KR20190102927A - Manufacturing method of nano-metal pine biochar for removing phosphorus and nano-metal pine biochar manufactured using the method - Google Patents

Abstract

The present invention relates to a pine bio tea producing method capable of removing phosphorus from sewage and, more specifically, to a method for producing bio tea by modifying the surface of bio tea with nanometal in order to increase the phosphorus adsorption performance of pine bio tea. To achieve the above purpose, the producing method of nanometal pine bio tea for removing phosphorus comprises: a first step of washing pine trees with flowing tap water; a second step of drying the pine trees indoors; a third step of producing pine sawdust by pulverizing the dried pine trees with a pulverizer; a fourth step of producing biomass by drying the produced pine sawdust at 75-85°Cfor three hours; a fifth step of processing the surface of the biomass by stirring the biomass in FeCl_3·6H_2O solution for two hours and drying the same; and a sixth step of pyrolyzing the biomass surface-processed after drying by injecting nitrogen gas at a flow rate of 2,500 cm^2/min in a pyrolyzer and blocking air from flowing into the pyrolyzer.

Description

Manufacturing method of nano-metal pine bio tea for phosphorus removal and nano-metal pine bio tea manufactured according to the present invention

The present invention relates to a pine bio-tea manufacturing method capable of removing phosphorus from sewage, and relates to a method for producing a bio-tea by modifying the surface of the bio- tea with nano-metal in order to increase the phosphorus adsorption performance of the pine bio-tea.

In response to the strengthening of effluent standards for total phosphorus in public sewage treatment plants, physical, chemical or biological treatment techniques have been developed to treat phosphorus in sewage treatment plant effluents. In most domestic sewage treatment plants, biological treatment alone cannot satisfy the enhanced water quality standards for total phosphorus, so the chemical coagulation + filtration, chemical coagulation + sedimentation, or chemical coagulation + flotation technologies are mainly installed after the sewage treatment process. to be.

However, this rear end total phosphorus treatment device has a problem that a large amount of flocculated sludge occurs, and additional treatment costs must be invested to treat the flocculated sludge. In addition, when the coagulated sludge generated after the post-stage treatment and the excess sludge generated in the main treatment process are mixed, it may be difficult to reuse the excess sludge.

To this end, in recent years, a technology for utilizing these agricultural and forest by-products as a biochar obtained when pyrolyzing under controlled conditions of air supply has been developed. ] And the like.

However, in the case of bio tea according to the prior art, it was mostly used as a direction for reducing greenhouse gases or as an agricultural soil improver to improve soil water retention or retention, and to treat wastewater containing a large amount of phosphorus. It was rarely used as a water treatment agent.

Since the surface of the biocar itself is negatively charged, there are many difficulties in adsorption and removal of phosphorus present in the form of anions (PO ₄ ^3- ) in sewage and wastewater.

Korean Patent Publication No. 2010-0117954

The present invention has been made to solve the above problems, an object of the present invention is to derive the optimum pine bio tea manufacturing conditions to easily adsorb the phosphorus present in the anion (PO ₄ ^3- ) form.

In addition, an object of the present invention is to provide a manufacturing condition of the nano-metal pine bio-tea by modifying the surface of the bio-tea with nano-metal in order to increase the phosphorus adsorption ability of the pine bio-tea.

Technical problems to be solved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned above will be clearly understood by those skilled in the art from the following description. Could be.

According to a feature of the present invention for achieving the above object, the present invention method for producing a nanometal pine bio-car for phosphorus removal is the first step of washing pine in distilled water; A second step of drying the pine indoors; A third step of preparing pine sawdust by crushing the dried pine with a grinder; A fourth step of preparing biomass by drying pine sawdust at 75 to 85 ° C. for 3 hours; A fifth step of adding the biomass to a FeCl ₃ .6H ₂ O solution, stirring for 2 hours, and then drying the biomass to surface-treat the biomass; And a sixth step of injecting the surface-treated biomass into a pyrolysis machine at a flow rate of 2500 cm 3 / min and pyrolyzing the air by blocking the inflow of air into the pyrolysis machine.

By the means for solving the above problems, the present invention can derive the optimum pine bio-tea manufacturing conditions to easily adsorb the phosphorus present in the anion (PO ₄ ^3- ) form.

In addition, the present invention can provide a nano-metal pine bio tea by modifying the surface of the bio tea with nano metal to increase the phosphorus adsorption capacity of the pine bio tea.

Figure 1 is a flow chart illustrating a method for producing a nano-metal pine bio tea for phosphorus removal.
Figure 2 is a photograph showing the biomass and surface morphology and structural analysis of pine sawdust using a scanning electron microscope (SEM).
Figure 3 is a graph showing the adsorption performance for the phosphate (bio) produced by the pine sawdust.
Figure 4 is a graph showing the adsorption performance for the phosphorus (phosphate) of bio-tea prepared using surface-modified pine sawdust.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings, in which the same reference numerals are denoted for components that perform the same function in FIGS. 1 to 4. Meanwhile, in the drawings and detailed description of the drawings, detailed descriptions and illustrations of specific technical configurations and operations of elements not directly related to technical features of the present invention are omitted, and only the technical configurations related to the present invention are briefly shown or Explained.

The present invention relates to a pine bio-tea manufacturing method capable of removing phosphorus from sewage, and relates to a method for producing a bio-tea by modifying the surface of the bio- tea with nano-metal in order to increase the phosphorus adsorption performance of the pine bio-tea. As a preliminary step for preparing pine sawdust, the first step S10 to the third step S30 may be performed first, and then biomass may be manufactured in the fourth step S40.

First step (S10) is to wash the pine in tap water. The washing is carried out to remove the impurities that may remain in the pine to increase the purity of the bio- tea produced by the present invention, the method may be different by the manufacturer.

Next, the second step (S20) is to dry the pine indoors. More specifically, the washed pine is preferably dried sufficiently for 3 to 4 days in a windy room.

When the pine is not dried, it is very difficult to grind in the third step (S30), and the concentration of the FeCl ₃ · 6H ₂ O solution to be mixed in the fifth step (S50) is low, the production of nanometal pine bio tea is very It can be difficult.

In addition, the washed pine is preferably dried in a windy room, it is preferable to carry out under the above conditions because the pine may be deteriorated when dried using a dryer.

Next, the third step (S30) is to crush the dried pine with a grinder to produce pine sawdust, No. 12 (1.7mm) to No. 80 (180㎛) size particles are produced. When the pulverization is manufactured in a size smaller than No. 12 (1.7 mm), the drying time is increased in the fourth step (S40) to be described below, or it is not sufficiently dried until the inside of the particles. In the case of S60), pyrolysis may be insignificant, and when the pulverization is pulverized into particles of No. 80 (180 μm) size, the surface modification time may be too long in the fifth step (S50), which will be described below, and the produced nanometal It is preferable to carry out under the above conditions since the effect of adsorption performance on the phosphate of the bio-tea is not significantly different.

Next, the fourth step (S40) is to dry the pine sawdust prepared at 75 to 85 ℃ for 3 hours to produce a biomass.

The prepared pine sawdust is less than 75 ℃ when the dried particles are not sufficiently dried, the thermal decomposition effect may be insignificant in the sixth step (S60) to be described below, if the drying is more than 85 ℃ the drying Since the used biomass may be deteriorated, it is preferable to carry out under the above conditions.

In addition, when the pine sawdust is dried for less than 3 hours, the pulverized particles may not be sufficiently dried. If the pulverized particles are dried for more than 3 hours, the dried biomass may be deteriorated. Since there exists a possibility, it is preferable to carry out on the said conditions.

Next, in step S50, the biomass is added to a FeCl ₃ .6H ₂ O solution, stirred for 2 hours, and dried to prepare a surface-modified biomass with iron chloride-biomass. Mixing the FeCl ₃ · 6H ₂ O is to make a bio-car having a magnetic surface by modifying the biomass, the FeCl ₃ · 6H ₂ O is preferably prepared in a concentration of 0.1 to 0.3M.

More specifically, the biomass into a FeCl ₃ · 6H ₂ O solution and stirred for 2 hours, FeCl ₃ · 6H ₂ O solution No. After removing using an 80 (180 μm) sieve and aging in an oven at a temperature of 80 ° C. for 2 hours to harden the coating of iron chloride on the biomass, the iron chloride-biomes are dried in a room and subjected to surface treatment.

When the biomass is added to a FeCl ₃ · 6H ₂ O solution and stirred for less than 2 hours, the biomass is mixed with the biomass so that the surface modification effect is low. When the biomass is stirred for more than 2 hours, the biomass and the iron chloride are coated. Since it may fall, it is preferable to carry out under the above conditions.

In addition, when the FeCl ₃ · 6H ₂ O solution is prepared in less than 0.1M concentration, as shown in Figure 4, the nanometal pine bio-car prepared by the present invention has a slight adsorption performance effect on the phosphate, 0.3M When the concentration is exceeded, the surface of the biomass may be so thick that the effect of adsorption performance on phosphate may be lowered, and the stirring time and aging time in the oven may be long, resulting in low efficiency. It is preferable.

Further, after stirring the biomass and FeCl ₃ · 6H ₂ O solution No. In the case of sieving less than 80 (180 μm) in size, the removal of the FeCl ₃ · 6H ₂ O solution may be insignificant. If the size exceeds 80 (180 μm), the fermentation is preferably carried out under the above conditions because the fermented chloride coated biobath is removed together and the yield is lowered.

In addition, when the FeCl ₃ · 6H ₂ O is removed and then aged in an oven at a temperature of less than 80 ℃, the coating surface of the iron chloride coated on the biomass easily fall or the effect is insignificant, FeCl exceeded 80 ℃ _In the case of coating ₃ · 6H ₂ O, the biomass coated with iron chloride may be deteriorated.

In addition, when the FeCl ₃ · 6H ₂ O is removed after aging in the oven for less than 2 hours, the coating surface of the iron chloride coated on the biomass is easily dropped or the effect is small, aging in the oven for more than 2 hours When the biomass coated with iron chloride is deteriorated or the coated surface is uneven, the phosphorescence adsorption capacity of the nanometal pine biocar manufactured according to the present invention may be lowered.

Next, the sixth step (S60) is injected into the biomass (iron chloride-biomass) of the dried and surface-treated at a flow rate of 2500 cm3 / min in the pyrolysis and blocking the inflow of air to the pyrolysis Pyrolyze

More specifically, the pyrolysis is carried out at a temperature of 200 to 700 ℃ for 2 hours, it is preferable to increase the temperature at a temperature increase rate of 7 ℃ / min to the temperature. The pyrolysis is gradually increased to a temperature of 7 ° C. per minute to prevent the iron chloride coated on the biomass from falling off or deforming. If the pyrolysis temperature is less than 7 ° C., the pyrolysis time may be too long, resulting in the coating surface contacting the surface of the biomass falling. If the pyrolysis temperature exceeds 7 ° C., the biomass is deformed during the pyrolysis. It is preferable to carry out under the above conditions since there is a risk of being damaged or altered.

In addition, the thermal decomposition, there is a problem that the adsorption performance effect on the phosphate is insignificant when pyrolysis at a temperature of less than 200 ℃, when compared to 500 ℃ when the thermal decomposition over 700 ℃ rather than the adsorption performance effect is lowered in the above conditions It is preferable to carry out.

In addition, when the pyrolysis is performed in less than 2 hours, the thermal decomposition is insignificant, and thus the effect of making the bio tea is insignificant. When the pyrolysis is performed for more than 2 hours, the manufactured nanometal pine bio tea may be deteriorated or the surface modified coating surface may fall. Since there exists a possibility, it is preferable to carry out on the said conditions.

Hereinafter will be described an embodiment of the method for preparing a phosphorus-free nanometal pine bio-tea.

(1) bio tea production

Pines were purchased from a specialized pine wholesale market and washed several times in running tap water. Fully washed pines were dried well in a windy room. The dried pine was crushed to produce sawdust, and then dried sufficiently in a windy room. No. of dried pine sawdust Passed through 12 (1.70mm) screen and No. Particles of size not over 80 (180 μm) were used in the experiment. The crushed biomass was dried at a temperature of 80 ° C. in a custom dryer (Hanyang Science Co., Ltd.) for 3 hours and pyrolyzed in a pyrolysis machine to produce bio tea. After weighing enough dry biomass, it was put in a pyrolysis machine and nitrogen gas was injected at a flow rate of 2500 cm 3 / min, and pyrolysis was started while blocking the inflow of air into the apparatus. The temperature was increased slowly at a rate of temperature increase of 7 ° C./min to the pyrolysis target temperature. Pyrolysis at 250 ° C., 400 ° C., 500 ° C., 600 ° C., and 700 ° C. for 2 hours to produce biotea required for the experiment at each temperature. In the present invention, the pine sawdust raw material is labeled Pine-R for convenience, and the bio-teas produced at 250 ° C, 400 ° C, 500 ° C, 600 ° C and 700 ° C are labeled as PB250, PB400, PB500, PB600 and PB700, respectively.

(2) Surface modified bio tea production

In order to surface-modify the biomass to make a magnetic bio tea, the dried and pulverized biomass is put into a FeCl ₃ .6H ₂ O solution of a predetermined concentration and stirred for 2 hours. FeCl ₃ · 6H ₂ O After the solution was removed, the solution was aged in an oven at 80 ° C. for 2 hours, and then the surface-treated biomass was completely dried. The biomass, completely dried with water, was injected into the pyrolyzer according to the method described above, and pyrolyzed at a predetermined temperature.

(3) Analysis of physical and chemical properties of bio tea

In order to analyze the bio-tea raw materials and the components of the bio-tea produced using an element analyzer (Element Analyzer) was measured the ratio of C, H, N, S, O contained in each of the materials. The element analyzer used was a Vario-Micro Cube model manufactured by Element Analyzer GmbH (Germany), and the elemental composition ratio of each material was measured by using sulfanilic acid as a standard with combustion temperature at 1,150 ℃. In order to analyze the effect of pyrolysis temperature on the shape and structure of the bio-tea, FE-SEM (Field Emission Scanning Electron Microscope: MIRA-3, Tescan, Czech Republic) was used to change the magnification and shape of each material. Photographed. The pore size and BET specific surface area of the biocar were measured using a 3Flex & TriStar 3020 model manufactured by Micrometrics (USA). Samples were raised to 100 ° C. using pretreatment equipment (VacPreP 061, Micrometrics, USA) and dried over vacuum for 3 hours and measured using nitrogen gas.

(4) Phosphorus adsorption experiment

K ₂ HPO ₄ used to make the phosphorus solution was purchased from Junsei Chemical Co., LTD (Tokyo, Jpan) as an analytical product with purity over 99%. By injecting a metal nano-bio pine difference in 0.2g K ₂ HPO ₄ 35mL solution of a given concentration and then stirred for 72 hours after removal of the particles in solution group scan filter to measure the PO ₄ ^3- concentration of the equilibrium state of the car Bio The adsorption performance for was evaluated.

In the following, the experimental results according to the above experiments are shown.

A. Elemental Analysis of Biomass and Bio-tea

The ratios of elements C, H, N, S, and O constituting each material measured using an element analyzer are shown in Table 1 below.

unit:% C H N S O Pine-r 46.6 6.4 0.1 0.1 41.8 PB250 52.6 5.6 0.1 0.0 37.7 PB400 76.0 3.8 0.2 0.1 15.8 PB500 82.9 3.1 0.2 0.3 9.6 PB600 84.6 2.3 0.5 0.4 7.8 PB700 89.7 1.4 0.4 0.4 3.9

The pine sawdust used to prepare the nanometal pine bio tea produced by the present invention contained 46.6% of carbon and the contents of hydrogen, nitrogen, sulfur and oxygen were 6.4%, 0.1%, 0.1% and 41.8%, respectively. It was. When pyrolysis of pine sawdust was performed at 250 ℃, the carbon content was 52.6%. As the pyrolysis temperature was gradually increased, the carbon content was increased. The composition ratio of oxygen in raw materials was 41.8%, but the ratio of oxygen in bio tea pyrolyzed at 700 ℃ was only 3.9%.

N. Biomass and Surface Morphology and Structural Analysis

The shape of the surface shape and structure of pine sawdust bio-tea prepared by pyrolysis of raw materials pine sawdust and pine sawdust as the magnification was changed by scanning electron microscope (SEM). Figure 2 (A) shows the surface shape and structure of pine sawdust, (B) is the surface shape and structure of the PB250, (C) is the surface shape and structure of the PB400, (D) is of the PB500 Surface shape and structure, (E) is the surface shape and structure of the PB600, (F) is the surface shape and structure of the PB700.

As shown in Figure 2, when comparing the structure of the bio-tea produced by pyrolysis of the pine sawdust and pine sawdust all the samples appear in a similar form in the low-magnification image as in the two seaweeds, but it was not easy to distinguish the shape It can be seen that the difference in the surface structure is apparent in images taken at high magnification. Materials Compared to pine sawdust, bio-cars made with pine sawdust have distinct voids on the surface, and the surface roughness increases and the porosity increases with increasing pyrolysis temperature.

If you look at the surface of the pine sawdust used to make the bio-tea under SEM, it can be observed that there are almost no voids on the surface of the biomass. Porosity is formed in the pores, and as the manufacturing temperature of the bio-tea gradually increases, the pores also increase. Table 2 shows the BET specific surface area and the BET specific surface area of bio tea according to pyrolysis temperature. In general, the BET specific surface area tended to increase with increasing pyrolysis temperature.

BET SurfaceArea (m ² / g) Pine-r 0.308 PB250 0.465 PB400 0.555 PB500 0.734 PB600 2.595 PB700 1.912

C. Adsorption Performance of Phosphorus on Bio-tea

In order to evaluate the adsorption performance of the bio-tea to the phosphorus (phosphate), the bio-tea prepared by the above method is added to the phosphorus (phosphate) 3mg / L solution and the phosphorus by the bio-tea as described in the phosphorus adsorption experiment ( phosphate) removal rate was measured. Figure 3 shows the phosphorus (phosphate) removal rate of the pine bio tea produced at each pyrolysis temperature. Pine sawdust biotea produced at the pyrolysis temperature of 250 ℃ showed no difference in phosphate removal rate from that produced at other pyrolysis temperatures. The phosphate removal rates of the five pine sawdust bioteas produced at different pyrolysis temperatures were all measured between 65% and 70% and showed similar phosphate removal rates.

In addition, FIG. 4 shows the nanometal pine sawdust bio tea pyrolyzed at 500 ° C. after surface treatment of biomass in a FeCl ₃ · 6H ₂ O solution at a constant concentration in the fifth step (S50) and the sixth step (S60). It shows the removal rate for phosphate. As shown in Figure 4, the pine sawdust surface-treated iron chloride-pine sawdust at five different concentrations ranging from 0.025M to 0.3M concentration of FeCl ₃ · 6H ₂ O solution by pyrolysis at a predetermined temperature for each FeCl ₃ Phosphate adsorption rate of nanometal pine bio tea was measured according to the surface treatment concentration of 6H ₂ O solution.

The PB500 represents pine sawdust biotea pyrolyzed at 500 ° C. without surface treatment, and P0.025M to P0.3M were prepared by thermal decomposition after surface treatment at a concentration of 0.025M to 0.3M in a FeCl ₃ · 6H ₂ O solution, respectively. Nanometal bio tea is shown. Phosphate removal rate of nanometal bio tea P0.025M prepared by surface treatment of pine sawdust in 0.025M FeCl ₃ · 6H ₂ O solution was 79.1%, higher than that of PB500 without surface treatment, and FeCl ₃ · 6H ₂ O Phosphorus removal was slightly decreased in the nanometal bio-tea P0.05M prepared by increasing the solution concentration at 0.05M. When the concentration of FeCl ₃ · 6H ₂ O surface treatment solution was increased to 0.1M, the adsorption rate of phosphate of nanometal bio-car increased significantly, and when the concentration of surface treatment solution was increased to 0.2M and 0.3M, The above effect was not observed, and the adsorption rate was similar to that of the phosphate adsorption of the nanometal bio-tea prepared at the concentration of 0.1M of the surface treatment solution.

By the means for solving the above problems, the present invention can derive the optimum pine bio-tea manufacturing conditions to easily adsorb the phosphorus present in the anion (PO43-) form.

In addition, the present invention can provide a nano-metal pine bio tea by modifying the surface of the bio tea with nano metal to increase the phosphorus adsorption capacity of the pine bio tea.

As such, the technical configuration of the present invention described above can be understood by those skilled in the art that the present invention can be implemented in other specific forms without changing the technical spirit or essential features of the present invention.

Therefore, the above-described embodiments are to be understood as illustrative and not restrictive in all respects, and the scope of the present invention is indicated by the following claims rather than the detailed description, and the meaning and scope of the claims and their All changes or modifications derived from an equivalent concept should be construed as being included in the scope of the present invention.

S10. A first step of washing pine tree under running tap water;
S20. A second step of drying the pine indoors;
S30. A third step of pulverizing the dried pine with a crusher to produce particles of size No. 12 (1.7 mm) to No. 80 (180 μm);
S40. A fourth step of preparing biomass by drying the pine sawdust at 75 to 85 ° C. for 3 hours;
S50. A fifth step of adding the biomass to a FeCl ₃ · 6H ₂ O solution, stirring for 2 hours, and then drying the biomass to surface-treat the biomass;
S60. A sixth step of injecting the surface-treated biomass into the pyrolyzer by injecting nitrogen gas at a flow rate of 2500 cm 3 / min and pyrolyzing by blocking the inflow of air to the pyrolyzer;

Claims (5)

Phosphorus-removed nanometal pine bio-tea, characterized in that produced from pine sawdust. The method of claim 1,
The pine sawdust is phosphorus-removed nanometal pine bio-tea, characterized in that the surface is coated with iron chloride. Washing, drying and crushing pine to prepare sawdust in the form of biomass;
Subjecting the biomass to a FeCl ₃ .6H ₂ O solution, stirring and drying the surface of the biomass;
And injecting nitrogen gas into the pyrolyzed surface-treated biomass after the drying, and pyrolyzing by blocking the inflow of air to the pyrolyzer, wherein the nanometal pine bio-tea for removal of phosphorus is manufactured. The method of claim 3,
The FeCl ₃ · 6H ₂ O solution is a method of producing a nano-metal pine bio tea for removal of phosphorus, characterized in that prepared in a concentration of 0.1 to 0.3M. The method of claim 3,
The pyrolysis is carried out for 2 hours, the method of producing a nano-metal pine bio tea for phosphorus removal, characterized in that to increase the temperature to a temperature increase rate of 7 ℃ / min to the temperature.

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