the tar, which are abandoned algae biomass in the aquaculture and harvesting process, It is the preparation stage.

Next, the step of preparing the sea tangle powder or the top powder is such that the particle size is from 0.05 to 3 mm, preferably from 0.15 to 2.0 mm, in order to improve the thermal decomposition reactivity and the specific surface area of kelp or tortoise.

Next, in the pyrolysis and cooling step, the tangle powder, the top powder, or a powder obtained by mixing the tangle powder and the top powder is injected into a thermal decomposition furnace and then heated at a temperature of from 3 to 10 ° C / min in an oxygen- And the mixture is pyrolyzed at 400 to 700 ° C for 1 to 2.5 hours while being kept at a temperature, followed by cooling to produce a bio-tea.

In detail, the pyrolysis and cooling step further comprises the step of flushing the pyrolysis furnace into which the kelp, chopped or mixed powder is injected with an inert gas before the temperature is increased to the pyrolysis temperature, The inert gas atmosphere was maintained at 0.01 to 0.1 L / min per 1 g of the biochip during the heating and cooling to the pyrolysis temperature.

More specifically, in the pyrolysis and cooling step, the rising rate to the pyrolysis temperature is preferably 5 to 10 ° C / min, and the pyrolysis temperature is 500 to 700 ° C, more preferably 500 to 600 ° C .

In addition, the tidal biochae, the topchiocha, or the biochain produced by the pyrolysis and cooling steps exhibits a yield of 20 to 45%. Preferably, the biocide exhibits a yield of 25 to 40%.

The bio-tea produced by the method according to the present invention exhibits heavy metal removal efficiency.

According to the present invention, the bio-tea for removing heavy metals is prepared by using seaweeds and seaweeds, which are seaweed biomass, from seaweed bio-tea, top-bioc tea or a mixture of them with a bio-car, and adsorbs and removes heavy metals such as cadmium, .

Specifically, when the tidal biocha, topba cha or a mixture thereof is agitated with a heavy metal for 10 to 40 minutes, it has a non-adsorptive power of 8.5 to 20 mg heavy metal / g bio-tea, 80% adsorption and removal.

More specifically, in the case of the above tideland bio-tea, when the mixture is agitated with cadmium, copper or zinc for 10 to 40 minutes, it has a non-adsorption capacity of 9 to 15 mg of heavy metal / g of bio-tea, In the case of the topbio tea, at least 85% or more of heavy metal adsorption is carried out with agitation for 10 to 40 minutes with cadmium, copper or zinc with at least 9-15 mg of heavy metal / And removal efficiency, and is characterized by exhibiting significantly improved adsorption and removal efficiencies, especially for copper.

In addition, the tidal biocha, the topba o cha or a mixture thereof may have a pH of 7.5 to 12, which is higher than that of the heavy metal, so that it can be easily removed by precipitating heavy metals.

As described above, the tidal bio-tea and the top bio-tea according to the present invention can be applied to the wastewater containing heavy metals and the contaminated soil as an adsorbent for heavy metal removal as it easily removes heavy metals.

Hereinafter, the present invention will be described in more detail by way of examples, but the scope of the present invention is not limited by the examples.

<Examples>

Manufacture of bio-tea

Production Example 1 Production of bio-tea according to the rate of temperature increase

The kelp and tortoise were washed and the salt was removed, followed by drying and pulverizing.

At this time, each of the crushed kelp and kotatsu was sieved and prepared so as to have a size of 0.18 mm to 1.7 mm.

Next, 50 g of the prepared kelp powder or 50 g of the top powder was poured into a pyrolysis furnace, which was made to be capable of nitrogen injection, and then flushed with nitrogen gas for 30 minutes.

Thereafter, the temperature was raised at a rate of temperature rise of 3 ° C / min, 5 ° C / min, 7 ° C / min, 10 ° C / min and 15 ° C / The kelp and tar were pyrolyzed at 500 ° C for a period of time. At this time, during an increase in temperature and pyrolysis process, nitrogen gas was introduced into the pyrolysis furnace at a rate of 0.05 L / min per 1 g of the biochroma material so as to prevent ignition due to air inflow, thereby maintaining the anaerobic atmosphere.

After completion of the pyrolysis, the furnace was allowed to cool. During the cooling, nitrogen gas was introduced at a rate of 15 mL / min.

Thus, kelp biocide and top biocide were prepared according to the temperature rise rates (3 ° C / min, 5 ° C / min, 7 ° C / min, 10 ° C / min and 15 ° C / min)

Production Example 2 Production of bio-tea according to thermal decomposition temperature

The kelp bio-tea and the top-bioc tea were prepared in the same manner as in Preparation Example 1, except that the temperature rise rate was 7 ° C / min and the thermal decomposition temperatures were 250, 400, 500, 600 and 700 ° C.

Bio-car analysis

&Lt; Example 1 > Analysis of Heavy Metal Adsorption Rate According to Temperature Rise Rate upon Pyrolysis

(3 占 폚 / min, 5 占 폚 / min, 7 占 폚 / min, 10 占 폚 / min and 15 占 폚 / min, respectively) prepared in Preparation Example 1 to analyze the degree of heavy metal adsorption of the bio- min) 2 g each of kelp bio tea and top bio tea were prepared and 40 mL of an aqueous solution of 500 mg / L of copper (Cu) was prepared as a heavy metal.

Next, each of the above-prepared 2 g portions of the kelp bio-tea and the top bio-tea prepared above was mixed with the copper prepared in the above 40 mL in a glass bottle and reacted for 30 minutes, and the concentration of the residual heavy metal was measured and shown in FIG.

Referring to FIG. 1, it can be seen that both of the seaweed bio-tea (FIG. 1A) and the top bio-tea (FIG. 2B) exhibit the highest heavy metal removal rate when they are produced at a temperature rise rate of 7 ° C./min.

&Lt; Example 2 > Analysis of heavy metal adsorption amount according to pyrolysis temperature

The preparation example 2 was prepared in the same manner as in Preparation Example 2 except that the thermal decomposition temperature was set to be 250 ° C, 400 ° C, 500 ° C, 600 ° C and 700 ° C, And the effect on heavy metal adsorption was analyzed.

First, to analyze the degree of heavy metal adsorption of tsuma biocha and topbaio tea, 2g of each of seaweed bio-tea and top bio tea according to the pyrolysis temperature of Preparation Example 2 was prepared, and cadmium (Cd), copper ) And zinc (Zn) were each prepared as 40 mL of an aqueous solution of 500 mg / L.

Next, each of the above prepared cadmium, copper and zinc prepared by 2 g of each of the kelp bio-tea and the top-bioc tea prepared according to the pyrolysis temperature and 40 mL of each of the prepared cadmium, copper and zinc were mixed in a glass bottle and reacted for 30 minutes. The non-adsorbed amount of each of cadmium and zinc was measured and is shown in FIG. However, the non-adsorbed amount of each heavy metal was also analyzed by the same method for the pine sawdust bio-tea prepared as the control group in the same manner as in Production Example 2 except that the pyrolysis temperature was different.

Referring to FIG. 2, it can be seen that the seaweed bio-tea and the top bio-tea exhibit significantly improved adsorption of copper, cadmium and zinc compared to the pine sawdust bio-tea, and a relatively high amount of heavy metal adsorption at 500 ° C or higher.

&Lt; Example 3 > Analysis of Heavy Metal Adsorption Ability According to Pyrolysis Temperature and Heavy Metal Concentration

In order to analyze the heavy metal adsorption capacity of the bio-tea according to the change of the pyrolysis temperature and the initial heavy metal concentration at the time of the production of the bio-tea, 0.5 g of the kelp biocar and the top- (Cd, Cu and Zn 1000, 1500, 2000, 2500, 3000 and 3500 mg / L) were connected and reacted in a shaker for 24 hours, and the adsorbed The amount of heavy metals was measured and is shown in Fig.

3, it can be seen that the amount of adsorbed per unit mass increases with the initial concentration of copper in the seawater and the topbio tea, indicating high selectivity to copper. Especially, in the case of the topbio tea, It can be confirmed that it exhibits more improved copper selectivity.

In the case of tidal bio-tea, copper is adsorbed at 235.8 mg Cu / g bioaccum at 700 ° C, cadmium adsorbed at 102.6 mg Cd / g bioaccum at 600 ° C, zinc is adsorbed at 500 ° C at 96.0 mg Zn / Adsorption can be confirmed.

<Example 4> pH analysis of bio-tea by thermal decomposition temperature

In order to analyze the pH change of the bio-tea according to the pyrolysis temperature during the preparation of the bio-tea, 2 g of each of the seaweed bio-tea and the top-bio tea according to the pyrolysis temperature of Preparation Example 2 was prepared, and the mixture was put in a 50 mL glass bottle. The pH was measured after contacting with a shaker (150 rpm) for 30 minutes and shown in FIG. However, the pH was also measured by the same method for pine sawdust biochain prepared by different pyrolysis temperatures as in Production Example 2 as a control, and kelp, green tea, and pine sawdust base materials before biochara production .

Referring to FIG. 4, it can be confirmed that at a pyrolysis temperature of 500 ° C. or higher, the high pH of the sea tangle and the chrysanthemum tea are high.

Example 5 Analysis of Removal Efficiency of Heavy Metal Carbons at 7 ° C / min and Pyrolysis Temperature of 500 ° C

In order to measure the efficiency of removing the heavy metals of the kelp bio-tea and the take-off bio-tea and the efficiency according to the pH of the bio-tea, the temperature rising rate and the thermal decomposition temperature were set to 7 캜 / Tea and top - bio tea.

2 g of each of the prepared kelp bio-tea and top bio-tea was prepared and 40 mL of an aqueous solution of 500 mg / L of cadmium (Cd), copper (Cu) and zinc (Zn) were prepared as heavy metals. Then, each of the above prepared cadaver, copper and zinc, prepared in 2 g portions, and 40 mL of each of the prepared kelp biochambers and topchiocha were mixed in a glass bottle and reacted for 30 minutes.

Thereafter, the filtrate was filtered with a 0.45 mL filter, and the heavy metal concentration was measured using an inductively coupled plasma (ICP). The change in heavy metal concentration and the change in pH according to the biochip are shown in FIG.

6 and Table 1 show the adsorption efficiency and the non-adsorbed amount of each of the biochars after the above test.

5 and 6, it was confirmed that the adsorption removal efficiency for cadmium and zinc was superior to that of the ttobioc tea, but the adsorption removal efficiency for cadmium and zinc was remarkably improved due to the high selectivity for the copper .

The pH change graph of FIG. 5 is obtained by mixing the prepared cadmium, copper, and zinc, and then adding pH and pH to the mixed heavy metal solution, respectively.

The pH of the initially prepared heavy metal solution (pH 5.02) was slightly acidic. When the pH of the initially prepared heavy metal solution (pH 5.02) was 30 minutes, the pH was changed to strongly basic at pH 11.29. The pH was changed to neutral at 8.01.

As can be seen from FIG. 4, when the pH of the kelp bio-tea and the top bio-tea was 10.5 or 8, respectively, when the pyrolysis temperature was 500 ° C, the kelp bio-tea and the top- As the pH is high, the heavy metal can be precipitated and removed by the pH difference.

From the above results, it can be seen that the seaweed bio-tea and the pick-off bio-tea show high adsorption to heavy metals and therefore can easily remove cadmium, copper and zinc, and can easily remove heavy metals .

(Unit: mg heavy metal / g bio tea) heavy metal Seaweed bio tea Topbio tea CD 10.8 9.4 Cu 10.5 > 10.9 Zn 11.0 10.7

&Lt; Example 6 >

(1) Fourier transform infrared spectroscopy (FT-IR) analysis

In order to confirm the surface functional groups of the kelp bio-tea and the top-bio tea, the tuna bio-tea and the top bio-tea prepared at the 7 ° C / min and the pyrolysis temperature of 500 ° C were FT-IR analyzed and shown in FIG. At this time, as a control, pine sawdust bio-tea was also subjected to FT-IR analysis under the same conditions.

Referring to FIG. 7, it can be confirmed that both of the seaweed biochae and the topchio tea contain more functional groups such as O-H and C-O-C, which are oxygen-bonded to the pine sawdust bio-tea.

From the above results, it can be seen that the adsorption efficiency of heavy metals is improved by the inclusion of surface functional groups containing oxygen element in the tidal bio-tea and the top-biodiesel.

(2) Elemental analysis

In order to analyze the elements of the kelp biochars and topchiocha, elemental analysis was performed on the kelp biochae and the topchibo tea prepared at 7 ° C / min and pyrolysis temperature of 500 ° C.

Figs. 8 and 9 are photographs and SEM photographs of the kelp base material, the kelp bio-tea, the top-molding material and the top-biocide.

10 is an analysis of the elements of each of the kelp base material and the prepared tuna bio-tea in the same manner.

FIG. 11 is a graph showing an analysis of the elements of each of the top and bottom tie materials according to the same method.

As a result, it can be confirmed that the carbon content is increased with the preparation of the bio-tea from both of the tuna bio-tea and the top bio-tea.

In addition, although the kelp bio-tea and the top-bioc tea were produced through pyrolysis, it was confirmed that they contained enough oxygen such as -OH, -COOH or COC including oxygen element to be comparable to the base material .

It is believed that the tidal bio-tea and the top-bio tea can easily adsorb and remove heavy metals as well as being rich in carbon content as well as containing functional groups including oxygen.

(3) Yield analysis

In order to analyze the yields of the kelp bio-tea and the top bio-tea according to the pyrolysis temperature, the yields of the kelp bio-tea and the top bio-tea prepared in Preparation Example 2 were analyzed and shown in FIG. At this time, as a control group, pine sawdust bio-tea was also analyzed under the same conditions.

Referring to FIG. 12, it can be seen that the tuna biocha and the topbao tea have relatively high yields compared to the pine sawdust bio-tea, and in particular, the high-biodegradability is shown in the case of the top-bio tea.

While the present invention has been described in connection with certain exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, And various modifications and variations are possible within the scope of the appended claims.

Claims (5)

Washing and drying the kelp and tar;
Crushing the dried kelp and tops, respectively, to prepare tallow powder and top powder each having a particle size of 0.05 to 3.0 mm; And
Heating the kelp, chopped powder or a mixture thereof in an oxygen-free atmosphere at a rate of 5 to 10 ° C / min to 500 to 600 ° C, and then pyrolyzing and cooling the mixture at 500 to 600 ° C .; ,
The bio-tea is a marine bio-tea, a top bio-tea or a mixture thereof. The pH is 7.5 to 12, the oxygen content of the whole component is 28 to 32%, and the non-adsorption power of 8.5 to 20 mg of heavy metal / g bio- And removing at least 80% of cadmium, copper and zinc.
delete delete A biocide for removing heavy metals, which is produced by the method for producing a bio-tea according to claim 1.
5. An adsorbent for removing heavy metals, comprising the bio-tea according to claim 4.

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