CN109503221B - Modified lignin chelated fertilizer and preparation method thereof - Google Patents
Modified lignin chelated fertilizer and preparation method thereof Download PDFInfo
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Abstract
The invention provides a modified lignin chelate fertilizer and a preparation method thereof, the method takes lignin as a raw material, the lignin is oxidized by hydrogen peroxide, the molecular weight of the oxidized lignin is reduced, the contents of hydroxyl and carboxyl in the lignin are greatly improved, then the lignin is further etherified, the contents of the hydroxyl and the carboxyl are increased, the etherification of the lignin is facilitated, the etherification efficiency is further improved, the content of the carboxyl in the lignin is increased, the chelating capacity of the lignin is improved, and then the chelate fertilizer is prepared by the synergistic effect of the modified lignin with strong chelating force and medium trace elements. The chelate fertilizer prepared by the invention is more beneficial to fertilizer compounding, and can obviously increase the crop absorption capacity. The lignin oxidation process is mild and stable, no toxic and harmful substances are generated in the oxidation process, and the preparation process is simple to operate, low in cost and easy for industrial large-scale production.
Description
Technical Field
The invention relates to a modified lignin chelate fertilizer and a preparation method thereof, belonging to the technical field of chelate fertilizer preparation.
Background
For plants, common trace elements mainly comprise iron (Fe), manganese (Mn), zinc (Zn), copper (Cu), molybdenum (Mo), boron (B) and chlorine (Cl), secondary elements mainly comprise silicon (Si), calcium (Ca), magnesium (Mg) and sulfur (S), and the elements are components or activators of various enzymes and participate in processes such as carbon assimilation, carbohydrate transport, nitrogen metabolism, redox and the like; they can promote plant growth, formation and development of reproductive organs, and enhance antibiotic effect. However, with the application of fertilizers containing no medium trace elements due to high concentration of nitrogen, phosphorus and potassium and the reduction of the application amount of organic fertilizers, the phenomenon that crops lack medium trace elements is shown on some soils, so that fertilizers containing medium trace elements are applied and supplemented in a targeted manner.
In modern agricultural production, the common medium trace element fertilizers are divided into inorganic state and organic state from raw materials, wherein the organic state mainly exists in a chelate form. The inorganic trace elements are difficult to be compatible during compounding due to the antagonism among the elements, and the organic trace elements exist in a metal ion state, so that the organic trace elements have the advantages of good stability, good compatibility and stability with various elements, contribution to crop absorption and the like. At present, much microelement fertilizer taking EDTA and humic acid as chelating agents is applied in China, but the EDTA chelating fertilizer is expensive and the main market is occupied by foreign manufacturers. The humic acid micro-fertilizer has the problems of poor chelating capacity, unstable chelate, difficult absorption by crops and the like.
The lignin is an aromatic natural high molecular polymer with a complex structure, has a three-dimensional reticular space structure, contains multiple functional groups, has strong chelating capacity, has more connection modes and different positions among lignin structural units, and is an environment-friendly biomass renewable resource. The lignin can be used as a plant growth stimulator, a fertilizer, a soil conditioner and the like in agriculture, and can be used as a chelating agent to prepare a chelated fertilizer by chelating medium trace elements. However, unmodified lignin has weak chelating ability and poor water solubility, and the prepared chelating fertilizer is not easy to be absorbed by crops and is not suitable for being used as a chelating agent, so the lignin needs to be modified by chemical modification.
Chinese patent document CN103396244A (application number: 201310322940.8) discloses a modified alkali lignin chelated zinc fertilizer and a preparation method thereof. Firstly, adding alkali lignin powder into water, adjusting the pH value, and dissolving into an aqueous solution with the mass percentage concentration of 30-40%; adding amino acid, dropwise adding epoxy chloropropane, heating to 75-95 ℃, and reacting for 2-3 h; adjusting the pH value to 10-12, dropwise adding bromoacetic acid, and reacting at 70-90 ℃ for 1-2 h; and finally, adjusting the pH value of the system to 5-7 by using a dilute hydrochloric acid solution, adding zinc sulfate, carrying out chelation reaction at 50-70 ℃ for 0.5-2 h, and obtaining the modified alkali lignin chelated zinc fertilizer after the reaction is finished. However, after the lignin prepared by the method is modified in multiple steps, the molecular weight is increased, and the prepared modified alkali lignin chelate fertilizer is not beneficial to later-stage absorption of crops. Chinese patent document CN101935255A (application No. 201010267997.1) provides a method for producing a lignin metal chelate fertilizer, which comprises the following steps performed in the following order: (1) preparing an aqueous solution with a certain concentration from industrial lignin salt in a dissolving tank; (2) transferring the prepared industrial lignin aqueous solution into a reaction container, and adjusting the pH value of the solution by using a pH regulator; (3) adding an oxidant and an initiator, starting a stirring device of a reaction container, fully and uniformly mixing, and adding inorganic salt containing medium and trace elements; (4) heating to a certain temperature and reacting for a specified time. The invention only uses hydrogen peroxide to oxidize industrial lignin without further carboxylation, and the oxidized lignin is used as a chelating agent, so that the chelating ability is limited and the chelating stability is poor.
Disclosure of Invention
Aiming at the defects of the prior art, in particular to the defects of limited chelating capacity of lignin for medium and trace elements, poor chelating stability and difficult later-period absorption of the lignin chelate fertilizer by crops in the prior art, the invention provides a modified lignin chelate fertilizer and a preparation method thereof. According to the method, the lignin is oxidized by using hydrogen peroxide and further etherified, so that the contents of hydroxyl and carboxyl in the lignin are improved, the chelating capacity is improved, and then the synergistic effect of the modified lignin with strong chelating capacity and medium trace elements is utilized to prepare the chelated fertilizer. The chelate fertilizer prepared by the invention is more beneficial to fertilizer compounding, and can obviously increase the crop absorption capacity. The preparation process has simple operation and low cost, and is easy for industrial large-scale production.
The technical scheme of the invention is as follows:
a preparation method of a modified lignin chelated fertilizer comprises the following steps:
(1) adding lignin powder into water, and uniformly stirring at room temperature to obtain a lignin solution A;
(2) adding a certain amount of hydrogen peroxide into the lignin solution A obtained in the step (1) while stirring, then adjusting the pH value of the system by using an acidic solution, heating, and stirring in a sealed manner to obtain a solution B;
(3) cooling the solution B obtained in the step (2) to room temperature, then dropwise adding an alkali liquor to adjust the pH value of the system, heating, stirring, then adding chloroacetic acid, heating, and stirring to obtain a solution C;
(4) and (3) cooling the solution C obtained in the step (3) to 40-60 ℃, then adjusting the pH value of the system to 5-7 by using an acidic solution, adding medium trace elements, stirring and reacting at 40-60 ℃ for 60-120 min, and naturally cooling after the reaction is finished to obtain the modified lignin chelated fertilizer.
According to the invention, the weight average molecular weight of the lignin in the step (1) is 1000-10000, and the lignin is a commercially available product;
preferably, the mass ratio of the lignin powder to the water in the step (1) is (0.05-0.5) to 1, and more preferably (0.1-0.4): 1.
according to the invention, the room temperature in the step (1) is preferably 20-30 ℃, and the stirring time at the room temperature is preferably 5-30 min.
According to the invention, preferably, the mass fraction of the hydrogen peroxide in the step (2) is 30%;
preferably, the mass ratio of the hydrogen peroxide to the lignin powder is (0.02-0.3): 1, more preferably (0.05 to 0.1): 1;
preferably, the adding mode of the hydrogen peroxide is dropwise adding, and the dropwise adding is completed in 5-30 minutes.
According to the present invention, it is preferable that the acidic solution in the step (2) is hydrochloric acid, nitric acid or sulfuric acid; more preferably, the mass fraction of the hydrochloric acid is 10-20%, the mass fraction of the nitric acid is 10-20%, and the mass fraction of the sulfuric acid is 10-20%;
preferably, in the step (2), the pH value of the system is adjusted to 5-7 by using an acidic solution, the temperature is increased to 50-90 ℃, and the closed stirring time is 60-180 min.
According to the invention, preferably, the alkali liquor in the step (3) is a sodium hydroxide solution, the mass fraction of the sodium hydroxide solution is 10-20%, and the addition is uniformly completed within 5-30 minutes;
preferably, the pH value of the system is adjusted to 10-12 by using alkali liquor, the temperature is increased to 30-50 ℃, and the stirring is carried out for 20-40 min.
According to the invention, preferably, the mass ratio of the chloroacetic acid to the lignin powder in the step (3) is (0.05-0.5): 1, more preferably (0.1 to 0.3): 1;
preferably, chloroacetic acid is added, then the temperature is raised to 60-90 ℃, and the stirring time is 60-120 min.
According to the present invention, preferably, the acidic solution in step (4) is one of hydrochloric acid, nitric acid or sulfuric acid; more preferably, the mass fraction of the hydrochloric acid is 10-20%, the mass fraction of the nitric acid is 10-20%, and the mass fraction of the sulfuric acid is 10-20%.
According to the invention, preferably, the mass ratio of the medium trace elements to the lignin powder in the step (4) is (0.03-0.5): 1, more preferably (0.05 to 0.2): 1;
preferably, the medium trace elements in the step (4) are calcium, magnesium, zinc, iron, copper and manganese;
preferably, the medium trace elements are added in the form of soluble inorganic compounds containing corresponding elements; further preferably, the medium trace elements are added, wherein the calcium element is calcium chloride or calcium nitrate, the magnesium element is magnesium chloride, magnesium sulfate or magnesium nitrate, the zinc element is zinc sulfate, zinc chloride or zinc nitrate, the iron element is ferric nitrate, ferrous sulfate, ferric chloride or ferrous chloride, the copper element is cupric sulfate, cupric nitrate or cupric chloride, and the manganese element is manganese sulfate, manganese nitrate or manganese chloride.
A modified lignin chelate fertilizer, which is obtained by the preparation method; the obtained modified lignin chelated fertilizer is a liquid fertilizer and can be used in any proportion with water.
The above-mentioned processes for the preparation of the invention, which are not specifically described, are in accordance with the prior art.
The invention has the following technical characteristics and beneficial effects:
1. according to the preparation method, the lignin is oxidized by using the hydrogen peroxide, the oxidation process is mild and stable, no toxic or harmful substance is generated in the oxidation process, the molecular weight of the oxidized lignin is reduced, and the contents of hydroxyl and carboxyl in the lignin are greatly improved; the increase of the content of hydroxyl and carboxyl is beneficial to the etherification of lignin, so that the etherification efficiency is improved, the content of the carboxyl of the lignin is increased, and the chelating capacity of the lignin is improved.
2. The modified lignin chelate fertilizer prepared by the method has good water solubility and is beneficial to the absorption of crops; the chelating fertilizer prepared by adopting the modified lignin as a chelating agent jointly promotes the growth of plants through the synergistic effect of the lignin and the medium trace elements.
3. The lignin used by the method is extracted from plant straws, is easy to obtain raw materials, has wide sources, is renewable, has low cost and belongs to an environment-friendly chelating agent.
4. The preparation method has simple process operation and low cost, and is easier for industrial large-scale production.
Detailed Description
The present invention will be further described with reference to the following examples, but is not limited thereto.
The raw materials used in the examples are conventional raw materials, and the equipment used is conventional equipment, commercially available products.
Example 1
A preparation method of a modified lignin chelated magnesium fertilizer comprises the following steps:
(1) adding 4kg of lignin powder into 10kg of water, stirring for 10min at room temperature, and uniformly stirring to obtain a lignin solution A;
(2) dropwise adding 1kg of 30% hydrogen peroxide into the solution A obtained in the step (1) during stirring, adjusting the pH value of the system to 5-7 by using 10% hydrochloric acid solution, heating to 70 ℃, and stirring in a closed manner for 120min to obtain a solution B;
(3) cooling the solution B obtained in the step (2) to room temperature, then dropwise adding a 10% sodium hydroxide solution into the solution B, adjusting the pH value of the system to 10-12, heating to 40 ℃, stirring for 30min, adding 0.8kg of chloroacetic acid, heating to 70 ℃, and stirring for 90min to obtain a solution C;
(4) and (3) cooling the solution C obtained in the step (3) to 50 ℃, adjusting the pH value of the system to 5-7 by using a hydrochloric acid solution with the mass fraction of 10%, adding 0.9kg of magnesium chloride, stirring and reacting at 50 ℃ for 90min, and naturally cooling after the reaction is finished to obtain the modified lignin chelated magnesium fertilizer.
The content of carboxyl in the modified lignin chelated magnesium fertilizer prepared by the embodiment is tested according to GB/T20374-2006, and the content of carboxyl in the modified lignin chelated magnesium fertilizer is 2.87mmol/g through the test; the content of magnesium ions in the modified lignin chelated magnesium fertilizer prepared in the embodiment is tested according to GB/T13080.2-2005, and the content of magnesium ions in the modified lignin chelated magnesium fertilizer is tested to be 51 mg/g.
Example 2
A preparation method of a modified lignin chelated iron fertilizer comprises the following steps:
(1) adding 3kg of lignin powder into 10kg of water, stirring for 5min at room temperature, and uniformly stirring to obtain a lignin solution A;
(2) dropwise adding 0.5kg of 30% hydrogen peroxide into the solution A obtained in the step (1) during stirring, adjusting the pH value of a system to 5-7 by using a 20% sulfuric acid solution, heating to 80 ℃, and stirring in a sealed manner for 150min to obtain a solution B;
(3) cooling the solution B obtained in the step (2) to room temperature, then dropwise adding a sodium hydroxide solution with the mass fraction of 20% into the solution B, adjusting the pH value of the system to 10-12, heating to 50 ℃, stirring for 20min, adding 0.3kg of chloroacetic acid, heating to 90 ℃, and stirring for 60min to obtain a solution C;
(4) and (3) cooling the solution C obtained in the step (3) to 60 ℃, adjusting the pH value of the system to 5-7 by using a sulfuric acid solution with the mass fraction of 20%, adding 1.8kg of ferrous sulfate, stirring and reacting at 60 ℃ for 60min, and naturally cooling after the reaction is finished to obtain the modified lignin chelated iron fertilizer.
The content of carboxyl in the modified lignin chelated iron fertilizer prepared in the embodiment is tested according to GB/T20374-2006, the content of carboxyl in the modified lignin chelated iron fertilizer is tested to be 2.87mmol/g, the content of iron ions in the modified lignin chelated iron fertilizer prepared in the embodiment is tested according to GB/T13080.2-200, and the content of iron ions in the modified lignin chelated iron fertilizer is tested to be 116 mg/g.
Example 3
A preparation method of a modified lignin chelated copper fertilizer comprises the following steps:
(1) adding 2kg of lignin powder into 10kg of water, stirring for 5min at room temperature, and uniformly stirring to obtain a lignin solution A;
(2) dropwise adding 0.2kg of 30% hydrogen peroxide into the solution A obtained in the step (1) during stirring, adjusting the pH value of a system to 5-7 by using 10% nitric acid solution, heating to 50 ℃, and stirring in a sealed manner for 180min to obtain a solution B;
(3) cooling the solution B obtained in the step (2) to room temperature, then dropwise adding a 10% sodium hydroxide solution into the solution B, adjusting the pH value of the system to 10-12, heating to 35 ℃, stirring for 40min, adding 0.3kg chloroacetic acid, heating to 65 ℃, and stirring for 120min to obtain a solution C;
(4) and (3) cooling the solution C obtained in the step (3) to 40 ℃, adjusting the pH value of the system to 5-7 by using a nitric acid solution with the mass fraction of 10%, adding 0.8kg of copper nitrate, stirring and reacting at 40 ℃ for 120min, and naturally cooling after the reaction is finished to obtain the modified lignin chelated copper fertilizer.
The content of carboxyl in the modified lignin chelated copper fertilizer prepared by the embodiment is tested according to GB/T20374-2006, and the content of carboxyl in the modified lignin chelated copper fertilizer is 2.97mmol/g through testing; the content of copper ions in the modified lignin chelated copper fertilizer prepared in the embodiment is tested according to GB/T13080.2-200, and the content of copper ions in the modified lignin chelated copper fertilizer is 122 mg/g.
Example 4
A preparation method of a modified lignin chelated manganese fertilizer comprises the following steps:
(1) adding 1kg of lignin powder into 10kg of water, stirring at room temperature for 5min, and uniformly stirring to obtain a lignin solution A;
(2) dropwise adding 0.05kg of 30% hydrogen peroxide into the solution A obtained in the step (1) during stirring, adjusting the pH value of a system to 5-7 by using 10% nitric acid solution, heating to 90 ℃, and stirring for 90min in a closed manner to obtain a solution B;
(3) cooling the solution B obtained in the step (2) to room temperature, then dropwise adding a 10% sodium hydroxide solution into the solution B, adjusting the pH value of the system to 10-12, heating to 50 ℃, stirring for 40min, adding 0.05kg of chloroacetic acid, heating to 80 ℃, and stirring for 120min to obtain a solution C;
(4) and (3) cooling the solution C obtained in the step (3) to 40 ℃, adjusting the pH value of the system to 5-7 by using a nitric acid solution with the mass fraction of 10%, adding 0.4kg of manganese nitrate, stirring and reacting at 40 ℃ for 120min, and naturally cooling after the reaction is finished to obtain the modified lignin chelated manganese fertilizer.
The content of carboxyl in the modified lignin chelated manganese fertilizer prepared by the embodiment is tested according to GB/T20374-2006, and the content of carboxyl in the modified lignin chelated manganese fertilizer is 2.75mmol/g through testing; the content of manganese ions in the modified lignin chelated manganese fertilizer prepared by the embodiment is tested according to GB/T13080.2-200, and the content of manganese ions in the modified lignin chelated manganese fertilizer is tested to be 112 mg/g.
Comparative example 1
A preparation method of a lignin chelated magnesium fertilizer comprises the following steps:
(1) adding 4kg of lignin powder into 10kg of water, stirring for 10min at room temperature, and uniformly stirring to obtain a lignin solution A;
(2) and (2) adding 0.9kg of magnesium chloride into the solution A obtained in the step (1), stirring and reacting for 90min at 50 ℃, and naturally cooling after the reaction is finished to obtain the lignin chelated magnesium fertilizer.
The content of carboxyl in the lignin chelated magnesium fertilizer prepared in the comparative example is tested according to GB/T20374-2006, the content of carboxyl in the lignin chelated magnesium fertilizer is 0.51mmol/g through the test, the content of magnesium ions in the lignin chelated magnesium fertilizer prepared in the comparative example is tested according to GB/T13080.2-2005, and the content of magnesium ions in the lignin chelated magnesium fertilizer is 6mg/g through the test.
Comparative example 2
A preparation method of a lignin chelated iron fertilizer comprises the following steps:
(1) adding 3kg of lignin powder into 10kg of water, stirring for 5min at room temperature, and uniformly stirring to obtain a lignin solution A;
(2) adding 1.8kg of ferrous sulfate heptahydrate into the solution obtained in the step (1), stirring and reacting at 60 ℃ for 60min, and naturally cooling after the reaction is finished to obtain the lignin chelated iron fertilizer.
The content of carboxyl in the lignin chelated iron fertilizer prepared in the comparative example is tested according to GB/T20374-2006, the content of carboxyl in the lignin chelated iron fertilizer is 0.57mmol/g through the test, the content of iron ions in the lignin chelated iron fertilizer prepared in the comparative example is tested according to GB/T13080.2-200, and the content of iron ions in the lignin chelated iron fertilizer is 8mg/g through the test.
Comparative example 3
A preparation method of a lignin chelated magnesium fertilizer comprises the following steps:
(1) adding 4kg of lignin powder into 10kg of water, stirring for 10min at room temperature, and uniformly stirring to obtain a lignin solution A;
(2) dropwise adding 1kg of 30% hydrogen peroxide into the solution A obtained in the step (1) during stirring, adjusting the pH value of the system to 5-7 by using 10% hydrochloric acid solution, heating to 70 ℃, and stirring in a closed manner for 120min to obtain a solution B;
(3) and (3) cooling the solution B obtained in the step (2) to room temperature, adding 0.9kg of magnesium chloride, stirring and reacting at 50 ℃ for 90min, and naturally cooling after the reaction is finished to obtain the lignin chelated magnesium fertilizer.
The content of carboxyl in the lignin chelated magnesium fertilizer is tested according to GB/T20374-2006, the content of carboxyl in the lignin chelated magnesium fertilizer is 1.21mmol/g through the test, the content of magnesium ions in the lignin chelated magnesium fertilizer is tested according to GB/T13080.2-2005, and the content of magnesium ions in the lignin chelated magnesium fertilizer is 12mg/g through the test.
Comparative example 4
A preparation method of a lignin chelated iron fertilizer comprises the following steps:
(1) adding 3kg of lignin powder into 10kg of water, stirring for 5min at room temperature, and uniformly stirring to obtain a lignin solution A;
(2) dropwise adding 0.5kg of 30% hydrogen peroxide into the solution A obtained in the step (1) during stirring, adjusting the pH value of a system to 5-7 by using a 20% sulfuric acid solution, heating to 80 ℃, and stirring in a sealed manner for 150min to obtain a solution B;
(3) and (3) cooling the solution B obtained in the step (2) to room temperature, adding 1.8kg of ferrous sulfate heptahydrate, stirring and reacting at 60 ℃ for 60min, and naturally cooling after the reaction is finished to obtain the lignin chelated iron fertilizer.
The content of carboxyl in the lignin chelated iron fertilizer prepared in the comparative example is tested according to GB/T20374-2006, the content of carboxyl in the lignin chelated iron fertilizer is 1.23mmol/g through the test, the content of iron ions in the lignin chelated iron fertilizer prepared in the comparative example is tested according to GB/T13080.2-200, and the content of iron ions in the lignin chelated iron fertilizer is 21mg/g through the test.
Test example: effect of chelated fertilizers on tomato growth
The effect of the chelated fertilizers prepared in example 1 and example 2 on tomato growth was verified by pot experiments.
1. Test time and place: the test was carried out in a greenhouse of 2016.10.30-2016.12.30, from Jinzheng ecological engineering group, GmbH. Tomato variety: aiji 112 (Pink tomato)
2. The test treatments were as follows:
the test is carried out in a pot culture mode, 5kg of soil per pot is treated for 7 times, the reference 0 is a water-soluble fertilizer, the reference 1 is lignin, magnesium chloride and a water-soluble fertilizer, the reference 1 'is the chelated magnesium fertilizer and the water-soluble fertilizer prepared in the comparative example 1, the test 1 is the modified lignin chelated magnesium fertilizer and the water-soluble fertilizer prepared in the example 1, the reference 2 is lignin, ferrous sulfate and a water-soluble fertilizer, the reference 2' is the chelated iron fertilizer and the water-soluble fertilizer prepared in the comparative example 2, the test 2 is the modified lignin chelated iron fertilizer and the water-soluble fertilizer prepared in the example 2, each treatment is repeated for 4 times, and the water-soluble fertilizer used in the test is a gold-positive 20-20-20 water-soluble fertilizer; see in particular the experimental design of table 1 below.
And (3) selecting tomato seedlings with consistent growth vigor, transplanting the tomato seedlings into a plastic pot, treating the tomato seedlings 10 days later, and applying fertilizer once every 15 days for 3 times. The dilution times are 600 times of the dilution times of the water-soluble fertilizer.
TABLE 1 design of the experiments
TABLE 2 Effect of the flush application of chelated fertilizers on the physiological growth indices of tomatoes
As can be seen from table 2, the controls 1, 1', 2' and the tests 1, 2 all had the effect of promoting tomato growth compared to the control 0; compared with the control 1 and the control 2, the chelated fertilizers prepared in the example 1 and the example 2 in the test 1 have the effect of promoting the growth and development of the tomatoes compared with the singly mixed fertilizer, which indicates that the singly mixed fertilizer does not have the function of chelating the fertilizer; it can be seen from the tomato growth indexes that, compared with the controls 1 'and 2', the modified lignin chelated fertilizers prepared by using the trace elements in the modified lignin chelation in the tests 1 and 2 have the use effects obviously higher than the unmodified lignin chelated fertilizers used in the controls 1 'and 2', and the lignin chelated fertilizers used in the controls 1 'and 2' have the same use effects as the lignin, inorganic salts and water-soluble fertilizers in the controls 1 and 2. As can be seen from the table above, the chelate fertilizer prepared by the invention can be absorbed by crops more easily, and plays a better role in promoting growth.
Claims (11)
1. A preparation method of a modified lignin chelated fertilizer comprises the following steps:
(1) adding lignin powder into water, and uniformly stirring at room temperature to obtain a lignin solution A; the weight average molecular weight of the lignin is 1000-10000; the mass ratio of the lignin powder to the water is (0.05-0.5) to 1;
(2) adding a certain amount of hydrogen peroxide into the lignin solution A obtained in the step (1) while stirring, then adjusting the pH value of a system to 5-7 by using an acidic solution, heating, and stirring in a sealed manner to obtain a solution B; the mass ratio of the hydrogen peroxide to the lignin powder is (0.02-0.3): 1;
(3) cooling the solution B obtained in the step (2) to room temperature, then dropwise adding an alkali liquor to adjust the pH value of the system, heating, stirring, then adding chloroacetic acid, heating, and stirring to obtain a solution C; the mass ratio of the chloroacetic acid to the lignin powder is (0.05-0.5): 1;
(4) and (3) cooling the solution C obtained in the step (3) to 40-60 ℃, then adjusting the pH value of the system to 5-7 by using an acidic solution, adding medium trace elements, stirring and reacting at 40-60 ℃ for 60-120 min, and naturally cooling after the reaction is finished to obtain the modified lignin chelated fertilizer.
2. The preparation method of the modified lignin chelated fertilizer as claimed in claim 1, wherein the mass ratio of the lignin powder to water in step (1) is (0.1-0.4): 1;
the room temperature in the step (1) is 20-30 ℃, and the stirring time at the room temperature is 5-30 min.
3. The preparation method of the modified lignin chelated fertilizer as claimed in claim 1, wherein the hydrogen peroxide solution in step (2) is 30% by mass; the mass ratio of the hydrogen peroxide to the lignin powder is (0.05-0.1): 1; the adding mode of the hydrogen peroxide is dropwise adding, and the hydrogen peroxide is uniformly dropwise added in 5-30 minutes.
4. The method for preparing the modified lignin chelated fertilizer as claimed in claim 1, wherein the acidic solution in step (2) is hydrochloric acid, nitric acid or sulfuric acid; the mass fraction of the hydrochloric acid is 10-20%, the mass fraction of the nitric acid is 10-20%, and the mass fraction of the sulfuric acid is 10-20%;
and (3) heating to 50-90 ℃ in the step (2), and sealing and stirring for 60-180 min.
5. The preparation method of the modified lignin chelated fertilizer as claimed in claim 1, wherein the alkali solution in step (3) is a sodium hydroxide solution, the mass fraction of the sodium hydroxide solution is 10-20%, and the sodium hydroxide solution is uniformly added dropwise in 5-30 minutes;
and adjusting the pH value of the system to 10-12 by using alkali liquor, heating to 30-50 ℃, and stirring for 20-40 min.
6. The preparation method of the modified lignin chelated fertilizer as claimed in claim 1, wherein the mass ratio of chloroacetic acid to lignin powder in step (3) is (0.1-0.3): 1; adding chloroacetic acid, heating to 60-90 ℃, and stirring for 60-120 min.
7. The method for preparing the modified lignin chelated fertilizer as claimed in claim 1, wherein the acidic solution in step (4) is hydrochloric acid, nitric acid or sulfuric acid; the mass fraction of the hydrochloric acid is 10-20%, the mass fraction of the nitric acid is 10-20%, and the mass fraction of the sulfuric acid is 10-20%.
8. The preparation method of the modified lignin chelated fertilizer as claimed in claim 1, wherein the mass ratio of the medium trace elements to the lignin powder in step (4) is (0.03-0.5): 1; the medium trace elements are calcium, magnesium, zinc, iron, copper and manganese.
9. The method for preparing a modified lignin chelated fertilizer as claimed in claim 8, wherein said trace elements are added in step (4) in the form of soluble inorganic compounds containing the corresponding elements.
10. The method for preparing the modified lignin chelated fertilizer as claimed in claim 9, wherein said medium trace elements are added, calcium element is calcium chloride or calcium nitrate, magnesium element is magnesium chloride, magnesium sulfate or magnesium nitrate, zinc element is zinc sulfate, zinc chloride or zinc nitrate, iron element is ferric nitrate, ferrous sulfate, ferric chloride or ferrous chloride, copper element is copper sulfate, copper nitrate or copper chloride, manganese element is manganese sulfate, manganese nitrate or manganese chloride.
11. A modified lignin-chelated fertilizer prepared by the method of any one of claims 1 to 10.
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