阅读说明：本技术 一种利用贻贝蒸煮液制备液体蛋白肥的方法 (method for preparing liquid protein fertilizer by using mussel cooking liquor ) 是由 王阳光 欧阳小琨 王南 杨立业 于 2019-10-10 设计创作，主要内容包括：本发明涉及肥料制备技术领域,针对贻贝蒸煮液中重金属含量超标无法利用的问题,提供一种利用贻贝蒸煮液制备液体蛋白肥的方法,包括以下步骤：1)将蛋白酶和改性壳聚糖按(0.5-2.5):1的质量比加入水中,加热反应后过滤得到处理剂；2)将贻贝蒸煮液和处理剂按(1-1.5):1的质量比混合,pH 6-8,30-50℃下搅拌反应6-10 h,结束后得酶解液；3)将酶解液在70-90℃、1500-2500 r/min搅拌条件下反应4-7 h,离心得液体蛋白肥。本发明的改性壳聚糖既能作为蛋白酶的载体增大酶解反应的反应面积,提高酶解效率,还能吸收重金属,得到重金属含量极低的液体蛋白肥。(The invention relates to the technical field of fertilizer preparation, and provides methods for preparing liquid protein fertilizer by using mussel cooking liquor, aiming at the problem that the heavy metal content in the mussel cooking liquor exceeds the standard and cannot be utilized, which comprises the following steps of 1) adding protease and modified chitosan into water according to the mass ratio of (0.5-2.5) to 1, heating for reaction and filtering to obtain a treating agent, 2) mixing the mussel cooking liquor and the treating agent according to the mass ratio of (1-1.5) to 1, stirring for reaction at the temperature of 6-8 and 30-50 ℃ for 6-10 h to obtain an enzymatic hydrolysate, and 3) reacting the enzymatic hydrolysate for 4-7 h at the temperature of 70-90 ℃ and the stirring temperature of 2500 r/min, and centrifuging to obtain the liquid protein fertilizer.)

1, method for preparing liquid protein fertilizer by using mussel cooking liquor, which is characterized by comprising the following steps:

1) adding protease and modified chitosan into water according to the mass ratio of (0.5-2.5) to 1, heating for reaction, and filtering to obtain a treating agent;

2) mixing mussel decoction and treating agent at mass ratio of (1-1.5) to 1, reacting at 30-50 deg.C with pH of 6-8 under stirring for 6-10 hr to obtain enzymatic hydrolysate;

3) reacting the enzymolysis liquid for 4-7 h at 70-90 ℃ under the stirring condition of 1500-.

2. The method for preparing liquid protein fertilizers from mussel cooking liquor according to claim 1, wherein the modified chitosan obtained in step 1) is prepared by dissolving chitosan in dilute acid solution, adding 1-2 times of 4-chlorobutyric acid, adding ethanol, reacting at 30-40 deg.C for 4-6 h, removing impurities after reaction, and drying the product to constant weight.

3. The method for preparing liquid protein fertilizer from mussel cooking liquor according to claim 2, wherein the modified chitosan is further treated by weighing modified chitosan, heating and stirring in water, dissolving, then adding epichlorohydrin and sodium hydroxide solution dropwise in sequence under stirring, reacting at 30-50 ℃ for 5-7 h, extracting and removing impurities after the reaction is finished, and drying the product to constant weight to obtain the cross-linked modified chitosan.

4. The method for preparing liquid protein fertilizer by using mussel cooking liquor according to of claim 2 or 3, wherein the drying condition is vacuum drying at 60-70 ℃.

5. The method for preparing liquid protein fertilizer by using mussel cooking liquor according to claim 2 or 3, wherein the extraction conditions are adding 1-3 times volume of extraction solvent, stirring, centrifuging, and reflux-extracting with Soxhlet extractor for 2-3 h.

6. The method for preparing liquid protein fertilizer by using mussel cooking liquor according to claim 1, wherein in step 1) the protease is prepared by mixing papain and trypsin in a volume ratio of (0.2-0.8) to 1.

7. The method for preparing liquid protein fertilizer by using mussel cooking liquor according to claim 1, wherein inorganic salts containing potassium or phosphorus are further added to the liquid protein fertilizer for compounding.

Technical Field

The invention relates to the technical field of fertilizer preparation, in particular to a method for preparing liquid protein fertilizer by using mussel cooking liquor, which is .

Background

The liquid protein fertilizer is kinds of crop fertilizer made of waste animal and plant protein, which contains lots of biological peptide, rich amino acid, and contains several major elements, trace elements, vitamins, etc. it can improve the disease resistance and stress resistance of plant by means of the synergistic action of said fertilizer and other effective components, can improve the quality of crop and promote plant growth, so that it is kinds of novel environment-protecting animal and plant protein fertilizer.

For example, mussel cooking liquor is a by-product produced in the process of processing mussels into frozen products or dried products, about 1.5 tons of cooking liquor can be produced by processing 1 ton of mussel products by using enzyme, and at present is directly discharged.

Disclosure of Invention

The invention provides methods for preparing liquid protein fertilizer by using mussel cooking liquor, aiming at overcoming the problem that the heavy metal content in the mussel cooking liquor exceeds the standard and cannot be utilized, wherein the modified chitosan can be used as a carrier of protease to increase the reaction area of enzymolysis reaction, improve the enzymolysis efficiency, absorb heavy metal and obtain the liquid protein fertilizer with extremely low heavy metal content.

In order to achieve the purpose, the invention adopts the following technical scheme:

method for preparing liquid protein fertilizer by using mussel cooking liquor, which is characterized by comprising the following steps:

1) adding protease and modified chitosan into water according to the mass ratio of (0.5-2.5) to 1, heating for reaction, and filtering to obtain a treating agent;

2) mixing mussel decoction and treating agent at mass ratio of (1-1.5) to 1, reacting at 30-50 deg.C with pH of 6-8 under stirring for 6-10 hr to obtain enzymatic hydrolysate;

3) reacting the enzymolysis liquid for 4-7 h at 70-90 ℃ under the stirring condition of 1500-.

The invention mixes protease and modified chitosan to react to obtain a treating agent, the protease can be adsorbed on the modified chitosan so as to increase the reaction area of enzymolysis reaction, the treating agent is added into mussel cooking liquor to carry out enzymolysis firstly to decompose protein into amino acid which is convenient to absorb, and then the modified chitosan is utilized to remove impurities such as heavy metal in the reaction liquor, so that the liquid protein fertilizer with extremely low heavy metal content is obtained.

Preferably, the preparation method of the modified chitosan in the step 1) comprises the following steps: dissolving chitosan in dilute acid solution, adding 1-2 times of 4-chlorobutyric acid, adding ethanol, reacting at 30-40 deg.C for 4-6 h, extracting to remove impurities, and drying to constant weight to obtain modified chitosan. The chitosan contains various active functional groups such as hydroxyl, amino and glycosidic bonds, so that the chitosan has stronger coordination capacity with metal ions. However, in the current reports, the adsorption performance of chitosan and its derivatives on cobalt ions is inferior to that of other metals such as copper ions and nickel ions. The invention introduces new functional groups on the chitosan to obtain the modified chitosan, thereby greatly improving the adsorption performance to cobalt ions.

Preferably, the modified chitosan is further treated as follows: weighing modified chitosan, heating and stirring the modified chitosan in water, dissolving the modified chitosan, then sequentially dropwise adding epoxy chloropropane and a sodium hydroxide solution under stirring, reacting the epoxy chloropropane for 5 to 7 hours at a temperature of between 30 and 50 ℃ with the use amount of 1 to 3 percent of the mass of the modified chitosan, extracting and removing impurities after the reaction is finished, and drying a product to constant weight to obtain the crosslinked modified chitosan. The modified chitosan and epoxy chloropropane are crosslinked to obtain crosslinked complex adsorption resin insoluble in acid, alkali and water, so that the modified chitosan is convenient to recycle in the application process, and meanwhile, the production cost is reduced and the production efficiency is improved on the basis of ensuring the adsorption efficiency. More importantly, the control of the using amount of the epichlorohydrin can enable the diameter of the gaps of the net structure to be close to that of the copper ions, so that the gaps have a pore adsorption effect when the copper ions are adsorbed, and the adsorption rate is improved.

Preferably, the drying conditions are vacuum drying at 60-70 ℃.

Preferably, the extraction conditions are adding 1-3 times of the volume of the reaction solution of extraction solvent, stirring, centrifuging, and extracting under reflux for 2-3h by a Soxhlet extractor.

Preferably, in the step 1), the protease is obtained by mixing papain and trypsin in a volume ratio of (0.2-0.8) to 1, and the enzymolysis efficiency of the papain and the trypsin in cooperation with each other is greater than that of enzymes alone.

Preferably, inorganic salt containing potassium or phosphorus is added into the liquid protein fertilizer for compounding. The nutrient substances of the liquid protein fertilizer mainly comprise amino acid and the like, and in order to make up for the deficiency of potassium and phosphorus elements in the liquid protein fertilizer, inorganic salt containing potassium or phosphorus elements can be added, so that the compatibility is more reasonable, and the liquid protein fertilizer has an improvement effect on crops and soil.

Therefore, the invention has the following beneficial effects: (1) the modified chitosan can be used as a carrier of protease to increase the reaction area of enzymolysis reaction and absorb heavy metal; (2) the modified chitosan obtained after the reaction of chitosan and 4-chlorobutyric acid greatly improves the adsorption performance to the chitosan cobalt ion; (3) after the modified chitosan and the epoxy chloropropane are crosslinked, the crosslinked complex adsorption resin which is insoluble in acid, alkali and water can be obtained, so that the modified chitosan and the epoxy chloropropane are convenient to recycle in the application process, and meanwhile, the production cost is reduced and the production efficiency is improved on the basis of ensuring the adsorption efficiency; more importantly, the use amount of the epichlorohydrin is controlled to enable the diameter of the gaps of the net structure to be close to that of the copper ions, so that the gaps have a pore adsorption effect when the epichlorohydrin adsorbs the copper ions, and the adsorption rate is improved; (4) the nutrient substances of the liquid protein fertilizer mainly comprise amino acid and the like, and in order to make up for the deficiency of potassium and phosphorus elements in the liquid protein fertilizer, inorganic salt containing potassium or phosphorus elements can be added, so that the compatibility is more reasonable, and the liquid protein fertilizer has an improvement effect on crops and soil.

Detailed Description

The technical solution of the present invention is further illustrated in step by the following specific examples.

In the present invention, unless otherwise specified, all the raw materials and equipment used are commercially available or commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.