KR101620543B1 - Amino acid-chitosan Composite Liquid Fertilizer Using Organic Waste and Preparation Method Therof - Google Patents

Abstract

The present invention relates to an amino acid-chitosan composite liquid fertilizer using livestock blood, and a method for producing the same. More specifically, when a liquid fertilizer is produced by making livestock blood reacted with a coagulant, a natural coagulant capable of exhibiting more excellent coagulating properties than a chemical coagulant is used to apply the liquid fertilizer to organic agricultural products produced without using a chemical fertilizer, and to utilize the liquid fertilizer in promoting the growth of agricultural products, increasing functional components of agricultural products, managing leisure facilities such as golf course turf, and managing landscaping and horticultural plants.

Description

TECHNICAL FIELD The present invention relates to an amino acid-chitosan complex liquid fertilizer and a method for preparing the same,

The present invention relates to an amino acid-chitosan complex solution using livestock blood and a method for producing the same.

The blood of livestock (pigs, cows, etc.) is a livestock by-product produced from slaughterhouses, and although it is a useful resource rich in various proteins, it is defined as waste in current law and has both sides that require appropriate treatment.

The constituents in livestock blood can be divided into water, organic matter and inorganic matter in an amount of 79.14%, 19.40% and 1.45%. Except moisture, organic matter is the most abundant in the blood, and the protein content is 18.22%, and 94% of the organic matter content is composed of protein. Albumin, globulin, fibrinogen, and hemoglobin are among the proteins that make up the livestock blood, with hemoglobin accounting for 14.02%.

As described above, the protein component, which accounts for 18% of the livestock blood, can be made into a good amino acid to be absorbed by the human body. However, only a very small amount of the bovine blood in the livestock blood has been distributed as a pre- Most are treated as waste except for some fertilizer raw materials.

In general, a ton of livestock blood requires 5 tons of water to be treated, and the wastewater treatment costs considerable costs including drugs, electricity, and labor. It is generally known that animals such as cattle require 1.2 to 1.5 cubic meters of water for each animal and 0.4 to 0.5 cubic meters of water for pigs. The slaughter house, which slaughters 3,200 sows per year and 244,300 pigs, costs about 260 million won for wastewater treatment. Therefore, discarding livestock blood from slaughterhouses is a major loss in economic and industrial aspects, and also a negative factor in cultural and social aspects. From this point of view, if the abandoned runaway blood is recycled, it will be possible to solve the environmental problems by the radical elimination of livestock blood and to create added value such as conversion to high value added resources, high economic value added effect, Therefore, it is urgent to develop new processing resources by utilizing livestock blood.

As a conventional technique utilizing livestock blood as a resource, Korean Patent Registration No. 10-0890918 entitled " Method for Producing Mineral-Bound Peptides Using Livestock Blood " discloses a method for producing a mineral-binding hydrolyzate from plasma proteins isolated from livestock blood And a method of isolating and producing a mineral-binding peptide having a high binding force to minerals by using a chromatographic method is disclosed in Korean Patent Publication No. 10-1462214 entitled " (Organic Coated Porous Granules and Method for Producing the Same) discloses a method for producing an organic coated porous granule and a method for producing the same, which comprises the step of forming an organic coating layer composed mainly of proteins on the surface of the granule using the blood of a livestock (bleeding), containing minerals such as zircon Water penetrates the pores inside the granules that make up the main ingredient. Discloses a technique for delaying the time for granulation for a feed for diatomaceous herbal composition or auxiliary feed supplement having excellent floatability.

On the other hand, the organic farming method is defined as a farming method that does not use chemical fertilizers and pesticides. In other words, as an agricultural method to grow vegetables and fruits without using chemical fertilizers or pesticides, the organic farming method, which appeared as a reflection on soil pollution and chemical fertilizer farming, naturally uses organic chemicals and microorganisms It is a farming method to grow crops using raw materials.

In order to produce liquid fertilizer by using livestock blood, a coagulant is added to the livestock blood to form a floc which is a contaminant, and then the liquid material of the clear filtrate obtained by solid-liquid separation is used as the liquid fertilizer. As described above, the flocculant used for reacting with the livestock blood is mainly composed of a cationic coagulant, and most of them use polyacrylamide, which is a synthetic chemical excellent in water solubility.

However, the coagulant of the synthetic chemical necessarily inevitably leaves the monomer, and if it is introduced into the environment, the low molecular weight substance or the monomer leaks due to decomposition. Particularly, the acrylamide, which is a monomer of polyacrylamide, Monomers and low molecular weight chains show strong toxicity and strong irritation. In addition, since it is reported that skin irritation is caused by causing paralysis of the central nervous system, there is a great potential danger. Above all, when the liquid fertilizer is manufactured using the coagulant, which is a synthetic chemical, It is not applicable to organic agricultural products which do not use chemical fertilizer.

Accordingly, in the present invention, when the livestock blood is biodegraded and reacted with the flocculant while the livestock is being developed using the abandoned livestock blood, by using the natural flocculant which can realize better flocculation characteristics than the existing flocculant, It is possible to produce a high quality amino acid-chitosan complex liquid fertilizer which can promote the growth of crops. Thus, the present invention has been completed.

Korean Patent Registration No. 10-0890918 Korean Patent Publication No. 10-1462214

The main object of the present invention is to provide an organic fertilizer utilizing the livestock blood and a method for producing the same.

In order to accomplish the above object, the present invention provides a method for preparing a liquid amino acid preparation, which comprises solubilizing livestock blood and then decomposing it by a biological method to obtain a liquid amino acid preparation; And reacting the liquid amino acid preparation with a natural flocculant. The present invention also provides a method for producing an amino acid-chitosan complex solution.

In a preferred embodiment of the present invention, the solubilization may be characterized by treating ultrasonic waves.

In a preferred embodiment of the present invention, the biological degradation may be characterized by using a complex enzyme.

In a preferred embodiment of the present invention, the natural flocculant is chitosan.

In one preferred embodiment of the present invention, the natural coagulant may be added in a volume ratio of 1 to 20 parts by volume based on 100 parts by volume of the liquid amino acid preparation.

In a preferred embodiment of the present invention, the step of reacting the liquid amino acid preparation with a natural flocculant may further include a step of solid-liquid separation.

In a preferred embodiment of the present invention, the solid-liquid separation is performed by at least one separation process selected from the group consisting of centrifugation, pressure separation, and gravity sedimentation separation.

In another embodiment, the present invention provides an amino acid-chitosan complex solution prepared by the above-described method.

In another embodiment of the present invention, there is provided a method for preparing a liquid amino acid preparation, which comprises solubilizing livestock blood and then decomposing it by a biological method using a complex enzyme consisting of Savinase and Flavourzyme to obtain a liquid amino acid preparation; And reacting the liquid amino acid preparation with a natural flocculant. The present invention also provides a method for producing an amino acid-chitosan complex solution.

The amino acid-chitosan complex solution according to the present invention can be applied to organic agricultural products that do not use chemical fertilizers by using a natural coagulant that can realize coagulation characteristics better than chemical flocculants when producing livestock by reacting livestock blood with flocculants However, it has an effect that it can be usefully applied to promotion of crop growth, increase of functional ingredients of crops, management of leisure facilities such as golf course lawn, and management of landscaping and horticultural crops.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flowchart showing a method for producing an amino acid-chitosan complex solution using livestock blood.
FIG. 2 is a graph showing protein solubilization rate according to elution of hemoglobin in blood cells of livestock blood before and after ultrasonic treatment according to frequency conditions.
FIG. 3 is a graph showing the protein solubilization ratio according to elution of hemoglobin in blood cells of livestock blood before and after the ultrasonic treatment according to irradiation density and irradiation time conditions.
4 is a graph showing protein conversion rates of livestock blood before and after ultrasonic treatment according to enzyme treatment conditions.
5 is a flowchart showing a method for producing an amino acid-chitosan complex solution including a solid-liquid separation process.
6 is a photograph showing the amino acid-chitosan complex liquid ratio before and after solid-liquid separation by a membrane filter press (Membrane filter press).
7 is a photograph before and after spraying the amino acid-chitosan complex solution with the crops.

The present invention relates to an amino acid-chitosan complex solution using livestock blood and a method for producing the same.

In the present invention, the term 'liquid' refers to a liquid fertilizer.

In the present invention, the term 'liquid amino acid preparation' refers to a liquid organic substance containing amino acids obtained by digesting livestock blood with proteolytic enzymes by a biological method.

As a result of intensive researches to produce high quality livestock using livestock blood which is an environmental problem in the present invention, it has been found that when livestock blood is solubilized and then decomposed by biological methods and then reacted with natural coagulant chitosan, -Chitosan complex liquid fertilizer can be produced, and the present invention has been completed.

Accordingly, the present invention, in view of this point, comprises solubilizing livestock blood as shown in Fig. 1 and then decomposing it by a biological method to obtain a liquid amino acid preparation; And reacting the liquid amino acid preparation with a natural flocculant. The present invention also provides a method for producing an amino acid-chitosan complex solution.

Hereinafter, a more detailed method for producing the amino acid-chitosan complex solution is described below.

First, livestock blood may be refrigerated or frozen in terms of odor reduction, prevention of decay, freshness maintenance, and the like.

The livestock blood that has undergone the refrigeration or freezing step may be subjected to a pulverizing treatment to efficiently solubilize the livestock blood. In this case, the pulverization step is not particularly limited as long as it is a pulverizable method, but it can be preferably carried out using a cutter type.

In the present invention, solubilization of livestock blood can be carried out by commonly known methods, but it is preferable to perform ultrasonic treatment. When such organic wastes are solubilized, there is an effect of eluting more proteins in biodegradation.

The conditions of the ultrasonic treatment are not particularly limited, but it is preferable to perform the ultrasonic treatment under the condition that the frequency is 20 to 28 kHz, the irradiation density is 0.1 to 2.0 W / mL, and the irradiation time is 20 to 40 minutes to increase the solubilization of proteins in the animal blood, It is preferable because it can decompose the protein.

As described above, when the frequency is adjusted to 20 to 28 kHz during the ultrasonic treatment, protein solubilization ratio is higher than that of untreated livestock blood, so that the protein can be efficiently decomposed. Also, when the ultrasonic wave irradiation time is increased, the solubilization ratio is increased. However, when considering the economical aspect, it is preferable that the irradiation density is 0.1 to 2.0 W / mL and the irradiation time is 20 to 40 minutes.

The present invention is characterized in that a biological method is used to decompose a protein in a solubilized livestock blood to obtain a liquid amino acid preparation. The biological degradation may treat microorganisms or proteolytic enzymes that secrete proteases. Proteolytic enzymes can be divided into endo-type enzymes which are cleaved in the interior of proteins according to the decomposition method and exo-type enzymes which are cleaved at the ends of proteins. For more efficient decomposition, endo-type enzymes -type) or exo-type (exo-type) enzymes are preferably used in combination.

Examples of the proteolytic enzymes include chymotrypsin, Alcalase, Savinase and Flavourzyme, and examples of the protease include Savinase and Pleborzyme Flavourzyme) is preferably used as a complex enzyme.

After the livestock blood is solubilized as described above, the obtained amino acid preparation can be directly used as a liquid but the natural flocculant is added in the present invention.

At this time, since the natural coagulant exhibits cohesiveness similar to that of a chemical flocculant by using chitosan, it can be used not only for organic agricultural products excluded from chemical components but also for promoting the growth of crops. Do.

Therefore, by using chitosan, a natural coagulant, it can be applied as an environmentally friendly organic liquid rather than a chemical liquid.

At this time, it is preferable that the chitosan is added in a ratio of 1 to 20 parts by volume relative to 100 parts by volume of the liquid amino acid preparation. If chitosan is added at a volume ratio of less than 1 part by volume per 100 parts by volume of the liquid amino acid preparation, the chitosan content is relatively low, which is insufficient to realize the function of chitosan. When the volume ratio is more than 20 parts, It is not only economical but also highly viscous because it can exhibit sufficient efficacy without adding it, making it difficult to produce liquid fertilizer.

In the present invention, it is preferable that the reaction of the liquid amino acid preparation with chitosan is rapid stirring at 50 to 70 rpm for 3 to 8 minutes and then slowly stirring at 20 to 40 rpm for 10 to 20 minutes. This is because in the initial stage of the reaction, rapid stirring is performed for 3 to 8 minutes at 50 to 70 rpm for rapid reaction of the liquid amino acid preparation and chitosan, but subsequent rapid stirring may interfere with the reaction of the liquid amino acid preparation and chitosan.

Since the chitosan, which is a natural high molecular substance, has an amino group, it is present in a cationic state in an aqueous solution, and the biodegraded livestock blood is anionic in an aqueous solution So that chitosan acts as a natural coagulant. Thus, after the amino acid-chitosan complex solution is aggregated with chitosan, the solid solution and the liquid solution can be separated into solid and liquid by performing additional solid-liquid separation as shown in FIG.

The solid-liquid separation can be carried out without particular limitation by a commonly known solid-liquid separation method such as centrifugation, pressure separation and gravity sedimentation separation.

As a result of the solid-liquid separation process, the solid dehydrated cake and the liquid amino acid-chitosan complex solution can be separated to produce an amino acid-chitosan complex solution of the final clear solution as shown in FIG.

From another point of view, the present invention can provide an amino acid-chitosan complex solution prepared by the above-described method.

As described above, the amino acid-chitosan complex solution according to the present invention can solve environmental problems by the radical elimination of livestock blood. In addition, it can be used for organic agricultural products that do not use chemical fertilizers by using natural coagulant that has excellent cohesiveness that can substitute for existing chemical flocculant. In addition, it promotes growth of crops, increases functional ingredients of crops, Management of landscaping, and management of horticultural crops.

In another aspect of the present invention, there is provided a method for preparing a liquid amino acid preparation, comprising the steps of: solubilizing the livestock blood and then decomposing it by a biological method using a complex enzyme consisting of Savinase and Flavourzyme to obtain a liquid amino acid preparation; And reacting the liquid amino acid preparation with a natural flocculant. The present invention also provides a method for producing an amino acid-chitosan complex solution.

As described above, when the solubilized livestock blood is decomposed by a biological method using a complex enzyme consisting of Savinase and Flavourzyme, the enzymes such as Savinase and Flavourzyme, It is preferable to use them in a more complex manner than in the case of using them alone in terms of effectively increasing the biological degradation reaction.

[Example]

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are only for illustrating the present invention and that the scope of the present invention is not construed as being limited by these embodiments.

Example 1 Ultrasonic Processing of Livestock Blood

The livestock blood was collected during the bleeding process, which occurred mostly during the slaughtering process. After collecting the samples, 1L of each sample was kept in the refrigerator for preservation of freshness, and not stored for more than 7 days from the sampling date. Since the livestock blood coagulates from the moment it exits to the outside of the body, the blood is homogenized and pulverized to proceed the ultrasonic pretreatment efficiently. The livestock blood was ground using a cutter type cutter at 10,000 rpm for 10 minutes.

Ultrasonic treatment was performed in a batch reactor in order to elute proteins in blood cells of the crushed livestock blood. First, for the continuous operation of the ultrasonic wave, the metering pump, the inlet and outlet vessels were connected to the reactor, and the ultrasonic oscillator was controlled by fixing a converter and a cooling fan. In order to effectively dissolve organic substances such as proteins in livestock blood, the frequency of protein and the irradiation conditions (density and time) were variously controlled to confirm the protein solubilization ratio according to elution of hemoglobin in blood cells of livestock blood, 1 to 2 and Figs. 2 to 3.

Frequency (kHz) Protein solubilization rate (%)  Unprocessed ultrasonic 92.46 20 96.87 24 94,67 28 94.61

As can be seen from Table 1 and FIG. 2, the protein solubilization ratio of the hematopoietic stem cells in the hematopoietic cells before and after the pretreatment with ultrasound was found to be 92.46 %, Indicating that solubilization of hemoglobin can be proceeded only by pulverization treatment. However, the solubilization ratio of the ultrasound-treated group was higher than that of the untreated group. Therefore, it was confirmed that the ultrasound-based pretreatment was required to efficiently utilize the hemoglobin.

In addition, it was confirmed that protein solubilization ratio was decreased as the frequency of ultrasonic wave increased, and protein solubilization ratio was not considered to be high due to high frequency. Based on the above results, the optimal frequency for ultrasonic treatment was 20 To 28 kHz.

0.1 W / mL 0.2 W / mL 0.3 W / mL 0.4 W / mL 0.5 W / mL 1 W / mL 1.5 W / mL 2 W / mL 0 min 87.68 87.68 87.68 87.68 87.68 87.68 87.68 87.68 10 min 88.72 91.505 89.28 92.355 94.13 89.705 91.94 89.72 20 min 89.415 91.84 91.77 93.15 95.315 92.535 93.24 92.56 30 min 89.665 93.14 92.345 93.465 96.065 92.885 93.545 93.84 40 min 90.295 93.765 92.555 93.855 96.92 93.515 94.08 95.445 50 min 91.1 93.77 92.665 94.02 97.72 94.63 95.545 96.31

As can be seen from Table 2 and FIG. 3, the protein solubilization rate of the hematopoietic stem cells after elution of the hematopoietic cells before and after the pretreatment was examined under various irradiation densities and irradiation times. As a result, The solubilization ratio increased with the increase of the solubilization ratio per hour. However, when the economical factor was taken into consideration, it was confirmed that the most optimum condition was observed for 20 to 40 minutes at 0.1 to 2.0 W / mL, which is the highest increase rate per hour.

≪ Example 2 > Biological degradation of ultrasound-treated livestock blood

As in Example 1, the lysozyme pretreated livestock blood was biodegraded to obtain a liquid amino acid preparation. The proteolytic enzymes Savinase and Flavourzyme were used for biological degradation.

First, 2% by weight of Savinase, 2% by weight of Flavourzyme, 2% by weight of total blood of livestock blood were ultrasonicated in an optimal condition of frequency 20 kHz, irradiation density 0.5 W / mL and irradiation time 30 minutes, ) And 1% by weight of Savinase and 1% by weight of Flavourzyme were added, and the resulting mixture was enzymatically decomposed at 100 rpm and 50 ° C for 4 hours to obtain a liquid amino acid preparation.

Table 3 and FIG. 4 show the results of the biological conversion of the livestock blood before and after the ultrasonication by enzymatic treatment under various conditions and measuring protein conversion.

Unprocessed ultrasonic (%) Ultrasonic pretreatment (%) 2% by weight Savinase < RTI ID = 0.0 > 8.37 11.51 2% by weight Flavourzyme < RTI ID = 0.0 > 5.48 28.25 1% by weight Savinase +
1% by weight Flavorzyme 18.34 53.06

As can be seen in Table 3 and FIG. 4, protein conversion from livestock blood before and after the ultrasonication was 1% by weight of 2% by weight Savinase and 2% by weight Flavourzyme, Protein conversion was significantly higher when the complex enzyme was mixed with Savinase and 1% by weight of flavorzyme.

In addition, the protein conversion rate in the ultrasound - treated group was higher than that in the untreated group, and it was confirmed that the pretreatment with the ultrasound enhanced the solubilization of the protein, thereby affecting the protein degradation efficiently.

<Example 3> Preparation of amino acid-chitosan complex solution

The amino acid-chitosan complex solution was prepared by reacting the liquid amino acid preparation obtained by biodegradation from Example 2 with chitosan as a natural coagulant.

First, the liquid amino acid preparation obtained from Example 2 was injected into a batch reactor, and then chitosan was added at a ratio of 1, 5, 10 and 20 parts by volume based on 100 parts by volume of the liquid amino acid preparation. The mixture of the liquid amino acid preparation and chitosan was rapidly stirred at 60 rpm for 5 minutes and then slowly stirred at 30 rpm for 15 minutes.

It was confirmed that Floc was formed by reacting the liquid amino acid preparation with chitosan. Next, in order to separate the formed flocs, a solid filtrate was obtained by separating solid and liquid by operating for 45 minutes using a membrane filterpress as shown in FIG. 5, Amino acid-chitosan complex solution was prepared.

Experimental Example 1 Measurement of Capillary Inhalation Time (CST) and Filtration Time (TTF)

The chitosan coagulant used in Example 3 was used based on the measurement results of capillary suction time (CST) and filtration time (TTF) in comparison with other chemical coagulants. To measure capillary suction time (CST) and filtration time (TTF), chitosan coagulant and chemical coagulant were added to 100 mL of enzyme digested blood at 5 volume ratio, and the reaction was performed for 30 minutes.

In order to examine the coagulability and dehydratability of chitosan used as a natural coagulant in the preparation of the amino acid-chitosan complex solution according to the present invention, the amount of chitosan used as a natural coagulant was compared with that of C-353P The capillary suction time (CST) and the filtration time (TTF) were measured.

The capillary suction time was measured by the capillary suction pressure (P = 15kPa) applied to the filter paper to measure the filtration ability and condition of the sludge. At this time, the better the dehydration property, the lower the value of the capillary suction time. For capillary suction time (CST), CST equipment (304 series, Kemik Co.) was used and 10 mL of enzyme-degraded blood reacted with coagulant was placed in the horn and the time was measured.

In addition, the filtration time measures the time taken for 50% of the sludge volume to escape. The better the dewaterability, the lower the value of the filtration time. To measure the filtration time (TTF), 25 mL of enzyme-digested blood was added to the Bottle Top Filter (F01-76-055, Thermo) and the filtration rate was measured using a Vaccum pump.

The results of measuring the capillary suction time and the filtration time from the above method are shown in Table 4 below.

analysis content Number of times Coagulant C-353P 860R Chitosan Capillary suction time (s) 10 ml One 693.0 375.3 186.4 2 681.1 374.8 193.2 3 646.7 375.0 190.0 medium 673.6 375.0 189.9 Filtration time (s) 25 ml One 913.04 398.2 310.73 2 944.4 401.85 302.48 3 920.93 419.09 306.11 medium 926.12 406.38 306.44

As shown in Table 4, the chemical coagulants C-353P and 860R showed higher capillary suction time and filtration time than the natural coagulant chitosan. Based on the above results, it was found that when livestock blood was reacted with chitosan, cohesiveness and dehydration were superior to those when chemical coagulant was used.

&Lt; Experimental Example 2 > Spray results of amino acid-chitosan complex solution

The amino acid-chitosan complex solution was prepared by adding 5 parts by volume of chitosan to 100 parts by volume of the amino acid-chitosan complex solution prepared in Example 3, and the solution was sprayed onto the crops to confirm whether or not the promotion of crop growth was affected.

It was not sprayed on the crops but sprayed around the soil and absorbed 1000 times per 10mL of the crops such as eggplant, radish, sesame leaf, onion, drop tomato and grass. Spraying was done once a month and the growth period was checked for at least 6 months.

As a result, as shown in FIG. 7, it was confirmed that the amino acid-chitosan complex solution prepared from the present invention can promote the growth of crops and turf.

While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereto will be. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (9)

Sonicating livestock blood, and then decomposing it into a complex enzyme consisting of Savinase and Flavourzyme to obtain a liquid amino acid preparation; And reacting the liquid amino acid preparation with chitosan,
Wherein the chitosan is added in a volume ratio of 1 to 20 parts by volume with respect to 100 parts by volume of the liquid amino acid preparation and rapidly stirred at 50 to 70 rpm for 3 to 8 minutes and then slowly stirred at 20 to 40 rpm for 10 to 20 minutes. &Lt; / RTI &gt;

delete delete delete delete The method according to claim 1, further comprising a step of reacting the liquid amino acid material with chitosan, followed by solid-liquid separation.
[7] The method of claim 6, wherein the solid-liquid separation is performed by at least one separation process selected from the group consisting of centrifugation, pressure separation, and gravity sedimentation separation.
An amino acid-chitosan complex safflower produced by the method of any one of claims 1, 6, and 7.

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