阅读说明：本技术 利用动物废毛制造可用做有机肥的产物的方法 (Method for producing product capable of being used as organic fertilizer by using animal waste hair ) 是由 张郁欣 蓝伟伦 陈昌成 于 2019-10-30 设计创作，主要内容包括：本发明公开了一种利用动物废毛制造可用做有机肥的产物的方法,主要是收集由动物毛或禽类羽毛集成的原料,利用pH值9以上的碱液溶解形成溶解液,再以弱酸性的酸液缓入中和,过滤筛除未溶物即可得用做有机肥的第一产物；再通过离心沉降、除水等过程,能进一步取得可用做有机肥的其他种类产物,能依需求有效地使用,不仅帮助于提升动物原料的附加经济价值,更能促进植物生长、抗日照、改善土壤等功效。(The invention discloses a method for preparing a product capable of being used as an organic fertilizer by utilizing waste animal hair, which is mainly characterized by collecting raw materials integrated by animal hair or poultry feather, dissolving the raw materials by utilizing alkali liquor with the pH value of more than 9 to form a dissolved solution, slowly neutralizing the dissolved solution by utilizing weak acidic acid liquor, filtering and screening undissolved substances to obtain a first product capable of being used as the organic fertilizer; and through the processes of centrifugal sedimentation, water removal and the like, other products which can be used as organic fertilizers can be further obtained and can be effectively used according to requirements, so that the method not only helps to improve the additional economic value of animal raw materials, but also has the effects of promoting plant growth, resisting sunlight, improving soil and the like.)

1. A method for producing a product which can be used as an organic fertilizer by using animal waste hair is characterized by comprising the following steps:

(a) collecting raw material integrated from animal hair or poultry feather;

(b) putting the raw materials into an alkali solution with the pH value of more than 9, wherein the alkali solution is a potassium hydroxide solution or a sodium hydroxide solution, carrying out hydrolysis reaction at the temperature of below 85 ℃, and continuously stirring for at least 0.5 hour to dissolve the raw materials to form a dissolved solution;

(c) slowly adding a weakly acidic acid solution into the stirred dissolved solution, wherein the acid solution is selected from phosphoric acid, formic acid, acetic acid, sulfuric acid or hydrochloric acid, and the dissolved solution is neutralized to a pH value of 5.0-9.0;

(d) and (4) screening out undissolved substances in the solution after neutralization in the step (c) by using a sieve with 20-50 meshes, and collecting filtrate to obtain a first product which can be used as an organic fertilizer.

2. The method of claim 1, further comprising:

(e) and (d) centrifugally settling the first product obtained in the step (d), and collecting supernatant after settling to obtain a second product which can be used as an organic fertilizer.

3. The method of claim 1, further comprising:

(e) and (d) centrifugally settling the first product obtained in the step (d), and collecting the settled precipitate to obtain a third product which can be used as an organic fertilizer.

4. The method of claim 1, further comprising:

(e) and (d) dehydrating and concentrating the first product obtained in the step (d) into powder, and collecting the powder to obtain a fourth product which can be used as an organic fertilizer.

5. The method of claim 2, further comprising:

(f) and (e) dehydrating and concentrating the second product obtained in the step (e) into powder, and collecting the powder to obtain a fourth product which can be used as an organic fertilizer.

6. The method of any one of claims 1 to 5, wherein the raw material of step (a) is selected from duck feathers, goose feathers or chicken feathers of poultry feathers.

7. The process of any of claims 1 to 5, wherein the weight ratio of the feedstock to the lye of step (b) is in the range of from 1: 5-1: 20.

8. The process according to any one of claims 1 to 5, wherein the alkaline solution in step (b) is a potassium hydroxide solution having a concentration of 2 to 10% (solid alkali content in water).

9. The method according to any one of claims 1 to 5, wherein the hydrolysis reaction in step (b) is carried out at a temperature of 60 to 80 ℃ and the stirring is continued for 0.5 to 4 hours.

10. The method according to any one of claims 1 to 5, wherein the acid solution in step (c) is a phosphoric acid solution, and is gradually added dropwise into a continuously stirred solution at a rotation speed of 100 to 300 rpm.

Technical Field

The invention relates to preparation of agricultural nutrients and recycling of animal waste raw materials, in particular to a product and a method capable of preparing keratin-containing industrial waste animal raw materials into organic fertilizer, nutritional agents or sun-screening agents and the like, which are beneficial to saving space and cost of industrial waste, promoting plant growth and improving soil.

Background

In recent hundred years, human pursuit progress and prosperity, utilize nature unconsciously, such as excessive development of land, pollution of various ecological environments, water resource scarcity, etc., even in intensive agriculture, use chemical fertilizer in a large amount, cause soil salt damage, acidification, make the human living environment worsen, the agricultural production also produces the problem along with, have already caused the world to have great worry; therefore, in recent years, improvement of agricultural environment and promotion of sustainable economy are important and targeted for government administration of various countries.

However, organic fertilizers with good performance and low price are rarely seen in the market, and the organic fertilizers which are suitable for the growth of soil microorganisms and can increase the fertility of soil are often higher in price than chemical fertilizers and are difficult to be widely utilized. As for the composting of livestock manure, the content ratio of nitrogen, phosphorus and potassium nutrients of different composts is difficult to predict, the poor growth of crops caused by uneven nutrients is generally caused by direct application, and most crop growers cannot breed a large amount of livestock and are difficult to produce the composts by themselves.

In addition, in the agricultural production areas with warm climate and changeable climate types, crops are easy to burn due to sunlight at high temperature and high solar radiation amount, holes and wounds which can be invaded by plant pathogenic bacteria are formed, and the yield and the quality are greatly influenced; at present, calcium carbonate materials and mixed resin are mostly used in agriculture, the mixture is sprayed on the surface of crops to serve as an anti-UV protective agent for preventing burning sun burning, but the method needs to clean a powder layer on the surface of the fruits in a dry brushing mode after the fruits are harvested and before the fruits are sold, and if the powder layer is covered thickly, the number of brushes or the dry brushing frequency needs to be increased for cleaning the powder layer, so that the fermentation of the surfaces of the fruits due to mechanical damage is promoted, the quality guarantee is influenced, and the commodity value is also influenced.

Therefore, improving the quality of the organic fertilizer and reducing the preparation cost are always the key points of research of manufacturers in related fields; although the slow-release urea fertilizer proposed in chinese patent No. 100384790 and its preparation method are known to have the characteristics of using animal keratin to prepare fertilizer, the preparation process is not deficient, such as the process from water washing to neutrality, and the loss of a large amount of water-soluble amino acids, i.e. a large amount of nutrients available for plants are wasted, and the finally produced keratin powder is difficult to be degraded by microorganisms in soil in a short time, and the fertilizer "urea" must be applied to accelerate decomposition, which causes inconvenience in application.

In view of the above, the present inventors have made extensive studies on effective reuse of waste animal materials and gain added value, and have completed the present invention through continuous experiments and studies.

Disclosure of Invention

The main purpose of the invention is to recycle the industrial waste animal raw material containing keratin, save the space of industrial waste, improve the environment, prepare the product which can be used as organic fertilizer by recycling low cost, and the obtained product can be directly used or used in a mode of being prepared and used as organic fertilizer, nutrient or sun-screening agent and the like, and can promote the growth of plants and improve the soil or resist light damage.

The invention mainly utilizes the industrial waste animal hair or bird feather, which can be used as a nutrient source rich in amino acid for plants to directly utilize after hydrolysis treatment, and utilizes the aromatic amino acid to help light absorption and absorb and filter ultraviolet rays (UVB and UVC) harmful to organisms.

The invention relates to a method for preparing a product capable of being used as an organic fertilizer by utilizing animal waste hair, which mainly comprises the following steps:

(a) collecting raw material integrated from animal hair or poultry feather; animal hair such as hair, wool, pig hair, cow hair and the like, poultry feather such as chicken feather, duck feather, goose feather, waterfowl and the like or down feather are preferably selected in practice, and the organic fertilizer with economic value can be prepared by using the waste hair containing keratin protein as a raw material after pretreatment processes such as flushing blood with clear water, dehydrating, drying, disinfecting and the like.

(b) Hydrolyzing the above raw materials by placing into alkaline solution with pH value above 9, and using alkaline reaction to destroy protein structure of animal fiber, break ionic bond and destroy disulfide bond, so as to hydrolyze protein into polypeptide; wherein, the alkali liquor can be potassium hydroxide solution or sodium hydroxide solution, but potassium hydroxide is preferred, and potassium component in the three elements of the fertilizer is obtained; the solubility of the hydrolysis reaction is increased along with the heating temperature, but the temperature is controlled below 85 ℃ to avoid the thermal denaturation of the protein; during hydrolysis reaction, because the feather density is low and is not easy to be soaked by alkali liquor, more than 90% of the raw materials are dissolved by continuously stirring for 0.5-4 hours to form a dissolved solution.

(c) Slowly adding a weakly acidic acid solution into the stirred solution to neutralize the pH value of the solution to 5.0-9.0, wherein the pH value is suitable for crops; wherein, the acid solution can be selected from phosphoric acid, formic acid, acetic acid, sulfuric acid or hydrochloric acid, but phosphoric acid is preferred, and besides organic components in the phosphoric acid, phosphate can be obtained, and the phosphate is one of three elements of the fertilizer; during neutralization treatment, acid solution prepared into weak acid is gradually dripped into continuously stirred dissolving solution, the stirring speed is preferably 100-300 rpm, and irreversible denaturation of protein caused by severe acid-base reaction is avoided to generate coagula.

(d) The undissolved substances (undissolved feathers, other solid impurities and the like) in the neutralized solution are screened out by using 20-50 meshes (the pore size is equivalent to 0.3-0.85 mm), and the filtrate is collected to obtain the feather keratin solution, which is the first product of the organic fertilizer, has wider molecular weight distribution and wide applicability, can be used as organic fertilizer, nutrient or sun-screening agent and other products, but can be directly used as fertilizer or nutrient, and is keratin amino acid quick-acting fertilizer.

According to the first product obtained in the above-mentioned step, it can be further undergone the process of centrifugal sedimentation treatment, and the supernatant liquor and precipitate after sedimentation can be respectively collected; the collected supernatant is a keratin peptide solution, is a second product which can be used as an organic fertilizer, has good hydrophilicity and small molecular weight, is polypeptide, has the same function and better sunlight resistance compared with a first product with wider molecular weight, is suitable for being used as a nano nutrient and a sun-screening agent to be sprayed on crops, can be absorbed and grown by the crops, can form a transparent film layer with UV resistance for preventing sunlight irradiation, cannot obstruct photosynthesis and respiration of the plants, and does not influence flowering and pollination; the collected precipitate is keratin precipitate, which is the third product of the present invention and may be used as organic fertilizer.

According to the first product or the second product obtained in the above steps, the invention can further carry out water removal treatment, and different preservation modes are formed through the processes of concentration and drying; in the process, a liquid first product or a liquid second product is subjected to concentration treatment and drying treatment, the volume of water is reduced to form powder, the concentration treatment mainly adopts a rotary reduced pressure concentration mode, the drying treatment adopts a spray drying or freeze drying mode, the water in the first product or the second product is removed to form powder, and the powder is collected to obtain the solid keratin powder.

In the above step, the weight ratio of the selected raw materials to the alkali liquor is 1: preferably 5-1: 20; the alkali liquor can be prepared by adopting solid alkali, and potassium hydroxide solution with the concentration of 2-10% (the content of the solid alkali in water) is preferably used; the temperature of the hydrolysis reaction is preferably 60-80 ℃, and the dissolution rate can reach 98%.

Through practical analysis, each keratin-rich product which can be used as an organic fertilizer or a crop sunscreen agent and contains 15-20% of organic matters, 2-4% of total nitrogen, 0.8-2.8% of total phosphoric anhydride, 1-5% of total potassium oxide and other components which are beneficial to crop growth and soil improvement; taking the second product keratin peptide solution as an example, the absorption intensity of the formed transparent film layer is detected by a UV-Vis spectrometer, the absorption value (Abs) is detected, the absorption value below the UV ultraviolet wavelength 320nmu is 4, and the absorption value between the UV ultraviolet wavelength 340nm and 320nm is 1-4; in addition, the first product, a keratin solution, is a mixture of the second product and the third product, also having a slightly weaker light absorption than the second product, while the fourth product, a dry (powder) of the first product or the second product, after redissolving, also has a light absorption equal to that of the first product or the second product.

In order to make the aforementioned objects, functions and features of the present invention more comprehensible, preferred embodiments accompanied with flow charts are as follows:

drawings

FIG. 1 is a block diagram of the preparation process of the present invention.

Description of the symbols:

S01-S06

A1 first product

A2 second product

A3 third product

A4 fourth product

B filtered material

Detailed Description

In the invention, in order to effectively utilize industrial waste animal raw materials to improve added value, the characteristics of high-efficiency mass production and low cost are basic requirements, the used equipment can meet the requirements of the whole process, the reaction tank, the centrifuge and the filter can be combined into a whole, more than 200 kilograms of feather materials can be put into each batch, although the reaction time is short through medicament and temperature control, the process is not required to be responded by most equipment, the mechanism is simple, the cleaning and the maintenance are convenient, and the personnel cost can be reduced by matching with an automatic control system. The main equipment is a reaction tank, in which an inner tank capable of relatively rotating is arranged, and the inner tank is equipped with a plurality of sieve holes (the size is about 20-50 meshes, and the pore diameter is about 0.3-0.85 mm), and is also equipped with a temperature control system for heating and raising temperature and a driving system for driving the inner tank to rotate.

In operation, as shown in fig. 1, the method of the present invention first performs the related operations of step S01, preparation and pretreatment. Wherein, the raw materials selected for the preparation of the raw materials can be the collection of animal hair or poultry hair, and the slaughtered poultry feather is preferably selected, such as duck feather, goose feather and chicken feather, wherein the raw materials contain sufficient animal fibers and can become organic fertilizers with economic value; the method comprises the steps of collecting waste raw materials (animal waste hair) from slaughterhouses or farms and the like, and then carrying out pretreatment such as flushing blood with clear water, dehydrating, drying, disinfecting and the like to obtain the raw materials with a little cutin, excrement and soil sand.

Then, the alkali treatment of step S02 is performed by preparing a corresponding alkali solution in the reaction tank, wherein the weight ratio of the raw material to the alkali solution is 5-20%, the alkali used for preparing the alkali solution is water-soluble, the concentration of the alkali used for preparing the alkali solution is controllable to 2-10% (the content of solid alkali in water), and sodium hydroxide or potassium hydroxide is usually used, but potassium hydroxide is preferred, so that the prepared product contains potassium; the pH of the prepared alkaline solution should be greater than 8, but is preferably set to be above 9 (generally, animal fibers are damaged in an alkaline solution with a pH of 8, and an alkaline solution with a pH of 12 can strongly destroy the fiber structure) so as to break ionic bonds and destroy disulfide bonds, so that proteins are hydrolyzed into polypeptides.

After the alkali liquor is prepared, putting raw materials in a proper proportion into the alkali liquor (putting into an inner groove), heating to a reaction temperature, driving the inner groove to rotate to form continuous stirring, fully soaking the raw materials in the alkali liquor for hydrolysis reaction, maintaining for 0.5-4 hours, and dissolving more than 90% of the raw materials to form a dissolved solution; the solubility is increased along with the reaction temperature, the dissolution time is shortened, but the reaction temperature is controlled below 85 ℃ to avoid the thermal denaturation of protein, the optimal temperature can be controlled between 60 ℃ and 80 ℃, the maximum rate of dissolution can reach 98 percent, and the raw materials are dissolved more thoroughly.

As for the raw materials of feather, because the surface of the feather is covered with sterol (sterol) and triphosphate (triphosphate ester), the feather has water repellency, low density, large volume and hard feather stem in the middle, and is not easy to be soaked under the liquid level, so that the hydrolysis can be carried out in a one-time input or continuous input mode; the one-step feeding is that quantitative raw materials and alkali liquor are sequentially fed into a reaction tank, after the outer cutin is damaged and softened by steaming and boiling for 30 minutes, the feather is stirred to be pressed below the liquid level of the alkali liquor, and the feather is soaked for 0.5 to 4 hours at constant temperature; the continuous feeding is to divide the feather into a small amount of feather which is continuously fed into the constant-temperature alkali liquor for many times, and continuously stir the feather until the feather is soaked in the alkali liquor to be dissolved.

After the raw materials are dissolved for a certain time (more than 90 percent of the raw materials are dissolved), the step S03 neutralization treatment is carried out, namely weakly acidic acid liquor is slowly added into the continuously stirred dissolving solution, and the pH value of the dissolving solution is neutralized to 5.0-9.0; in this neutralization step S03, the solution is neutralized mainly with an acid to an acid-base range suitable for plants, pH 5.0 or more and 9.0 or less, and a common acid such as formic acid, acetic acid, sulfuric acid, hydrochloric acid, phosphoric acid can be used, but preferably phosphoric acid, and phosphoric acid is used, and in addition to an organic component, a phosphate salt is present, which is one of three elements of a fertilizer. In practical operation, the acid solution is adjusted to weak acid, the weak acid is added into the stirred dissolving solution drop by drop to reduce the pH value, the stirring speed is preferably 100-300 rpm, and the irreversible denaturation of the protein caused by the violent strong acid and strong base neutralization is avoided to generate coagulants.

After the neutralization is finished, filtering in step S04, and screening undissolved substances (such as the undissolved raw materials and solid impurities such as coagulates) in the solution after the neutralization by using sieve holes (20-50 meshes) opened in an inner groove in the reaction tank; after the filter B is removed by screening, the obtained filtrate, namely feather keratin solution, is a first product A1 which can be used as an organic fertilizer, has wider molecular weight distribution and wider applicability, can be directly or further used for products such as organic fertilizers, nutritional agents or sun-screening agents, and can be directly used as fertilizers in practice to be keratin amino acid quick-acting fertilizers.

The first product A1 can be directly used as a quick-acting fertilizer, and can be further processed to obtain more products which can be used as organic fertilizers; as shown in the figure, step S05 is performed, the obtained first product is subjected to centrifugal sedimentation treatment, and the settled supernatant and precipitate are respectively collected, the collected supernatant is a keratin peptide solution, which is a second product a2 that can be used as an organic fertilizer of the present invention, has good hydrophilicity and small molecular weight, is polypeptide, has more excellent sun-proof effect, is practically suitable to be used as a nano nutrient and a sun-proof agent, and is sprayed on crops to form a transparent film layer, so that the film layer has the UV resistance and the sun-proof property, can not only provide the crop nutrition, but also does not block the photosynthesis and respiration of the plants, and does not influence flowering pollination; the collected precipitate is keratin precipitate, is a third product A3 which can be used as an organic fertilizer, is more hydrophobic and has large molecular weight, and is practically applied to soil to be used as a long-acting fertilizer.

In addition, the first product A1 and the second product A2 obtained in the invention can also be subjected to water removal treatment to obtain other products which can be used as organic fertilizers, and the products are preserved in different forms; as shown in the figure, step S06 is performed to perform dewatering processes such as concentration and drying on the liquid first product or second product, so as to reduce the volume of moisture and form powder, the concentration process mainly adopts a rotary reduced pressure concentration mode, the drying process adopts a spray drying or freeze drying mode, moisture in the first product or second product is removed to form powder, and the powder is collected to obtain solid keratin powder.

In the following, several preferred embodiments of the invention are illustrated:

the first embodiment is as follows:

step S01, preparing materials and preprocessing, unhairing from duck farm and local regulation program, cleaning, drying and sterilizing, and collecting feather as raw material.

Step S02, performing an alkali treatment process, adding 1 liter of 5.6% (1mol/L) potassium hydroxide solution into a reaction tank, continuously injecting 200 g of duck feather raw material, and adding the feather raw material while stirring to wet the surface of the feather with the potassium hydroxide solution; the solution is heated and kept at the constant temperature of 80 ℃ and stirred for about 2 hours, so that more than 90 percent of feathers are dissolved to form a dissolved solution.

Step S03, neutralization treatment is performed, a 0.1M phosphoric acid solution is prepared, and added dropwise to the stirred solution obtained in step S02, and the alkaline solution is neutralized to pH 8.

And step S04, performing filtration treatment, namely extracting air by using a screen with a 30-mesh sieve mesh to filter the dissolved solution, and filtering out a filter B (undissolved raw materials, solid impurities and the like) larger than the sieve mesh to obtain a first product A1 (keratin dissolved solution) which can be used as a keratin amino acid quick-acting fertilizer.

Step S05, carrying out centrifugal sedimentation treatment, centrifuging the first product A1 by a conventional method to obtain a supernatant and a precipitate, wherein the supernatant is a second product A2 (keratin peptide solution) and can be used as a quick-acting fertilizer, and the precipitate is a third product A3 (keratin) and can be used as a long-acting fertilizer.

Step S06, performing a water removal treatment; firstly, a rotary decompression concentrator is used, the temperature of a water bath is 80 ℃, and the volume of water in a solvent (a first product A1 or a second product A2) is reduced by 50%; drying with a common freeze dryer at a condensation temperature of-40 deg.C to-50 deg.C, a vacuum value of 5-6 mTorr, and a shelf temperature of 10-20 deg.C to obtain a fourth product A4 (keratin powder), which is water-soluble and can be redissolved in water, and can be used as keratin solid fertilizer, or mixed with other plant growth regulator or fertilizer.

Example two:

step S01, preparing materials and preprocessing, unhairing from chicken farm and local regulation program, cleaning, drying and sterilizing, and collecting feather as raw material.

Step S02, alkali treatment process, wherein 200 g of chicken feather material is put into the reaction tank, and then 2 l of 8.4% potassium hydroxide solution is added. Adding a potassium hydroxide solution while wetting the surface of the feather with the potassium hydroxide solution via stirring; the solution was heated and held at 80 ℃ and stirred for about 0.5 hour to dissolve more than 90% of the feathers, forming a solution.

Step S03, neutralization treatment is performed, a 0.1M phosphoric acid solution is prepared, and the solution is added dropwise to the stirred solution obtained in step S02 to neutralize the alkaline solution to pH 7.

And step S04, performing filtration treatment, namely extracting air by using a screen with a 30-mesh sieve mesh to filter the dissolved solution, and filtering out a filter B (undissolved raw materials, solid impurities and the like) larger than the sieve mesh to obtain a first product A1 (keratin dissolved solution) which can be used as a keratin amino acid quick-acting fertilizer.

Step S05, carrying out centrifugal sedimentation treatment, centrifuging the first product A1 by a conventional method to obtain a supernatant and a precipitate, wherein the supernatant is a second product A2 (keratin peptide solution) and can be used as a quick-acting fertilizer, and the precipitate is a third product A3 (keratin) and can be used as a long-acting fertilizer.

Step S06, performing a water removal treatment; firstly, a rotary decompression concentrator is used, the temperature of a water bath is 80 ℃, and the volume of water in a solvent (a first product A1 or a second product A2) is reduced by 50%; drying with a common freeze dryer at a condensation temperature of-40 deg.C to-50 deg.C, a vacuum value of 5-6 mTorr, and a shelf temperature of 10-20 deg.C to obtain a fourth product A4 (keratin powder), which is water-soluble and can be redissolved in water, and can be used as keratin solid fertilizer, or mixed with other plant growth regulator or fertilizer.

According to the operation process of the invention, various products rich in organic substances such as keratin and the like can be obtained from industrial waste animal raw materials, so that the products can be directly used as organic fertilizers or mixed with other regulators or fertilizers, the products prepared by using waste materials at low cost can be reused for crop plants, the growth of the plants is promoted, the soil is improved, the added value of the waste animal raw materials can be greatly improved, the invention is helpful for improving the industrial economic benefit, and the application of the method is provided.

The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and all extensions, modifications, simple changes and equivalents made by the technical means of the present invention should fall within the scope of the claims of the present invention.