Organic water-soluble fertilizer containing alginic acid and preparation method thereof

Abstract

The invention relates to the technical field of fertilizer manufacturing, and discloses an alginic acid-containing organic water-soluble fertilizer and a preparation method thereof.The alginic acid-containing organic water-soluble fertilizer is prepared from humic acid, potassium nitrate, urea phosphate, monopotassium phosphate, urea, micronutrient element-loaded phytic acid and alginic acid components and tap water; phytic acid and alginic acid are prepared by loading negatively charged phytic acid onto a negatively charged alginic acid matrix by a quaternary ammonium salt type connecting agent through electrostatic acting force; the micronutrient element loaded phytic acid and alginic acid component is obtained by loading micronutrient elements by phytic acid and alginic acid through an ion coordination effect; the use amount of the water is that 0.5-0.6 L of water is added into each kilogram of solid components. The alginic acid-containing organic water-soluble fertilizer prepared by the invention has the beneficial technical effects of slowly releasing micronutrient elements and improving the utilization rate of micronutrient in the fertilizer.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of fertilizer manufacturing, in particular to a kind of organic water-soluble fertilizer containing alginic acid and a preparation method thereof. BACKGROUND

[0002] Water-soluble fertilizer is a liquid or solid fertilizer used for irrigation fertilization, foliar fertilization, soilless culture, seed soaking and root dipping, etc. Alginic acid is a polysaccharide that provides main energy metabolism for plants, and has obvious beneficial effects on plants and soil. Organic water-soluble fertilizer containing alginic acid is a natural, organic, non-toxic and efficient fertilizer. Phytic acid is a negatively charged natural organic phosphoric compound that can chelate with metal ions and provide phosphorus nutrition for plants. In addition, alginic acid has the function of chelating metal ions due to its negative charge, which can enhance the chelating ability of alginic acid for trace nutrients, slowly release trace nutrients when added to fertilizer, prolong the effective supply time of nutrients in soil, avoid chemical reaction of trace nutrients with soil ions, and thus improve the utilization rate of trace nutrients in fertilizer. SUMMARY

[0003] The present application provides a kind of organic water-soluble fertilizer containing alginic acid and a preparation method thereof. By preparing phytic acid-alginic acid component loaded with trace nutrients and adding it to organic water-soluble fertilizer, the technical goal of slow release of trace nutrients and improvement of utilization rate of trace nutrients in fertilizer can be achieved.

[0004] To achieve the above-mentioned purpose, the present application adopts the following technical scheme:

[0005] A kind of organic water-soluble fertilizer containing alginic acid, comprising the following raw materials by weight:

[0006] 4-8 parts of humic acid;

[0007] 1-5 parts of potassium nitrate;

[0008] 14-24 parts of urea phosphate;

[0009] 2-6 parts of potassium dihydrogen phosphate;

[0010] 0.1-1.5 parts of urea;

[0011] 2-6 parts of phytic acid-alginic acid component loaded with trace nutrients;

[0012] Phytic acid-alginic acid is prepared by loading negatively charged phytic acid onto negatively charged alginic acid matrix through electrostatic force using quaternary ammonium salt type linker. The mass ratio of alginic acid, quaternary ammonium salt type linker and phytic acid is 1:(0.9-1.5):1.

[0013] The phytic acid@alginate component loaded with trace nutrients is obtained by loading the trace nutrients with phytic acid@alginate through ion coordination.

[0014] The trace nutrients are one or a combination of more than one of copper, zinc, iron and manganese;

[0015] The mass ratio of trace nutrients to phytic acid@alginic acid is (0.5-1):(14.5-20);

[0016] Tap water: add 0.5-0.6L of water per kilogram of solid components.

[0017] Furthermore, the preparation method of the quaternary ammonium salt linker is:

[0018] Based on the quaternization reaction mechanism, quaternary ammonium epoxide is prepared using triethylamine containing nitrogen nutrients required by plants and epichlorohydrin containing chlorine nutrients required by plants as raw materials;

[0019] Based on the carboxyl / hydroxyl-epoxy ring-opening mechanism, a quaternary ammonium salt linker was prepared using epoxidized quaternary ammonium salt and soil conditioner citric acid as raw materials.

[0020] Furthermore, the quaternary ammonium salt type linker is any one of a quaternary ammonium salt type linker, a triquaternary ammonium salt type linker or a diquaternary ammonium salt type linker.

[0021] Furthermore, the preparation method of the epoxidized quaternary ammonium salt is:

[0022] Epichlorohydrin is added dropwise to triethylamine, the pH value is adjusted to 8-9, and the reaction is carried out for 1-3 hours, followed by filtration, washing, impurity removal, and vacuum drying to obtain an epoxidized quaternary ammonium salt.

[0023] Furthermore, the preparation method of the quaternary ammonium salt linker is:

[0024] Adding epoxidized quaternary ammonium salt and citric acid to acetone, adjusting the pH value to 7-8, and reflux reaction for 6-10 hours, adjusting the pH value to neutral, evaporating, washing, recrystallizing, and vacuum drying to obtain a quaternary ammonium salt type linker.

[0025] Furthermore, the preparation method of the phytic acid@alginic acid component loaded with trace nutrients is:

[0026] Add alginic acid to deionized water, stir ultrasonically, add phytic acid, stir and mix evenly, add a quaternary ammonium salt linker, stir at a rate of 200-400 r / min for 2-4 hours, add trace nutrients, stir and mix evenly, adjust the pH value to 7-8, react at 40-60°C for 3-5 hours, filter, and dry to obtain a phytic acid@alginate component loaded with trace nutrients.

[0027] The beneficial effects of the present invention are as follows:

[0028] The invention uses triethylamine containing nitrogen nutrients required by plants, epichlorohydrin containing chlorine nutrients required by plants, and citric acid, a soil conditioner, as raw materials to prepare a quaternary ammonium salt type linker. Based on electrostatic force, the quaternary ammonium salt type linker loads negatively charged phytic acid onto a negatively charged alginate matrix to enhance the ability of the alginate matrix to chelate trace nutrients. The trace nutrients are loaded through ion coordination to prepare a phytic acid@alginate component loaded with trace nutrients. The component provides nitrogen, phosphorus, and chlorine sources. When added to fertilizer, the component releases the trace elements under the action of soil microorganisms, thereby extending the effective supply time of the trace nutrients in the soil. DETAILED DESCRIPTION

[0029] Experimental Example 1:

[0030] Alginic acid has the ability to chelate trace elements, but the chelated product is unstable. Phytic acid contains multiple phosphate groups and has strong chelating ability. Therefore, phytic acid can be combined with alginic acid to improve the chelating ability of alginic acid. However, alginic acid and phytic acid are only connected by hydrogen bonds, and the connection effect is poor. Based on this, triethylamine containing nitrogen nutrients required by plants, epichlorohydrin containing chlorine nutrients required by plants, and citric acid, a soil conditioner, are used as raw materials. Based on the quaternization reaction mechanism and the carboxyl / hydroxyl-epoxy ring-opening mechanism, a quaternary ammonium salt linker is prepared. Based on electrostatic force, the quaternary ammonium salt linker is used to load the negatively charged phytic acid onto the negatively charged alginate matrix to achieve the improvement of the chelating ability of the alginate matrix.

[0031] 1. The specific preparation steps of the quaternary ammonium salt linker are:

[0032] Step 1: 2.3 g of epichlorohydrin was added dropwise to 3.5 g of triethylamine, and the pH value was adjusted to 9. After reacting for 1.5 h, the mixture was filtered under reduced pressure, washed with acetone, and rotary evaporated to remove impurities. The mixture was dried in vacuo to obtain an epoxidized quaternary ammonium salt;

[0033] Step 2: Add 7.8 g of epoxidized quaternary ammonium salt and 1.9 g of citric acid to acetone, adjust the pH value to 8, reflux for 8 hours, adjust the pH value to neutral, rotary evaporate, wash with acetone, recrystallize, and vacuum dry to obtain a four-season ammonium salt type linker;

[0034] Among them, the chemical structural formula of the four-season ammonium salt type linker is:

[0035] ;

[0036] By adjusting the amount of epoxidized quaternary ammonium salt, diquaternary ammonium salt type linkers and triquaternary ammonium salt type linkers can be prepared.

[0037] II. Preparation of phytic acid-alginic acid component loaded with trace elements, as follows:

[0038] 5 g of alginic acid (item number BKR7852, content (carboxyl group) (on a dry basis): 19-25%, purchased from Shanghai Ruike Biotechnology Co., Ltd.) was added to 200 mL of deionized water, and after ultrasonic stirring for 15 min, 3.5 mL of phytic acid was added, and after stirring and mixing uniformly, 8 g of tetramethylammonium salt type linker was added, and stirred at a speed of 300 r / min for 3 h, and then 0.7 g of copper sulfate pentahydrate, 0.8 g of zinc sulfate heptahydrate, 0.8 g of ferrous sulfate heptahydrate, and 0.5 g of manganese sulfate monohydrate were added, and stirred and mixed uniformly, and the pH value was adjusted to 8 with sodium hydroxide solution, and after reaction at 60°C for 4 h, filtration and drying were performed, to obtain a phytic acid-alginic acid component loaded with trace elements.

[0039] Example 1:

[0040] An alginic acid-containing organic water-soluble fertilizer, comprising the following raw materials in parts by weight:

[0041] 4.8 parts of humic acid (purchased from Yingxian Hongjie Fertilizer Co., Ltd.);

[0042] 2 parts of potassium nitrate;

[0043] 15 parts of urea phosphate;

[0044] 3 parts of potassium dihydrogen phosphate;

[0045] 0.1 part of urea;

[0046] 3 parts of phytic acid-alginic acid component loaded with trace elements (prepared in Experimental Example 1);

[0047] Water; wherein the amount of water is added at a ratio of 0.56 L of water per kilogram of solid components;

[0048] An alginic acid-containing organic water-soluble fertilizer, and the specific preparation method thereof is as follows:

[0049] First step, heat the water to 60°C, and then add the humic acid according to the formula ratio, stir and dissolve, add the potassium nitrate, stir and dissolve, add the urea phosphate, stir and dissolve, add the potassium dihydrogen phosphate, stir and dissolve, add the urea, stir and dissolve, add the phytic acid-alginic acid component loaded with trace elements, stir and mix for 5 h, and then cool to room temperature to obtain a mixed solution;

[0050] Second step, sand mill the mixed solution, stir, and then perform canning to obtain the alginic acid-containing organic water-soluble fertilizer.

[0051] Example 2:

[0052] An organic water-soluble fertilizer containing alginic acid, comprising the following raw materials by weight:

[0053] 6.5 parts of humic acid (purchased from Yingxian Hongjie Fertilizer Co., Ltd.);

[0054] 2.5 parts of potassium nitrate;

[0055] 18 parts of urea phosphate;

[0056] 4 parts of potassium dihydrogen phosphate;

[0057] 0.6 parts of urea;

[0058] 3 parts of phytic acid@alginic acid component loaded with trace elements (prepared in Experimental Example 1);

[0059] Water; wherein the amount of water is added according to the proportion of 0.6 L of water per kg of solid components;

[0060] An organic water-soluble fertilizer containing alginic acid, and the specific preparation method thereof is:

[0061] First step, heat the water to 60℃, add humic acid according to the formula proportion, stir and dissolve, add potassium nitrate, stir and dissolve, add urea phosphate, stir and dissolve, add potassium dihydrogen phosphate, stir and dissolve, add urea, stir and dissolve, add phytic acid@alginic acid component loaded with trace elements, stir and mix for 5h, then cool to room temperature to obtain a mixed solution;

[0062] Second step, sand mill the mixed solution, stir and then bottle to obtain an organic water-soluble fertilizer containing alginic acid.

[0063] Example 3:

[0064] An organic water-soluble fertilizer containing alginic acid, comprising the following raw materials by weight:

[0065] 8 parts of humic acid (purchased from Yingxian Hongjie Fertilizer Co., Ltd.);

[0066] 4 parts of potassium nitrate;

[0067] 22 parts of urea phosphate;

[0068] 5 parts of potassium dihydrogen phosphate;

[0069] 1 part of urea;

[0070] 5 parts of phytic acid@alginic acid component loaded with trace elements (prepared in Experimental Example 1);

[0071] Water; wherein the amount of water is added according to the proportion of 0.59 L of water per kg of solid components;

[0072] An organic water-soluble fertilizer containing alginic acid, and the specific preparation method thereof is:

[0073] First step, heating water to 60℃, according to the formula proportion to which add humic acid, stirring to dissolve, add potassium nitrate, stirring to dissolve, add urea phosphate, stirring to dissolve, add potassium dihydrogen phosphate, stirring to dissolve, add urea, stirring to dissolve, add phytic acid alginate component loaded with trace elements, stirring and mixing for 5h, then cooled to room temperature, to obtain a mixed solution;

[0074] Second step, the mixed solution is sanding, stirring, and then tanking to obtain alginate-containing organic water-soluble fertilizer.

[0075] Performance test:

[0076] I. Determination of organic matter content

[0077] The organic matter content in the alginate-containing organic water-soluble fertilizer prepared in Examples 1-3 was detected according to the method in standard NY / T 1976-2010, and the results are shown in Table 1:

[0078] Table 1 Test results of organic matter content

[0079] No. Organic matter content (g / L) Example 1 125.79 Example 2 124.06 Example 3 131.56

[0080] II. Determination of nutrient content

[0081] The nitrogen, phosphorus and potassium nutrients in the alginate-containing organic water-soluble fertilizer prepared in Examples 1-3 were detected according to the method in standard NY / T 1977-2010, and the results are shown in Table 2:

[0082] Table 2 Test results of nutrient content

[0083] No. Nitrogen (N) (g / L) phosphorus (P2O5) / (g / L) potassium (K2O) / (g / L) Example 1 78.5 89.3 37.6 Example 2 77.7 84.9 38.2 Example 3 77.6 82.3 41.7

[0084] III. Determination of trace element content

[0085] The contents of trace elements copper, zinc, iron and manganese in the alginate-containing organic water-soluble fertilizer prepared in Examples 1-3 were detected according to the method in standard NY / T 1974-2010, and the content of trace element chlorine in the alginate-containing organic water-soluble fertilizer prepared in Examples 1-3 was detected according to standard NY / T 1117-2010, and the results are shown in Table 3:

[0086] Table 3 Test results of trace element content

[0087] No. Copper (g / L) Zinc (g / L) Iron (g / L) Manganese (g / L) Example 1 0.778 0.795 0.680 0.671 Example 2 0.610 0.632 0.537 0.529 Example 3 0.791 0.810 0.691 0.682

[0088] IV. Application experiment

[0089] The soil is selected as sandy loam, and is planted in the open air. The bitter wheat is selected as the test seedling, the growth period is 50 days, the spraying can is used according to the conventional watering level, the spraying can is 10L, the application is 2 times during the period, and the application is 1 time every 7 days. The seaweed acid-containing organic water-soluble fertilizer prepared in the examples 1-3 is diluted by 1000 times, the clear water is set as the control group, the test is carried out on the basis of the conventional fertilization of the test seedling, the fertilizer is poured for the first time after the bitter wheat is transplanted and planted for 15 days, then the fertilizer is poured on the 7th day and the 14th day after the first time, the agronomic characters of the bitter wheat are measured on the 35th day, and the results are shown in Table 4.

[0090] Table 4 Agronomic characters of bitter wheat

[0091] No. Plant height (cm) Leaf number (pieces) Fresh weight per plant (g) Example 1 38.87 7.2 41.31 Example 2 38.21 6.9 40.98 Example 3 37.92 6.7 40.15 Control group 33.12 6.1 36.21

[0092] As shown in Table 4, after the seaweed acid-containing organic water-soluble fertilizer prepared in the examples 1-3 is diluted by 1000 times, the bitter wheat is poured, compared with the clear water control group, the promoting effect on the plant height, the leaf number and the fresh weight of single plant of the bitter wheat is obvious.

Claims

1. An organic water-soluble fertilizer containing alginic acid, characterized in that: The invention comprises the following raw materials in parts by weight: 4-8 parts humic acid; 1-5 parts potassium nitrate; 14-24 parts of urea phosphate; 2-6 parts potassium dihydrogen phosphate; 0.1-1.5 parts of urea; 2-6 parts of phytic acid@alginic acid component loaded with trace nutrients; Phytic acid@alginate is prepared by loading negatively charged phytic acid onto a negatively charged alginate matrix via electrostatic force using a quaternary ammonium salt linker. The mass ratio of alginate, quaternary ammonium salt linker, and phytic acid is 1:(0.9-1.5):

1. The phytic acid@alginate component loaded with trace nutrients is obtained by loading the trace nutrients with phytic acid@alginate through ion coordination. The trace nutrients are one or a combination of more than one of copper, zinc, iron and manganese; The mass ratio of trace nutrients to phytic acid@alginic acid is (0.5-1):(14.5-20); Tap water: add 0.5-0.6L of water per kilogram of solid components.

2. The organic water-soluble fertilizer containing alginic acid according to claim 1, characterized in that: The preparation method of the quaternary ammonium salt linker is: Based on the quaternization reaction mechanism, quaternary ammonium epoxide is prepared using triethylamine containing nitrogen nutrients required by plants and epichlorohydrin containing chlorine nutrients required by plants as raw materials; Based on the carboxyl / hydroxyl-epoxy ring-opening mechanism, a quaternary ammonium salt linker was prepared using epoxidized quaternary ammonium salt and soil conditioner citric acid as raw materials.

3. The organic water-soluble fertilizer containing alginic acid according to claim 2, characterized in that: The quaternary ammonium salt type linker is any one of a quaternary ammonium salt type linker, a triquaternary ammonium salt type linker or a diquaternary ammonium salt type linker.

4. The organic water-soluble fertilizer containing alginic acid according to claim 2, characterized in that: The preparation method of the epoxidized quaternary ammonium salt is: Epichlorohydrin is added dropwise to triethylamine, the pH value is adjusted to 8-9, and the reaction is carried out for 1-3 hours, followed by filtration, washing, impurity removal, and vacuum drying to obtain an epoxidized quaternary ammonium salt.

5. The organic water-soluble fertilizer containing alginic acid according to claim 2, characterized in that: The preparation method of the quaternary ammonium salt linker is: Adding epoxidized quaternary ammonium salt and citric acid to acetone, adjusting the pH value to 7-8, and reflux reaction for 6-10 hours, adjusting the pH value to neutral, evaporating, washing, recrystallizing, and vacuum drying to obtain a quaternary ammonium salt type linker.

6. The organic water-soluble fertilizer containing alginic acid according to claim 1, characterized in that: The preparation method of the phytic acid@alginic acid component loaded with trace nutrients is as follows: Add alginic acid to deionized water, stir ultrasonically, add phytic acid, stir and mix evenly, add a quaternary ammonium salt linker, stir at a rate of 200-400 r / min for 2-4 hours, add trace nutrients, stir and mix evenly, adjust the pH value to 7-8, react at 40-60°C for 3-5 hours, filter, and dry to obtain a phytic acid@alginate component loaded with trace nutrients.