Composite synergistic titanyl sulfate water-soluble fertilizer and preparation method thereof

Abstract

The invention relates to a composite synergistic titanyl sulfate water-soluble fertilizer and a preparation method thereof, and belongs to the field of water-soluble fertilizer production, the composite synergistic titanyl sulfate water-soluble fertilizer comprises the following substances by weight: 2.5 parts of titanyl sulfate, 0.8 part of EDTA, 1.6 parts of manganese sulfamate, 40-50 parts of calcium ammonium nitrate, 5 parts of lysine chelated zinc, 60-80 parts of potassium dihydrogen phosphate, and 500 parts of deionized water. According to the invention, titanyl sulfate, EDTA and manganese sulfamate are compounded according to a specific low proportion, and through a synergistic effect of chelating synergism and accurate regulation and control of carbon metabolism, ion interference is avoided, and dual enhancement of the activity and quality improvement effect of the titanium fertilizer is realized at the same time; according to the invention, the chelating effect of EDTA can improve the solubility, the stability and the bioavailability of metal ions; the manganese sulfamate can promote conversion balance of oxygen and carbon dioxide in plants at low concentration, activate carbon metabolism key enzymes and improve sugar synthesis efficiency and utilization rate.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of water-soluble fertilizer production, in particular to a composite synergistic titanyl sulfate water-soluble fertilizer and a preparation method thereof. BACKGROUND

[0002] Titanium fertilizer, as a new type of plant growth regulator, has the effects of promoting photosynthesis, enhancing stress resistance, improving yield and quality, etc. in agricultural production. However, it has low solubility and poor stability in use, and titanium ions are easy to complex and lose effectiveness, so it is difficult to play a high-efficiency role. Therefore, there is an urgent need for a product that can improve the solubility and stability of titanium fertilizer. SUMMARY

[0003] The application provides a composite synergistic titanyl sulfate water-soluble fertilizer and a preparation method thereof to solve the defects in the prior art.

[0004] The application is implemented by the following technical solutions: A composite synergistic titanyl sulfate water-soluble fertilizer, comprising the following components in parts by weight: 2.5 parts of titanyl sulfate, 0.8 parts of EDTA, 1.6 parts of manganese aminosulfonate, 40-50 parts of calcium ammonium nitrate, 5 parts of lysine chelated zinc, 60-80 parts of potassium dihydrogen phosphate, and 500 parts of deionized water.

[0005] The composite synergistic titanyl sulfate water-soluble fertilizer as described above, wherein the purity of the titanyl sulfate is above 98%.

[0006] The composite synergistic titanyl sulfate water-soluble fertilizer as described above, wherein the purity of the EDTA is above 99%.

[0007] The composite synergistic titanyl sulfate water-soluble fertilizer as described above, wherein the purity of the manganese aminosulfonate is above 99%.

[0008] The composite synergistic titanyl sulfate water-soluble fertilizer as described above, wherein the purity of the calcium ammonium nitrate is above 98%.

[0009] The composite synergistic titanyl sulfate water-soluble fertilizer as described above, wherein the purity of the lysine chelated zinc is above 98.5%.

[0010] The composite synergistic titanyl sulfate water-soluble fertilizer as described above, wherein the purity of the potassium dihydrogen phosphate is above 99%.

[0011] A preparation method of a composite synergistic titanyl sulfate water-soluble fertilizer, comprising the following steps: Step one: titanyl sulfate, EDTA, manganese aminosulfonate, calcium ammonium nitrate, lysine chelated zinc, potassium dihydrogen phosphate, and deionized water are weighed according to the ratio; Step two: titanyl sulfate and EDTA are added to deionized water and stirred to dissolve; Step three: slowly add manganese sulfamate and continue to stir to dissolve; Step four: add calcium ammonium nitrate, lysine chelated zinc and potassium dihydrogen phosphate and continue to stir to dissolve; Step five: adjust the pH value; Step six: filter out impurities; Step seven: after the sub-packaging, the composite synergistic titanyl sulfate water-soluble fertilizer is obtained.

[0012] The stirring and dissolving speed in step two is 300 r / min, the stirring and dissolving temperature is 30 DEG C, and the stirring and dissolving time is 30 min. The stirring and dissolving speed in step three is 300 r / min, the stirring and dissolving temperature is 25 DEG C, and the stirring and dissolving time is 20 min. The stirring and dissolving speed in step four is 300 r / min, the stirring and dissolving temperature is 30 DEG C, and the stirring and dissolving time is 40 min.

[0013] The pH value in step five is adjusted to 5.5-6.5. The 0.45 mu m filter membrane is used for filtering out impurities in step six.

[0014] The advantages of the present application are as follows: the titanyl sulfate, EDTA and manganese sulfamate are compounded in a specific low ratio (2.5:0.8:1.6) in the present application, the synergistic effect of chelation and precise regulation of carbon metabolism is achieved, the ion interference is avoided, and the dual enhancement of the activity and quality of titanium fertilizer is realized; the chelation of EDTA in the present application can improve the solubility, stability and bioavailability of metal ions; the manganese sulfamate in the present application can promote the balance of oxygen and carbon dioxide conversion in the plant body at a low concentration, activate the key enzymes of carbon metabolism, and improve the sugar synthesis efficiency and utilization rate; the unique effect of EDTA chelation and manganese sulfamate in carbon metabolism (oxygen and carbon dioxide conversion, sugar synthesis and utilization) has not been jointly developed, and the precise matching of low proportion of manganese sulfamate can avoid ion competition interference. DETAILED DESCRIPTION

[0015] To make the purpose, technical scheme and advantages of the embodiments of the present application clearer, the technical scheme in the embodiments of the present application will be described clearly and completely below in combination with the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0016] A compound synergistic water-soluble fertilizer containing titanium sulfate oxysulfate comprises the following components in parts by weight: 2.5 parts titanium sulfate oxysulfate, 0.8 parts EDTA, 1.6 parts manganese aminosulfonate, 40-50 parts calcium ammonium nitrate, 5 parts lysine chelated zinc, 60-80 parts potassium dihydrogen phosphate, and 500 parts deionized water.

[0017] Specifically, the purity of the titanium oxysulfate described in this embodiment is above 98%.

[0018] Specifically, the purity of EDTA described in this embodiment is above 99%.

[0019] More specifically, the manganese aminosulfonate described in this embodiment has a purity of over 99%.

[0020] More specifically, the purity of the calcium ammonium nitrate described in this embodiment is above 98%.

[0021] Furthermore, the purity of the lysine chelated zinc described in this embodiment is above 98.5%.

[0022] Furthermore, the potassium dihydrogen phosphate described in this embodiment has a purity of over 99%.

[0023] A method for preparing a compound synergistic sulfate-titanium oxysulfate water-soluble fertilizer includes the following steps: Step 1: Weigh out titanium oxysulfate, EDTA, manganese sulfamate, calcium ammonium nitrate, zinc lysine chelate, potassium dihydrogen phosphate, and deionized water according to the specified ratio. Step 2: Add titanium oxysulfate and EDTA to deionized water and stir to dissolve; Step 3: Slowly add manganese aminosulfonate and continue stirring to dissolve; Step 4: Add calcium ammonium nitrate, lysine chelated zinc, and potassium dihydrogen phosphate and continue stirring to dissolve; Step 5: Adjust the pH value; Step Six: Filtering to remove impurities; Step 7: After repackaging, the compound enhanced sulfuric acid titanium dioxide water-soluble fertilizer is obtained.

[0024] Specifically, in step two of this embodiment, the stirring speed is 300 r / min, the stirring temperature is 30℃, and the stirring time is 30 min.

[0025] Specifically, in step three of this embodiment, the stirring speed is 300 r / min, the stirring temperature is 25℃, and the stirring time is 20 min.

[0026] More specifically, in step four of this embodiment, the stirring speed is 300 r / min, the stirring temperature is 30℃, and the stirring time is 40 min.

[0027] Furthermore, in step five of this embodiment, the pH value is adjusted to 5.5-6.5.

[0028] Furthermore, in step six of this embodiment, a 0.45μm filter membrane is used for filtration and impurity removal.

[0029] Example Step 1: Weigh out 2.5 parts of titanium oxysulfate, 0.8 parts of EDTA, 1.6 parts of manganese sulfamate, 40-50 parts of calcium ammonium nitrate, 5 parts of lysine chelated zinc, 60-80 parts of potassium dihydrogen phosphate, and 500 parts of deionized water according to the following ratio. Step 2: Add titanium oxysulfate and EDTA to deionized water and stir to dissolve. The stirring speed is 300 r / min, the stirring temperature is 30℃, and the stirring time is 30 min. Step 3: Slowly add manganese aminosulfonate and continue stirring to dissolve. The stirring speed is 300 r / min, the stirring temperature is 25℃, and the stirring time is 20 min. Step 4: Add calcium ammonium nitrate, lysine chelated zinc, and potassium dihydrogen phosphate and continue stirring to dissolve. The stirring speed is 300 r / min, the stirring temperature is 30℃, and the stirring time is 40 min. Step 5: Adjust the pH value to 5.5-6.5; Step 6: Filtration to remove impurities, using a 0.45μm filter membrane; Step 7: After repackaging, the compound enhanced sulfuric acid titanium dioxide water-soluble fertilizer is obtained.

[0030] Comparative Example Step 1: Weigh out 2.5 parts of titanium oxysulfate, 0.8 parts of EDTA, 40-50 parts of calcium ammonium nitrate, 5 parts of lysine chelated zinc, 60-80 parts of potassium dihydrogen phosphate, and 50-1.6 parts of deionized water according to the following ratio. Step 2: Add titanium oxysulfate and EDTA to deionized water and stir to dissolve. The stirring speed is 300 r / min, the stirring temperature is 30℃, and the stirring time is 30 min. Step 3: Add calcium ammonium nitrate, lysine chelated zinc and potassium dihydrogen phosphate and continue stirring to dissolve. The stirring speed is 300 r / min, the stirring temperature is 30℃, and the stirring time is 40 min. Step 4: Adjust the pH value to 5.5-6.5; Step 5: Filtration to remove impurities, using a 0.45μm filter membrane; Step 6: After repackaging, the compound enhanced sulfuric acid titanium dioxide water-soluble fertilizer is obtained.

[0031] Performance verification The performance of the examples and comparative examples was tested using the following methods: Solubility determination: The solubility concentrations of titanium ions and manganese ions in the composite system were determined by atomic absorption spectrophotometry. Ion compatibility evaluation: The turbidity change of the system after mixing with common fertilizer ions was measured by a turbidimeter (turbidity ≤ 5 NTU indicates compatibility). Retention time detection: using isotope labeling method ( 48 Ti、 54 Mn) tracks the dynamic accumulation and metabolic rate of titanium and manganese ions in plants; Carbon metabolism related indicators: The activities of sucrose synthase (SS) and sucrose phosphate synthase (SPS) in leaves and the content of soluble sugars (glucose, fructose, sucrose) in fruits were measured, and the sugar conversion rate (sugar accumulation / total photosynthetic product amount) was calculated. Oxygen and carbon dioxide conversion efficiency: The oxygen release rate of the light reaction and the CO2 fixation rate of the dark reaction in leaves were measured using a photosynthesis instrument.

[0032] Specific spraying treatment: The examples and comparative examples were diluted 700 times and sprayed on the leaves once each during the flowering and fruit expansion stages of the crops; Photosynthetic index determination: Net photosynthetic rate (Pn), chlorophyll SPAD value, photosynthetic utilization rate, maximum photochemical efficiency of photosystem II (Fv / Fm) and CO2 assimilation rate were measured. Stress resistance evaluation: Through drought stress (irrigation stoppage for 10 days) / low temperature stress (daytime 10℃ / nighttime 5℃, lasting for 7 days) experiments, crop survival rate, relative leaf water content (RWC), proline content and malondialdehyde (MDA) content were measured. Quality index testing: Determine the uniformity of fruit color change (ΔE value of colorimeter), sugar content (soluble solids content, TSS), sugar-acid ratio and sulfate absorption (ion-selective electrode method).

[0033] result The compound-enhanced titanium oxysulfate water-soluble fertilizer prepared in the examples achieved a titanium ion retention rate of 92% and a manganese ion retention rate of 95% after storage at 40℃ for 30 days. Furthermore, the chelating effect of EDTA on titanium ions (forming a stable Ti-EDTA complex with a stability constant logK=17.3) was not interfered with by manganese aminosulfonate, and the weak complexation of manganese ions with EDTA (Mn-EDTA logK=14.0) reduced the competition of free manganese for titanium ions, maintaining the homogeneity of the system. Compared with the compound-enhanced titanium oxysulfate water-soluble fertilizer prepared in the comparative examples, the addition of manganese aminosulfonate increased leaf SS activity by 18%-22%, SPS activity by 15%-19%, and the dark reaction CO2 fixation rate by 20%-25%, providing sufficient triose phosphate precursor for sugar synthesis.

[0034] Retention time analysis: Isotope tracking showed that the half-life of titanium ions in the leaves of the compound enhanced titanium oxysulfate water-soluble fertilizer prepared in the example was 5.2 days, which was 26.8% longer than that of the compound enhanced titanium oxysulfate water-soluble fertilizer prepared in the comparative example (4.1 days); the half-life of manganese ions was 4.5 days, which could form a "synergistic retention effect" with titanium ions and continuously promote carbon metabolism; Enhanced photosynthesis: The photosynthetic utilization rate of the compound enhanced titanium oxysulfate water-soluble fertilizer prepared in the example reached 30%-35%, which was significantly higher than that of the compound enhanced titanium oxysulfate water-soluble fertilizer prepared in the comparative example (25%-30%). At the same time, the Fv / Fm value was increased by 8%-10% compared with the compound enhanced titanium oxysulfate water-soluble fertilizer prepared in the comparative example (enhanced light reaction stability), and the CO2 assimilation rate was increased by 20%-23% compared with the compound enhanced titanium oxysulfate water-soluble fertilizer prepared in the comparative example (improved dark reaction efficiency), confirming the synergistic enhancement mechanism of "light reaction-dark reaction". Enhanced stress resistance: The compound synergistic titanium oxysulfate water-soluble fertilizer prepared in the example showed a crop survival rate of 78% under drought stress, which was 20% higher than that of the compound synergistic titanium oxysulfate water-soluble fertilizer prepared in the control group (65%). The MDA content was 12%-15% lower than that of the compound synergistic titanium oxysulfate water-soluble fertilizer prepared in the control group, and the proline content was 15%-18% higher than that of the compound synergistic titanium oxysulfate water-soluble fertilizer prepared in the control group, indicating that the synergistic effect can reduce oxidative damage.

[0035] Color-changing effect: The fruit ΔE value (color-changing uniformity) of the compound enhanced titanium oxysulfate water-soluble fertilizer prepared in the example was 12%-15% lower than that of the compound enhanced titanium oxysulfate water-soluble fertilizer prepared in the comparative example (the lower the value, the more uniform the color-changing), and the color-changing completion time was shortened by 2-3 days; the sulfate absorption was increased by 10%-12% compared with the compound enhanced titanium oxysulfate water-soluble fertilizer prepared in the comparative example, and the activity of color-changing related enzymes (such as carotenoid synthase) was increased by 15%-20% compared with the compound enhanced titanium oxysulfate water-soluble fertilizer prepared in the comparative example; Sugar content and conversion rate: The TSS content of the fruit prepared by the compound enhanced titanium oxysulfate water-soluble fertilizer in the example reached 12.5%-14.0%, which was 8%-12% higher than that of the compound enhanced titanium oxysulfate water-soluble fertilizer prepared in the comparative example (11.0%-12.0%); the sugar conversion rate reached 65%-70%, which was 15%-18% higher than that of the compound enhanced titanium oxysulfate water-soluble fertilizer prepared in the comparative example (55%-60%), confirming the promoting effect of manganese aminosulfonate on sugar synthesis and accumulation; This invention, through multiple formulation experiments, determined that a mass ratio of 2.5:0.8:1.6 represents the optimal balance of "efficient dissolution of titanium ions - precise control of manganese ions - no ion competition": EDTA (0.8) can fully chelate titanium ions (2.5) to form a stable complex, while a low proportion of manganese sulfamate (1.6) can activate carbon metabolism enzymes without causing excessive Mn. 2+ With Ti 4+Competing for EDTA coordination sites (achieving selective chelation through differences in stability constants); EDTA solves the bottleneck of "solubility-stability" in titanium fertilizer, and manganese aminosulfonate solves the bottleneck of "photosynthetic product conversion". Together with titanium oxysulfate, they form a closed loop of "raw material-efficiency enhancement-function", achieving full-chain efficiency enhancement "from photosynthetic efficiency improvement to quality improvement".

[0036] In this invention, titanium ions enhance light capture efficiency by stabilizing the photosystem structure, EDTA prolongs its action time, and manganese aminosulfonate accelerates the conversion of photosynthetic products (three-carbon compounds) into sucrose by activating enzymes such as SS and SPS, forming a highly efficient cycle of "light energy absorption - product synthesis - material accumulation".

[0037] In this invention, titanium ions enhance membrane stability, and manganese sulfamate promotes proline synthesis. The two work synergistically to reduce membrane lipid peroxidation (MDA reduction) under stress, while simultaneously increasing the accumulation of photosynthetic products to provide a material basis for stress resistance, forming a stress resistance network of "structural protection-material support".

[0038] Compared with traditional titanium fertilizers, this invention achieves a "triple breakthrough" through low-proportion compound enhancement: solubility is increased by 20%-30%, photosynthetic utilization rate is increased by 5%-10%, and sugar conversion rate is increased by 15%-20%. The use of low-proportion manganese sulfamate reduces raw material costs and avoids the potential toxicity risks of high concentrations of manganese ions. At the same time, the preparation process does not require special equipment, and field spraying with a 700-fold dilution is simple. The raw material cost is reduced by 10%-15% compared with similar products, making it feasible for large-scale production and promotion.

[0039] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A compound synergistic sulfate-titanium sulfate water-soluble fertilizer, characterized in that: The substance comprises the following components in parts by weight: 2.5 parts titanium oxysulfate, 0.8 parts EDTA, 1.6 parts manganese sulfamate, 40-50 parts calcium ammonium nitrate, 5 parts lysine chelated zinc, 60-80 parts potassium dihydrogen phosphate, and 500 parts deionized water.

2. The composite synergistic sulfate-titanium oxysulfate water-soluble fertilizer according to claim 1, characterized in that: The purity of the titanium oxysulfate is above 98%.

3. The compound synergistic sulfate-titanium oxysulfate water-soluble fertilizer according to claim 1, characterized in that: The purity of the EDTA is above 99%.

4. The compound synergistic sulfate-titanium oxysulfate water-soluble fertilizer according to claim 1, characterized in that: The purity of the manganese aminosulfonate is above 99%.

5. The composite synergistic sulfate-titanium oxysulfate water-soluble fertilizer according to claim 1, characterized in that: The purity of the calcium ammonium nitrate is above 98%.

6. The composite synergistic sulfate-titanium water-soluble fertilizer according to claim 1, characterized in that: The purity of the lysine chelated zinc is above 98.5%.

7. The composite synergistic sulfate-titanium oxysulfate water-soluble fertilizer according to claim 1, characterized in that: The purity of the potassium dihydrogen phosphate is above 99%.

8. A method for preparing a compound synergistic sulfate-titanium oxysulfate water-soluble fertilizer, characterized in that: Includes the following steps: Step 1: Weigh out titanium oxysulfate, EDTA, manganese sulfamate, calcium ammonium nitrate, zinc lysine chelate, potassium dihydrogen phosphate, and deionized water according to the specified ratio. Step 2: Add titanium oxysulfate and EDTA to deionized water and stir to dissolve; Step 3: Slowly add manganese aminosulfonate and continue stirring to dissolve; Step 4: Add calcium ammonium nitrate, lysine chelated zinc, and potassium dihydrogen phosphate and continue stirring to dissolve; Step 5: Adjust the pH value; Step Six: Filtering to remove impurities; Step 7: After repackaging, the compound enhanced sulfuric acid titanium dioxide water-soluble fertilizer is obtained.

9. The preparation method of a composite synergistic oxytitanium sulfate water-soluble fertilizer according to claim 8, characterized in that: In step two, the stirring speed is 300 r / min, the stirring temperature is 30℃, and the stirring time is 30 min. In step three, the stirring speed is 300 r / min, the stirring temperature is 25℃, and the stirring time is 20 min. In step four, the stirring speed is 300 r / min, the stirring temperature is 30℃, and the stirring time is 40 min.

10. The method for preparing a composite synergistic oxytitanium sulfate water-soluble fertilizer according to claim 8, characterized in that: In step five, the pH value is adjusted to 5.5-6.5; In step six, a 0.45μm filter membrane is used for filtration and impurity removal.