Bovine woolskin biomass organic fertilizer and preparation method thereof

Abstract

The invention discloses a cattle woolskin biomass organic fertilizer and a preparation method thereof, and belongs to the technical field of compound fertilizers, aiming at main components of cattle and sheep corpses and furs, the project adopts a method of combining biological enzymolysis and microbial zymophyte hydrolysis to perform harmless and resourceful treatment on the corpses and furs, so that efficient utilization of resources is realized; the prepared cow wool skin biomass organic fertilizer has high nutrition, can promote crop growth, and can reduce the content of heavy metals in soil; activated cow wool skin biomass powder is used as a matrix, the surface of the matrix is loaded with an iron-based metal framework, the surface porosity and roughness of biomass can be remarkably improved, the biomass can be endowed with the heavy metal chelating capacity through the iron-based metal framework, and the influence of heavy metal on crops is avoided.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of compound fertilizer, and particularly relates to a biomass organic fertilizer for cow and sheep skins and a preparation method thereof. BACKGROUND

[0002] There is a lack of perfect corpse processing facilities in Haiyan County, and corpses are basically buried or burned. Previously, skin resources were mainly used to prepare leather, but with the increasingly prominent environmental problems in recent years, the leather market is bleak, and the utilization rate of skin resources is not high. At present, the purchase price of sheepskin is about 3-10 yuan per piece, and the purchase price of cowhide is about 20-90 yuan per piece, which leads to low enthusiasm of breeders in pretreatment of cow and sheep skins, and the cow and sheep skins are directly discarded. Burial of cow and sheep corpses requires a large site and cannot completely process the corpses, which can easily damage the environment; the burning method can easily cause secondary pollution to the air, and finally cause environmental pollution; the corpses and skins are randomly discarded, which produces a foul odor, breeds mosquitoes and flies in summer, and pollutes rivers, lakes and underground water after rainwater washing, which endangers human health. In addition, the corpses and skins are rich in organic matter, protein and oil, and direct discarding and burial of the corpses and skins causes waste of resources.

[0003] Therefore, it is necessary to harmlessly and resourcefully process the cow and sheep corpses and skins in Haiyan County, solve the environmental problems and effective utilization of resources, and currently, the cow and sheep corpses and skins are processed by various methods. The burial method requires a large site and has potential hazards to underground water; the burning method produces dust and gas, which can easily cause secondary pollution to the air; the chemical preparation method and the fermentation method can completely process the animal corpses and skins and have high product added value, such as meat and bone meal, animal oil or organic fertilizer, and do not pollute the environment, and are the current trend of harmless processing of corpses and skins. However, the two methods have a long period and occupy a large site. SUMMARY

[0004] The application aims to provide a biomass organic fertilizer for cow and sheep skins and a preparation method thereof, and the biomass organic fertilizer for cow and sheep skins has high nutrition, can promote crop growth, and can reduce the content of heavy metals in soil.

[0005] The application can be achieved by the following technical scheme.

[0006] A preparation method of a biomass organic fertilizer for cow and sheep skins comprises the following steps:

[0007] Step one: after the cattle and sheep carcasses and hides are sterilized by potassium hydroxide, they are subjected to enzymatic hydrolysis by heat-resistant bacillus, protease K and alkaline protease to obtain bones and filtrate, then the bones are dried and ground to obtain cattle and sheep hide biomass powder; the filtrate is treated by a filter press to obtain mixed nutrients.

[0008] Step two: the cattle and sheep hide biomass powder is calcined to obtain pretreated biomass, and then the pretreated biomass is treated by a potassium hydroxide solution to obtain activated cattle and sheep hide biomass powder.

[0009] Step three: the activated cattle and sheep hide biomass powder is used as a carrier surface to hydrothermally synthesize an iron-based metal framework containing amino groups to obtain composite cattle and sheep hide biomass powder.

[0010] Step four: after polymerization, the acrylic acid is esterified with humic acid under the action of triethylamine, and the molecular chains are intertwined to obtain a humic acid interpenetrating composite.

[0011] Step five: the composite powder is prepared by amidation reaction between the carboxyl groups contained on the surface of the humic acid interpenetrating composite and the amino groups on the surface of the composite cattle and sheep hide biomass powder; the composite powder and the mixed nutrients are stirred and mixed at a mass ratio of 5:3 to obtain cattle and sheep hide biomass organic fertilizer.

[0012] Further, the specific preparation steps of the cattle and sheep hide biomass powder are as follows:

[0013] The cattle and sheep carcasses and hides are cut into blocks of 5-6 cm 3 in size, transferred to a reaction kettle, then deionized water and potassium hydroxide are added to adjust the pH value to 8-9, steam is introduced into the reaction kettle, heated to 100-110℃, and kept for 30-40 min to kill the spoilage bacteria and pathogenic bacteria on the carcasses and hides, then cooled to 50-60℃, then 2.2-2.4 x 10 9 CFU / g of heat-resistant bacillus are added, then protease K is added, and stirring is continued for 45-48 h, after the reaction is completed, alkaline protease is added, and stirring is continued for 24-26 h, then filtration is performed to separate the bones and the filtrate, the bones are dried and ground to obtain cattle and sheep hide biomass powder.

[0014] Further, the usage ratio of the cattle and sheep carcasses, hides, deionized water, potassium hydroxide, heat-resistant bacillus, protease K and alkaline protease is 80-90 g:20-30 g:500-600 mL:8-10 g:0.5-0.7 g:0.6-0.8 g:0.6-0.8 g.

[0015] Further, the specific preparation steps of the mixed nutrients are as follows:

[0016] After the filtrate is processed by a filter press, the fine ash solids are separated from the soluble matter to obtain mixed nutrients.

[0017] Furthermore, the specific preparation steps for activated bovine and sheepskin biomass powder are as follows:

[0018] After drying the cow and sheep wool biomass powder in a drying oven at 68-70℃ for 1-2 hours, it is placed in a tube furnace with argon gas at a flow rate of 48-50 cm / min and heated to 580-600℃. The reaction is continued for 90-100 minutes to obtain pretreated biomass. The pretreated biomass and a 50-60% potassium hydroxide solution are stirred and mixed at a ratio of 30-40 g: 150-200 mL for 28-30 hours. The mixture is then dried in a drying oven at 68-70℃ for 20-22 hours. After drying, it is placed in a tube furnace with argon gas at a flow rate of 48-50 cm / min and heated to 840-900℃. The reaction is continued for 90-100 minutes, and the mixture is allowed to cool naturally to obtain activated cow and sheep wool biomass powder.

[0019] Furthermore, the specific preparation steps for the composite bovine and sheepskin biomass powder are as follows:

[0020] A solution of 2,5-diaminoterephthalic acid and N,N-dimethylformamide was added to a polytetrafluoroethylene-lined autoclave and stirred for 30-50 minutes at 20-25°C and 500-600 r / min. Then, ferric chloride and activated bovine and sheepskin biomass powder were added, and the mixture was heated to 120-130°C and reacted for 24-26 hours. The mixture was then allowed to cool naturally to room temperature, filtered, and the filter cake was washed 2-4 times with methanol solution and deionized water, respectively. The cake was then vacuum dried at 60-70°C for 1.5 hours to obtain composite bovine and sheepskin biomass powder.

[0021] Furthermore, the ratio of 2,5-diaminoterephthalic acid, N,N-dimethylformamide solution, ferric chloride, and activated bovine and sheepskin biomass powder is 85-90g:750-800mL:35-40g:55-60g.

[0022] Furthermore, the specific preparation steps of the humic acid interpenetrating complex are as follows:

[0023] Humic acid powder, an acrylic acid solution with a neutralization degree of 50-65%, and deionized water were added to a reaction vessel. Nitrogen gas was introduced for protection, and the reaction was stirred at 80-95℃ and 500-600 r / min for 1-2 h. After cooling to 50-60℃, ammonium persulfate as an initiator and hydroxymethylacrylamide as a crosslinking agent were added to the reaction vessel, and stirring was continued for 1-2 h. Then, triethylamine as a catalyst was added, and stirring was continued for 1-2 h. The mixture was filtered, and the filter cake was washed 2-4 times with deionized water and anhydrous ethanol, respectively. The mixture was then vacuum dried at 60-70℃ for 1-2 h to obtain the humic acid interpenetrating complex.

[0024] Furthermore, the ratio of humic acid powder, acrylic acid solution, deionized water, ammonium persulfate, hydroxymethylacrylamide, and triethylamine is 40-50g: 100-120mL: 2-3L: 2-3g: 1-2g: 2-3g.

[0025] Furthermore, the specific preparation steps of the composite powder are as follows:

[0026] The composite bovine and sheepskin biomass powder, anhydrous ethanol, and deionized water were added to a reaction vessel and stirred for 10-12 minutes at 60-70℃ and 500-600 r / min. Then, the humic acid interpenetrating complex and N,N'-dicyclohexylcarbodiimide were added, and stirring was continued for 8-9 hours. The mixture was filtered, and the precipitate was washed 2-4 times with deionized water and anhydrous ethanol. The precipitate was then vacuum dried at 60-70℃ for 1-2 hours to obtain the composite powder.

[0027] Furthermore, the ratio of compound cow and sheep wool biomass powder, anhydrous ethanol, deionized water, humic acid interpenetrating complex and N,N'-dicyclohexylcarbodiimide is 50-60g: 120-140mL: 400-500mL: 15-20g: 2-3g.

[0028] The beneficial effects of this invention are:

[0029] 1. The bovine and sheep wool biomass organic fertilizer prepared by this invention uses bovine and sheep carcasses and wool as raw materials. It adopts a combination of biological enzymatic hydrolysis and microbial fermentation hydrolysis for harmless and resource-based treatment, thereby achieving efficient utilization of resources. The prepared bovine and sheep wool biomass organic fertilizer is highly nutritious, can promote crop growth, and can reduce the content of heavy metals in the soil.

[0030] 2. This invention utilizes proteinase K for efficient and rapid enzymatic hydrolysis and degradation of collagen in hides and keratin in hair; it employs alkaline protease in conjunction with proteinase K to further enhance protein decomposition in hides; proteinase K and alkaline protease exhibit high efficiency and speed in the enzymatic hydrolysis of protein components in tissues, organs, and blood of cattle and sheep carcasses; it utilizes thermoresistant Bacillus fermentation, synergistically with protease hydrolysis, to promote the effective degradation of carcasses and hides; and after the filtrate is processed by a filter press, fine ash solids and soluble matter are separated, and the main products of the resulting mixed nutrients are protein hydrolysates—small peptides and amino acids, which can significantly promote crop growth as nutrients.

[0031] 3. The bovine and sheepskin biomass organic fertilizer of the present invention uses activated bovine and sheepskin biomass powder as a matrix and loads an iron-based metal skeleton on the surface, which can significantly increase the surface porosity and roughness of the biomass. Furthermore, the iron-based metal skeleton can endow the biomass with the ability to chelate heavy metals, thus avoiding the impact of heavy metals on crops.

[0032] 4. The composite powder of the present invention undergoes an amidation reaction between a humic acid interpenetrating complex and a composite cow and sheep wool biomass powder, resulting in a stable composite. Humic acid can react chemically with minerals in the soil to form stable soil aggregates, thereby improving soil structure and making the soil looser. Humic acid has good hydrophilicity, and the physical structure formed by the original intermolecular forces is easily destroyed after absorbing water. The interpenetrating structure and the fixing effect of the composite cow and sheep wool biomass powder can help maintain the original physical structure, allowing it to better maintain its structure after absorbing water, thus improving its service life and stability. Attached Figure Description

[0033] Figure 1 This is a diagram of the enzymatic hydrolysis process of wool.

[0034] Figure 2 This is a diagram showing the effect of enzymatic hydrolysis of wool.

[0035] Figure 3 This is a diagram showing the degradation of woolly sheepskin.

[0036] Figure 4 This is a diagram showing the degradation of hairy cowhide.

[0037] Figure 5 This is a diagram showing the detection of decomposition products from cowhide.

[0038] Figure 6 This is a graph showing the detection of decomposition products of sheepskin. Detailed Implementation

[0039] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0040] Example 1: A method for preparing a cow and sheep wool biomass organic fertilizer, comprising the following steps:

[0041] S1: Cut 80g of cattle / sheep carcasses and 20g of fur into 5cm pieces. 3 The small, block-shaped pieces were transferred to a reaction vessel, then 500 mL of deionized water and 8 g of potassium hydroxide were added. The pH was adjusted to 8, steam was introduced into the reaction vessel, and the mixture was heated to 100°C and kept at that temperature for 30 minutes to kill any putrefactive bacteria and pathogens on the carcass and fur. The temperature was then lowered to 50°C, and 0.5 g of a mixture with an effective viable count of 2.2 × 10⁻⁶ bacteria was added. 9 CFU / g of thermostable Bacillus was added, followed by the addition of 0.6g of proteinase K (enzyme 1), and stirring was continued for 45 hours. After the reaction was completed, 0.6g of alkaline protease (enzyme 2) was added, and stirring was continued for 24 hours. The mixture was filtered to separate the bone from the filtrate. The bone was dried and ground to obtain cow and sheep wool biomass powder. The filtrate was processed by a filter press to separate the fine ash solids from the soluble matter, resulting in a mixed nutrient solution.

[0042] S2: After drying the cow and sheep wool biomass powder in a drying oven at 68°C for 1 hour, place it in a tube furnace, introduce argon gas at a flow rate of 48 cm / min, heat to 580°C, and continue the reaction for 90 minutes to obtain pretreated biomass; mix 30 g of pretreated biomass with 150 mL of 50% potassium hydroxide solution for 28 hours, then dry it in a drying oven at 68°C for 20 hours, and then place it in a tube furnace, introduce argon gas at a flow rate of 48 cm / min, heat to 840°C, and continue the reaction for 90 minutes, and then cool naturally to obtain activated cow and sheep wool biomass powder.

[0043] S3: Add 85g of 2,5-diaminoterephthalic acid and 750mL of N,N-dimethylformamide solution to a polytetrafluoroethylene-lined autoclave. Stir for 30min at 20℃ and 500r / min. Then add 35g of ferric chloride and 55g of activated bovine and sheepskin biomass powder. Heat to 120℃ and continue the reaction for 24h. Cool naturally to room temperature, filter, and wash the filter cake twice with methanol solution and deionized water, respectively. Dry under vacuum at 60℃ for 1.5h to obtain composite bovine and sheepskin biomass powder.

[0044] S4: Add 40g of humic acid powder, 100mL of acrylic acid solution with a neutralization degree of 50% and 2L of deionized water to a reaction vessel, purge with nitrogen for protection, and stir at 80℃ and 500r / min for 1h. Cool to 50℃, add 2g of ammonium persulfate as an initiator and 1g of hydroxymethylacrylamide as a crosslinking agent to the reaction vessel, and continue stirring for 1h. Then add 2g of triethylamine as a catalyst, and continue stirring for 1h. Filter, wash the filter cake twice with deionized water and anhydrous ethanol, respectively, and dry under vacuum at 60℃ for 1h to obtain the humic acid interpenetrating complex.

[0045] S5: Add 50g of compound bovine and sheep wool biomass powder, 120mL of anhydrous ethanol and 400mL of deionized water to a reaction vessel, stir for 10min at 60℃ and 500r / min, then add 15g of humic acid interpenetrating complex and 2g of N,N'-dicyclohexylcarbodiimide, continue stirring for 8h, filter, wash the precipitate twice with deionized water and anhydrous ethanol, and vacuum dry at 60℃ for 1h to obtain the compound powder; mix the compound powder and mixed nutrients at a mass ratio of 5:3 to obtain bovine and sheep wool biomass organic fertilizer.

[0046] Example 2: A method for preparing a cow and sheep wool biomass organic fertilizer, comprising the following steps:

[0047] S1: Cut 85g of cattle / sheep carcasses and 25g of fur into 5.5cm pieces. 3 The small, block-shaped pieces were transferred to a reaction vessel, then 550 mL of deionized water and 9 g of potassium hydroxide were added. The pH was adjusted to 8.5, steam was introduced into the reaction vessel, and the mixture was heated to 105°C and kept at this temperature for 35 minutes to kill the putrefactive bacteria and pathogens on the carcass and fur. The temperature was then lowered to 55°C, and then 0.6 g of a substance with an effective viable count of 2.3 × 10⁻⁶ bacteria was added. 9 CFU / g of thermostable Bacillus was added, followed by the addition of 0.7g of proteinase K (enzyme 1), and stirring was continued for 46.5h. After the reaction was completed, 0.7g of alkaline protease (enzyme 2) was added, and stirring was continued for 25h. The mixture was filtered to separate the bone from the filtrate. The bone was dried and ground to obtain cow and sheep wool biomass powder. The filtrate was processed by a filter press to separate the fine ash solids from the soluble matter, resulting in a mixed nutrient solution.

[0048] S2: After drying the cow and sheep wool biomass powder in a drying oven at 69°C for 1.5 hours, place it in a tube furnace, introduce argon gas at a flow rate of 49 cm / min, heat to 590°C, and continue the reaction for 95 minutes to obtain pretreated biomass; mix 35 g of pretreated biomass with 175 mL of 55% potassium hydroxide solution for 29 hours, then dry it in a drying oven at 69°C for 21 hours, and then place it in a tube furnace, introduce argon gas at a flow rate of 49 cm / min, heat to 870°C, and continue the reaction for 95 minutes, and then cool naturally to obtain activated cow and sheep wool biomass powder.

[0049] S3: Add 87.5g of 2,5-diaminoterephthalic acid and 775mL of N,N-dimethylformamide solution to a polytetrafluoroethylene-lined autoclave. Stir for 40min at 22.5℃ and 550r / min. Then add 37.5g of ferric chloride and 57.5g of activated bovine and sheepskin biomass powder. Heat to 125℃ and continue the reaction for 25h. Cool naturally to room temperature, filter, and wash the filter cake three times with methanol solution and deionized water respectively. Dry under vacuum at 65℃ for 1.5h to obtain composite bovine and sheepskin biomass powder.

[0050] S4: Add 45g of humic acid powder, 110mL of acrylic acid solution with a neutralization degree of 57.5% and 2.5L of deionized water to a reaction vessel, purge with nitrogen for protection, and stir at 87.5℃ and 550r / min for 1.5h. Cool to 55℃, add 2.5g of ammonium persulfate as an initiator and 1.5g of hydroxymethylacrylamide as a crosslinking agent to the reaction vessel, and continue stirring for 1.5h. Then add 2.5g of triethylamine as a catalyst, and continue stirring for 1.5h. Filter, wash the filter cake three times with deionized water and anhydrous ethanol respectively, and dry under vacuum at 65℃ for 1.5h to obtain the humic acid interpenetrating complex.

[0051] S5: Add 55g of compound cow and sheep wool biomass powder, 130mL of anhydrous ethanol and 450mL of deionized water to a reaction vessel, stir for 11min at 65℃ and 550r / min, then add 17.5g of humic acid interpenetrating complex and 2.5g of N,N'-dicyclohexylcarbodiimide, continue stirring for 8.5h, filter, wash the precipitate three times with deionized water and anhydrous ethanol, and vacuum dry at 65℃ for 1.5h to obtain the compound powder; mix the compound powder and mixed nutrients at a mass ratio of 5:3 to obtain cow and sheep wool biomass organic fertilizer.

[0052] Example 3: A method for preparing a cow and sheep wool biomass organic fertilizer, comprising the following steps:

[0053] S1: Cut 90g of cattle / sheep carcasses and 30g of fur into 6cm pieces. 3The small, block-shaped pieces were transferred to a reaction vessel, then 600 mL of deionized water and 10 g of potassium hydroxide were added. The pH was adjusted to 9, steam was introduced into the reaction vessel, and the mixture was heated to 110°C and kept at this temperature for 40 minutes to kill the putrefactive bacteria and pathogens on the carcass and fur. The temperature was then lowered to 60°C, and then 0.7 g of a substance with an effective viable count of 2.4 × 10⁻⁶ bacteria was added. 9 CFU / g of thermostable Bacillus was added, followed by the addition of 0.8g of proteinase K (enzyme 1), and stirring was continued for 48 hours. After the reaction was completed, 0.8g of alkaline protease (enzyme 2) was added, and stirring was continued for 26 hours. The mixture was filtered to separate the bone from the filtrate. The bone was dried and ground to obtain cow and sheep wool biomass powder. The filtrate was processed by a filter press to separate the fine ash solids from the soluble matter, resulting in a mixed nutrient solution.

[0054] S2: After drying the cow and sheep wool biomass powder in a drying oven at 70°C for 2 hours, place it in a tube furnace, introduce argon gas at a flow rate of 50 cm / min, heat to 600°C, and continue the reaction for 100 minutes to obtain pretreated biomass; mix 40 g of pretreated biomass with 200 mL of 60% potassium hydroxide solution for 30 hours, then dry it in a drying oven at 70°C for 22 hours, and then place it in a tube furnace, introduce argon gas at a flow rate of 50 cm / min, heat to 900°C, and continue the reaction for 100 minutes, and then cool naturally to obtain activated cow and sheep wool biomass powder.

[0055] S3: Add 90g of 2,5-diaminoterephthalic acid and 800mL of N,N-dimethylformamide solution to a polytetrafluoroethylene-lined autoclave. Stir for 50min at 25℃ and 600r / min. Then add 40g of ferric chloride and 60g of activated bovine and sheepskin biomass powder. Heat to 130℃ and continue the reaction for 26h. Cool naturally to room temperature, filter, and wash the filter cake four times with methanol solution and deionized water, respectively. Dry under vacuum at 70℃ for 1.5h to obtain composite bovine and sheepskin biomass powder.

[0056] S4: Add 50g of humic acid powder, 120mL of acrylic acid solution with a neutralization degree of 65% and 3L of deionized water to a reaction vessel, purge with nitrogen for protection, and stir at 95℃ and 600r / min for 2h. Cool to 60℃, add 3g of ammonium persulfate as an initiator and 2g of hydroxymethylacrylamide as a crosslinking agent to the reaction vessel, and continue stirring for 2h. Then add 3g of triethylamine as a catalyst, and continue stirring for 2h. Filter, wash the filter cake 4 times with deionized water and anhydrous ethanol respectively, and dry under vacuum at 70℃ for 2h to obtain the humic acid interpenetrating complex.

[0057] S5: Add 60g of compound cow and sheep wool biomass powder, 140mL of anhydrous ethanol and 500mL of deionized water to a reaction vessel, stir for 12min at 70℃ and 600r / min, then add 20g of humic acid interpenetrating complex and 3g of N,N'-dicyclohexylcarbodiimide, continue stirring for 9h, filter, wash the precipitate 4 times with deionized water and anhydrous ethanol, and vacuum dry at 70℃ for 2h to obtain the compound powder; mix the compound powder and mixed nutrients at a mass ratio of 5:3 to obtain cow and sheep wool biomass organic fertilizer.

[0058] Comparative Example 1: Based on Example 3, the composite bovine and sheepskin biomass powder in step S5 was replaced with the activated bovine and sheepskin biomass powder in step S3.

[0059] Comparative Example 2: Based on Example 3, the humic acid interpenetrating complex in step S5 was omitted.

[0060] Comparative Example 3: Based on Example 3, the composite powder prepared in step S5 was replaced with a mixture of composite cow and sheep wool biomass powder and humic acid interpenetrating complex in a mass ratio of 60:20.

[0061] Performance tests were conducted on the ox and sheep wool biomass organic fertilizers prepared in Examples 1-3 and Comparative Examples 1-3. Twelve test sites were set up in Haiyan County, each covering an area of ​​10 mu (approximately 0.67 hectares). 30 kg / mu (approximately 20 kg / hectare) of ox and sheep wool biomass organic fertilizer was applied. The test crop was sunflower, variety SH361, with a row spacing of 100 cm, a row spacing of 40 cm, and a plant spacing of 60 cm, resulting in 1588 seedlings per mu (approximately 1000 plants / hectare). Irrigation time was 0, irrigation frequency was 0, and irrigation volume was 0 m³ / mu (approximately 0.067 hectares). The growth of the sunflowers was observed. The soil cadmium content was measured 6 and 12 months after the application of the ox and sheep wool biomass organic fertilizer according to ISO 10381-4:2003. The results are shown in Table 1.

[0062] Table 1 Performance Test Table of Cow and Sheep Wool Biomass Organic Fertilizer

[0063]

[0064] As can be seen from Table 1, after applying the cow and sheep wool biomass organic fertilizer prepared in Examples 1-3, the plant height, stem diameter and disc diameter of sunflowers were significantly better than those of the comparative example, while the empty shell rate and cadmium content were significantly lower than those of the comparative example. This indicates that the cow and sheep wool biomass organic fertilizer prepared in this invention has high nutritional value, can promote crop growth, and can reduce the heavy metal content in the soil.

[0065] Comparative Example 1 replaced the composite cow and sheep wool biomass powder with activated cow and sheep wool biomass powder. The iron-based metal skeleton is the key structure for chelating heavy metals in the soil. At the same time, it can increase the porosity and roughness of biomass, and improve the adsorption capacity for nutrient peptides and amino acids. The decrease in porosity leads to a reduction in nutrient adsorption, unstable release rate, insufficient nutrient acquisition by crops, and a decrease in crop yield and quality.

[0066] Comparative Example 2 discarded the humic acid interpenetrating complex. The core function of the humic acid interpenetrating complex is to improve soil structure and maintain its own physical structure stability. It is a key component connecting nutrient supply and soil adaptability. Without the chemical reaction between humic acid and soil minerals, the soil is difficult to form stable aggregates, resulting in decreased air permeability and water retention, hindered crop root growth, and increased empty shell rate. Without the interpenetrating structure of humic acid, the structure is prone to disintegration when exposed to water during subsequent use, and nutrients are easily lost with rainwater.

[0067] Comparative Example 3 replaced the composite powder with a mixture of composite cow and sheep wool biomass powder and humic acid interpenetrating complex in a mass ratio of 60:20. The composite powder was a chemical bond formed by the amidation reaction of humic acid interpenetrating complex and composite biomass through N,N'-dicyclohexylcarbodiimide catalysis, rather than a simple physical mixture. Humic acid and composite biomass are only physically bonded, and they are easily separated during use due to stirring, watering and other operations, and cannot exert a synergistic effect at the same time. Physical mixing cannot form an interpenetrating structure. After humic acid absorbs water, the intermolecular forces are destroyed and the structure disintegrates. It can neither stabilize and improve the soil, nor help retain nutrients, and ultimately the empty shell rate increases.

[0068] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the invention.

Claims

1. A method for preparing a cattle and sheep fur biomass organic fertilizer, characterized in that, It comprises the following steps: Step one: after the cattle and sheep carcasses and skins are sterilized by potassium hydroxide, they are subjected to enzymatic hydrolysis by heat-resistant bacillus, protease K and alkaline protease to obtain bones and filtrate, then the bones are dried and ground to obtain cattle and sheep skin biomass powder; the filtrate is treated by a filter press to obtain mixed nutrients; Step two: the cattle and sheep skin biomass powder is calcined to obtain pretreated biomass, which is then treated with a potassium hydroxide solution to obtain activated cattle and sheep skin biomass powder; Step three: the activated cattle and sheep skin biomass powder is used as a carrier to hydrothermally synthesize an iron-based metal framework containing amino groups on the surface to obtain composite cattle and sheep skin biomass powder; Step four: after polymerization, the acrylic acid is esterified with humic acid under the action of triethylamine, and the molecular chains are intertwined to obtain a humic acid interpenetrating composite; Step five: the composite powder is prepared by amidation reaction between the carboxyl groups on the surface of the humic acid interpenetrating composite and the amino groups on the surface of the composite cattle and sheep skin biomass powder; the composite powder and the mixed nutrients are stirred and mixed at a mass ratio of 5:3 to obtain cattle and sheep skin biomass organic fertilizer.

2. The method according to claim 1, characterized in that, The specific preparation steps of the cattle and sheep skin biomass powder are as follows: The cattle and sheep carcasses and pelts are cut into 5-6 cm 3 sized blocks, transferred to a reaction kettle, then deionized water and potassium hydroxide are added, the pH value is adjusted to 8-9, steam is introduced into the reaction kettle, heated to 100-110℃, and kept for 30-40 min, so that the spoilage bacteria and pathogenic bacteria carried on the carcasses and pelts are killed, the temperature is lowered to 50-60℃, then 2.2-2.4×10 9 CFU / g of heat-resistant bacillus are added, then protease K is added, and stirring is continued for 45-48 h, after the reaction is completed, alkaline protease is added, and stirring is continued for 24-26 h, filtration is performed, the bones are separated from the filtrate, the bones are dried in the sun, and grinding is performed to obtain cattle and sheep pelt biomass powder.

3. The method according to claim 2, characterized in that, The use amount ratio of the cattle and sheep carcasses, skins, deionized water, potassium hydroxide, heat-resistant bacillus, protease K and alkaline protease is 80-90g:20-30g:500-600mL:8-10g:0.5-0.7g:0.6-0.8g:0.6-0.8g.

4. The method according to claim 1, characterized in that, The specific preparation steps of the mixed nutrients are as follows: After the filtrate is treated by a filter press, the fine ash solids and the soluble substances are separated to obtain the mixed nutrients.

5. The method according to claim 1, characterized in that, The specific preparation steps of the activated cattle and sheep skin biomass powder are as follows: The cattle and sheep skin biomass powder is dried in a drying oven at 68-70℃ for 1-2h, then placed in a tube furnace, argon gas with a flow rate of 48-50cm / min is introduced, heated to 580-600℃, and continued to react for 90-100min to obtain pretreated biomass; The pretreated biomass and a potassium hydroxide solution with a mass fraction of 50-60% are stirred and mixed at a use amount ratio of 30-40g:150-200mL for 28-30h, then dried in a drying oven at 68-70℃ for 20-22h, then placed in a tube furnace, argon gas with a flow rate of 48-50cm / min is introduced, heated to 840-900℃, and continued to react for 90-100min, and then naturally cooled to obtain activated cattle and sheep skin biomass powder.

6. The method according to claim 1, wherein the method is characterized by, The specific preparation steps of the composite cattle and sheep skin biomass powder are as follows: 2,5-diaminoterephthalic acid and N,N-dimethylformamide solution into the polytetrafluoroethylene lined autoclave, stirring at 20-25℃ and 500-600r / min for 30-50min, then adding iron chloride and activated cow and sheep skin biomass powder, heating to 120-130℃, continuing to react for 24-26h, naturally cooling to room temperature, filtering, washing the filter cake with methanol solution and deionized water for 2-4 times respectively, vacuum drying at 60-70℃ for 1.5h, obtaining the composite cow and sheep skin biomass powder; The amount ratio of the 2,5-diaminoterephthalic acid, N,N-dimethylformamide solution, iron chloride and activated cow and sheep skin biomass powder is 85-90g:750-800mL:35-40g:55-60g.

7. The method according to claim 1, characterized in that, The specific preparation steps of the humic acid interpenetrating composite are as follows: humic acid powder, acrylic acid solution with neutralization degree of 50-65% and deionized water into the reaction kettle, purging with nitrogen protection, stirring at 80-95℃ and 500-600r / min for 1-2h, cooling to 50-60℃, adding ammonium persulfate and hydroxymethyl acrylamide into the reaction kettle, continuing to stir for 1-2h, then adding triethylamine, continuing to stir for 1-2h, filtering, washing the filter cake with ionized water and anhydrous ethanol for 2-4 times respectively, vacuum drying at 60-70℃ for 1-2h, obtaining the humic acid interpenetrating composite; The amount ratio of the humic acid powder, acrylic acid solution, deionized water, ammonium persulfate, hydroxymethyl acrylamide and triethylamine is 40-50g:100-120mL:2-3L:2-3g:1-2g:2-3g.

8. The method according to claim 1, characterized in that, The specific preparation steps of the composite powder are as follows: composite cow and sheep skin biomass powder, anhydrous ethanol and deionized water into the reaction kettle, stirring at 60-70℃ and 500-600r / min for 10-12min, then adding humic acid interpenetrating composite and N,N'-dicyclohexyl carbodiimide, continuing to stir for 8-9h, filtering, washing the precipitate with deionized water and anhydrous ethanol for 2-4 times, vacuum drying at 60-70℃ for 1-2h, obtaining the composite powder.

9. The method according to claim 8, characterized in that, The amount ratio of the composite cow and sheep skin biomass powder, anhydrous ethanol, deionized water, humic acid interpenetrating composite and N,N'-dicyclohexyl carbodiimide is 50-60g:120-140mL:400-500mL:15-20g:2-3g.

10. A cattle and sheep fur biomass organic fertilizer, characterized in that, Prepared by the preparation method of any one of claims 1-9. Prepared by the preparation method of any one of claims 1-9.

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