KR101703850B1

KR101703850B1 - Environment-friendly water-bloom adsorbent using heat-treated wood and manufacturing method thereof

Info

Publication number: KR101703850B1
Application number: KR1020150187442A
Authority: KR
Inventors: 강석구; 이창구; 최철; 류지창; 이현재; 양승민
Original assignee: 충남대학교 산학협력단
Priority date: 2015-12-28
Filing date: 2015-12-28
Publication date: 2017-02-08

Abstract

A method of manufacturing an environmentally-friendly green tea remover according to a preferred embodiment of the present invention comprises the steps of S1) chipping wood to a predetermined size or less using an industrial chipping device, S2) treating the wood material obtained after the chipping step at 150 ° C to 500 ° C And S3) a step of converting the surface charge of the heat-treated woody material by mixing the heat-treated woody material that has undergone the heat-treatment and semi-carbonization step with an aqueous solution of the cationic polyelectrolyte, Characterized in that the surface of the carbonized wood chips or wood chips is surface-modified by using a cationic polyelectrolyte aqueous solution to adsorb and remove the green tea by the potential difference.

Description

TECHNICAL FIELD [0001] The present invention relates to a green algae remover using heat-treated wood,

The present invention relates to a green algae remover using heat treated wood, and more particularly, to an environmentally friendly algae remover which absorbs and removes a green algae on its surface through surface modification of heat treated wood, and a method for producing the same.

Due to the current climate change, green tides occur in early summer rivers and fresh water lakes every year due to abnormal weather such as drought and heat. Recently, it has been recognized as a social problem due to an increase in the frequency of the occurrence of green tides (see Table 1 below). Currently, there are three stages of algae warning, bird alert, and bird algae occurrence through the Law Concerning the Protection of Water Quality and Aquatic Ecosystem.

division '09 Year '10 '11 '12 '13 '14 system 244 177 131 204 82 165 Notice 201 163 131 161 82 158 Warning 43 14 - 43 - 7 Outbreak - - - - - -

In addition, the notice of green algae, which occurred in early summer rivers and fresh water lakes, and which disappeared in autumn, has been issued as a warning by mid-November as of 2014 (see Table 2).

The concentration of green tide has increased due to the decrease in the amount of water in autumn and fresh water lake in autumn, and the warning announcement continues until mid-November.

However, due to the occurrence of most of the recent green algae, the harmful cyanobacteria, which are advantageous for overproduction of rivers and fresh water lakes, cause blooms on the surface of water to increase the turbidity in the water and consume water oxygen, . The toxin production threatens the health, and this hobby causes the consumption of more energy in the water purification process, and the drinking water value is deteriorating.

Current green algae removal methods include loess spraying, aberrations, algae removal lines, and ultrasonic algae eliminators. Of these, loess is an agglomerate spraying agent used more than 80% when domestic green tides occur. In the case of loess, the processing cost (in tons) is low. However, the recommended dose is about 100g to 400g / m ³ , but the actual spray amount is about 1000g / m ^{3, which means} that much more than the recommended amount.

There is also a possibility of secondary environmental pollution due to excessive repeated use of loess (damaging forest land for securing loess and ecosystem disturbance). There is also the risk of collective deaths in the gills of the aphrodites using excessive loess. The coagulated sedimentation in the lake basin results in faster rates and greater amounts of algae in the next year due to re-dissolution. In addition, it costs more than 400 billion won each year to remove green algae, resulting in economic loss. In addition, when a large amount of green algae is decayed, it is decomposed in the lower layer, and due to the anoxic condition of the lower layer, there is a risk of leaching of components such as iron and manganese contained in the soil, .

Therefore, there is an urgent need to develop a green algae remover that can remove the green algae more effectively at a low cost, while being environmentally friendly, which does not cause the problems of secondary environmental pollution.

Accordingly, it is an object of the present invention to provide an eco-friendly algae remover using heat-treated wood that can solve the problems of the prior art as described above and can effectively remove green algae as compared with yellow clay used for removing existing algae, And a method thereof.

Therefore, a method of manufacturing an environmentally-friendly green tea remover according to a preferred embodiment of the present invention comprises the steps of S1) chipping wood to a predetermined size or less using an industrial chipping device, and S2) And S3) a step of converting the surface charge of the heat-treated woody material by mixing the heat-treated woody material that has undergone the heat-treatment and semi-carbonization step with an aqueous solution of the cationic polymer electrolyte Characterized in that the surface of the semi-carbonized heat-treated wood chips or wood chips is surface-modified by using a cationic polymer electrolyte to adsorb and remove the green tea by the potential difference.

Preferably, the cationic polyelectrolyte aqueous solution is a cationic polyacrylamide aqueous solution.

Preferably, the aqueous solution of the cationic polyacrylamide is an aqueous solution prepared by using a cationic polyacrylamide solid content of not less than 3 wt% and not more than 7 wt% based on the weight of the heat-treated wood material.

Also, in the heat-treatment and semi-carbonization step (S2), the temperature of the carbonization apparatus is raised to 150 to 500 DEG C, and the wood chip is supplied into the rotary drum rotating in the carbonization apparatus about the horizontal axis And the rotary drum is heated by the heating means while rotating the rotary drum to perform rapid thermal annealing.

And a drying step of drying at a temperature of 100 to 110 DEG C after the step S3).

Also, in the step S1), the wood is characterized by being a pest-damaging tree of the pine wilt disease or oak wilt disease.

Further, after the heat-treatment and semi-carbonization step (S2), the wood-based material is pulverized by a pulverizer, and screen-passing particles of 4 mesh or less are used in the step S3).

Therefore, according to the present invention, there is provided an eco-friendly green tea remover using a heat-treated wood which is eco-friendly and can effectively remove green algae at a lower cost as compared with yellow clay used for removing existing greenhouse, and a method for manufacturing the same.

In addition, it is expected that the effect of the treatment of the pest damage tree and the removal of the green algae can be expected by using the semi-carbonized heat-treated wood flour of the present invention, which is increasing each year, .

FIG. 1 is a graph showing the zeta potential of an activated charcoal, wood powder, yellow loess and semi-carbonized heat treated wood powder used in the present invention as a result of the zeta potential experiment of each sample,
FIG. 2 is a graph showing a zeta potential comparison according to the concentration of the algicidal agent according to the present invention,
FIG. 3 is a graph showing the experimental results of iodine adsorption of the algicide according to the present invention,
Fig. 4 is a graph showing experimental results of visual observation of removing green algae from each sample.

A method of manufacturing an environmentally-friendly agar agar detergent according to a preferred embodiment of the present invention includes the steps of chipping wood to a predetermined size or less using an industrial chipping device, and a step of laminating the wood material obtained after the chipping step at a processing temperature of 150 to 500 ° C A step of crushing the lignocellulous material that has undergone the semi-carbonization step with a crusher to recover screen-pass fractions of 4 mesh or less; and a step of recovering the heat-treated ligneous material recovered after crushing by cationic Treating the lignocellulosic material by mixing with the aqueous solution of the polymer electrolyte to convert the surface charge of the heat-treated lignin material and then drying at 100 to 110 ° C.

Hereinafter, a method for producing an environmentally-friendly algal remover according to the present invention will be described in detail.

1. Timber cutting and chipping steps

In the present invention, as a raw material, wood is cut to a depth of about 1 m, and then chipping and crushing are carried out through an industrial chipping or the like to a size of about 10 cm or so including barks. The woody material used as the main material at this time is common bamboo, pine, larch pine, larch, pine wood, radiant pine, eucalyptus, melancholy, kerosene, birch, chestnut, It is possible to use various mixed species with evolving history including white oak, oak oak, oak, cherry tree, Yoshino cherry tree, acacia tree, weighted tree, poplar, and acacia from Vietnam. In addition, there are trees, twigs, Low added value raw materials such as woody by-products, pine tree reindeer damage trees, and pine tree damage diseases such as oak tree blooms can also be used. In addition, agricultural by-products such as rice hull, straw, and sugar cane residue can be utilized.

2. Thermal processing step

After the above chipping and shredded wood chips are transferred to a drying and carbonizing chamber, the furnace temperature of the wood drying and carbonizing equipment is raised to the processing temperature of 150-500 ° C according to the present invention, and then the chipped wood chips are rapidly thermally processed . At this time, in the present invention, since the raw material is put in a state of reaching a high temperature of 150 to 500 캜 and heat-treated rapidly, the wood chip is heat-treated by wood roasting to prevent the wood raw material from being carbonized. To this end, in the present invention, a wood chip is supplied into a rotary drum rotating around a horizontal axis instead of a conventional carbonization furnace, and the rotary drum is heated by a heating means including a gas burner while the rotary drum is rotated by a motor, Rapidly thermally process. Therefore, it takes a long time to heat-treat the existing carbonaceous furnace, and continuous production is impossible. However, in the present invention, the wood chips are subjected to the heat treatment successively, whereby the heat treatment can be performed quickly at low cost.

In this step, the rapid high-temperature drying and thermal processing treatments are carried out in such a manner that as volatile substances such as moisture, carbon monoxide and carbon dioxide, acetic acid, and methanol are removed and charcoal is produced State. That is, when the wood treatment range of the present invention is divided into the carbon content, the carbon content of the char is 90 to 100 wt% or less, the carbon content of the charcoal is in the range of 40 to 50 wt% %, And as a preferred embodiment, more than 50 wt% and less than 80 wt%.

In this way, the wood chips are rapidly dried and heat-treated in the same manner as described above within 72 hours. After the heat treatment, the wood chips are immediately taken out or cooled to room temperature.

3. Grinding process

The semi-carbonized wood chips recovered through the above thermal processing step are subjected to a crushing process through a crusher (or chipping) dedicated to the wood chip. In this grinding process, the wood chip can be further subjected to a fibrousizing process with a dedifferer or a grinder after grinding with a wood chip grinder or grinding with a grinder.

In order to mix with the aqueous solution of the polymer electrolyte, which will be described later, the woody material that has been subjected to the pulverizing process is preferably recovered from the screen passing through 4 mesh (# 4) or less. A screen having a size of 4 mesh (# 4) or less includes 4 meshes and a screen having a smaller scale than four meshes. The screen is not necessarily limited thereto. The present step can be omitted.

4. Manufacturing process of aqueous solution of cationic polyelectrolyte

Next, a cationic polyelectrolyte aqueous solution is prepared. The cationic polyelectrolyte aqueous solution is for surface modification of the heat-treated woody material obtained as described above, and the zeta potential (Zeta Potential) of the general greenhouse water is about 29.69 mV. Meanwhile, in the present invention, the zeta potential of the heat-treated wood material (semi-carbonized wood chips / wood chips) treated as described above has the same electric charge of about 52.5 mV. Therefore, in order to remove the greenhouse which is negatively charged, the cationic polyelectrolyte aqueous solution is prepared in order to convert the surface charge of the heat-treated woody material obtained in the above process into positive charge and to adsorb and remove the green tea on the surface thereof. In the present invention, the aqueous solution of the cationic polymer electrolyte is prepared by mixing water (or distilled water) at the end of the cationic polymer electrolyte solid content and stirring at a temperature of 100 ° C or lower at a stirring speed of 200 rpm or more for 1 hour or more, and the cationic polymer electrolyte The concentration of aqueous solution was adjusted to 0.1% ~ 1% by weight. In the present invention, as the cationic polyacrylamide, a cationic polyelectrolyte based on a quaternary amine system is used as the cationic polyelectrolyte. Polyacrylamide is widely used as soil amendment agent and is effective in stabilizing the formation of the entrance of the soil surface. It has the effect of increasing the permeability during irrigation and reducing soil erosion, and is generally used for increasing the retention in the papermaking process. The cationic polyacrylamide Is a strong cationic polyelectrolyte which is harmless to the human body and has no problem of elution due to C, H, O, N compounds. In addition to the cationic polyacrylamide, which is a quaternary amine system, cationic polyelectrolytes of primary amine, secondary amine and tertiary amine series can be used. Polyethyleneimine (PEI), Polyethylene oxide (PEO), and Poly aluminum chloride (PAC) are examples of tertiary amines.

5. Manufacturing process of eco-friendly algal remover

In this step, the heat-treated wood material prepared in advance is added to the above-mentioned cationic polyelectrolyte aqueous solution, and the mixture is stirred at a stirring speed of 200 rpm or more at a temperature of 100 ° C or less for 1 hour or more and dried at 105 ± 5 ° C for 24 hours. Thereby forming a algal remover.

[Performance test example]

In order to compare the effect of removing the green algae, the same mass of the sample was added to the number of green algae to compare the surface charge of the algae remover, the yellow soil and the activated carbon according to the present invention, Green algae removal experiments were performed.

1) The algae removing agent according to the present invention used in the experiment was a semi-carbonized heat treated wood and a cationic polyacrylamide-based polymer. In the present invention, the algae removing agent is a wood chip, in which a pine wood chip having a water content of 12% is put into a carbonizing machine, the temperature of the furnace is raised to the atmospheric temperature of 220 ° C, and the inside of the furnace is thermally processed Respectively. After the heat treatment, the mixture was pulverized by a pulverizer and passed through a 200 mesh screen.

The aqueous solution of the cationic polyelectrolyte contained about 0.1 g, 0.3 g, 0.5 g, 0.7 g, and 0.9 g, which corresponded to 1%, 3%, 5%, 7%, and 9% After mixing the distilled water at the end of the cationic polyacrylamide solid content, the mixture was stirred at 90 ° C to obtain a predetermined viscosity, which was then stirred again with the semi-carbonized wood. At this time, stirring was carried out at 90 DEG C for 5 hours. After that, it was dried at 105 ± 5 ° C for 24 hours and finally prepared.

2) Zeta Potential Measurement Experiment

In this experiment, zeta potential measurement experiments were conducted to measure surface charge of yellow loess, activated carbon, general wood, and heat treated wood powder used in the present invention. In order to measure the surface charge of each sample, 2% by weight of each sample was dissolved in water to a concentration of 2%, and the zeta potential was measured using AFG ANALYTIC GMBH equipment. The results of measurement of the zeta potential of each sample are shown in Fig. In FIG. 1, activated carbon, wood powder, semi-carbonized heat-treated wood powder (TWP) used in the present invention, and zeta potential of loess are shown from the left side.

As shown in FIG. 1, the Zeta Potential of activated carbon, wood powder and loess was similar, and the lowest value was 52.5 mV in the case of the bentonite powder used in the present invention. For reference, Zeta Potential shows a lower value as the number of OH is larger.

Next, about 0.1 g, 0.3 g, 0.5 g, 0.7 g and 0.9 g of cationic polyacrylic acid corresponding to 1%, 3%, 5%, 7% and 9% (TWP C-PAM) of the present invention, prepared as described above, using an amide solid fraction (corresponding to TWP C-PAM 1 wt%, 3 wt%, 5 wt%, 7 wt%, and 9 wt% Potential was measured. FIG. 2 shows the measured zeta potential as the concentration of the cationic polyacrylamide aqueous solution was increased as a result of the zeta potential measurement according to the present invention with respect to the concentration (wt%). In addition, it was possible to increase the potential up to +31.2 mV when the cationic polyacrylamide aqueous solution (C-PAM) was 9 wt%, and confirmed the possibility of removal by the potential difference of the number of green algae (? 29.69 mV) by the cationic polymer treatment.

3) Measurement of iodine adsorption power

Then, an iodine adsorption test was conducted to evaluate the liquid adsorbing ability of the present invention of the present invention (KS M 1802 activated carbon test method).

FIG. 3 is a graph showing the results of the iodine adsorption test according to the present invention. As the concentration of the cationic polyacrylamide (C-PAM) aqueous solution was increased, the iodine adsorption power was increased and the highest value was observed at 7 wt% of TWP C-PAM. Generally, in the case of activated carbon, iodine adsorption power of 600 mg / g or more is considered to have an adsorption performance. Based on these criteria, it can be considered that iodine adsorption performance is more than 3 wt% of TWP C-PAM in the present invention.

4) Visual observation of algae removal efficiency

Next, a visual observation experiment of removing green algae was carried out. For this purpose, the volume of the green algae was adjusted to 400 ml in the beaker, and 5 g of each sample was added to the green algae to observe the removal of the algae.

FIG. 4 is a graph showing an experiment for removing a green algae. FIG. 4 is a graph showing an experiment for removing a green algae. FIG. 4 is a graph showing an experiment for removing a green algae. %, 3wt%, 5wt%, and 7wt%) were added to the green algae water. In the visual observation experiment of removal of the green algae, samples were applied to the number of green algae, and when 4 hours had elapsed, the green algae removal was the best in 5 wt% of TWP C-PAM. Therefore, from the viewpoint of cost efficiency, TWP C-PAM is considered to have a high efficiency of 3 wt% or more and 7 wt% or less.

On the other hand, due to global warming and climatic conditions, the number of forest pests is increasing irregularly due to the influx and spread of forest pests in forests. In 2014, the total area of forest pests damage to the nation is 127,000 ha, which is distributed on a huge scale corresponding to the area of Ulsan Metropolitan City. In the present invention, semi-carbonized wood powder obtained by heat-treating wood as a raw material is used as a raw material. In this case, when the pine woodworm or oak wilt disease which is increasing every year is processed into a bentonized wood powder of the present invention, It is expected that the effect of two seats will be achieved by removing the algae and dealing with the sickness damage.

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, but, on the contrary, It will be apparent to those skilled in the art that various modifications may be made.

Claims

S1) chipping the wood to a predetermined size or less using an industrial chip,
S2) subjecting the woody material obtained after the chipping step to heat treatment at a treatment temperature of 150 ° C to 500 ° C for a predetermined period of time to half-
S3) mixing the heat-treated wood material through the heat-treatment and semi-carbonization step with an aqueous solution of a cationic polyelectrolyte to convert the surface charge of the heat-treated wood material,
In the step S3), the cationic polyelectrolyte aqueous solution is a cationic polyacrylamide aqueous solution,
In the heat treatment and semi-carbonization step (S2), the temperature of the carbonization apparatus is raised to 150 to 500 DEG C, and the wood chips are supplied into the rotary drum rotating in the carbonization apparatus about the horizontal axis by heat treatment, Wherein the rotary drum is heated by the heating means while rapidly rotating the drum, and subjected to rapid heat treatment.

delete

The method according to claim 1,
Wherein the aqueous solution of the cationic polyacrylamide is an aqueous solution prepared by using a solid cationic polyacrylamide solid content of not less than 3 wt% and not more than 7 wt% based on the weight of the heat-treated lignocellulosic material.

delete

The method according to claim 1,
And drying at a temperature of 100 to 110 ° C after the step (S3).

The method according to claim 1,
Wherein the wood in step S1) is a pest-damaged tree of the pine wilt disease or oak wilt disease.

The method according to claim 1,
Characterized in that the woody material is pulverized by a pulverizer after the heat-treatment and semi-carbonization (S2) and the pulverized woody material is used in the step S3).

8. The method of claim 7,
Wherein the lumber material is pulverized by the pulverizer, and a screen passage of 4 mesh or less is used in the step S3).

An eco-friendly algae remover using heat-treated wood produced by the manufacturing method according to any one of claims 1, 3, and 8.