CN114773129A - Hard water resistant water-soluble fertilizer and application thereof - Google Patents
Hard water resistant water-soluble fertilizer and application thereof Download PDFInfo
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- CN114773129A CN114773129A CN202210439277.9A CN202210439277A CN114773129A CN 114773129 A CN114773129 A CN 114773129A CN 202210439277 A CN202210439277 A CN 202210439277A CN 114773129 A CN114773129 A CN 114773129A
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- potassium
- phosphoric acid
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- hard water
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/80—Soil conditioners
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B11/00—Fertilisers produced by wet-treating or leaching raw materials either with acids in such amounts and concentrations as to yield solutions followed by neutralisation, or with alkaline lyes
- C05B11/04—Fertilisers produced by wet-treating or leaching raw materials either with acids in such amounts and concentrations as to yield solutions followed by neutralisation, or with alkaline lyes using mineral acid
- C05B11/10—Fertilisers produced by wet-treating or leaching raw materials either with acids in such amounts and concentrations as to yield solutions followed by neutralisation, or with alkaline lyes using mineral acid using orthophosphoric acid
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Soil Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Fertilizers (AREA)
Abstract
The application discloses water-soluble fertilizer of anti hard water and application thereof includes: polyphosphoric acid humic acid ammonium potassium humate; and a base fertilizer; wherein, the polyphosphoric acid humic acid ammonium potassium: the mass ratio of the basic fertilizer is 1-99: 1-99, the polyphosphoric acid ammonium humate potassium is prepared by reacting phosphoric acid, potassium humate, ammonia and a condensing agent, wherein the phosphoric acid: the mass ratio of the potassium humate is 10: 1-10: 10, phosphoric acid: the ammonia molar ratio is 1: 1-1: 3, phosphoric acid: the mass ratio of the condensing agent is 10: 0.1-10: 5 this application anti hard water effect is stable, and has the fertilizer ratio of broad.
Description
Technical Field
The application particularly relates to a hard water resistant water-soluble fertilizer and application thereof.
Background
Humic acid contains various functional groups with chemical activity and biological activity, improves the soil structure, adjusts the pH value of the soil, enhances the buffer capacity of the soil, stimulates the growth and the reproduction of beneficial microorganisms in the soil, enhances the functions of fertilizers and the like, and is widely applied in agriculture. However, due to the rise of facility agriculture, the humic acid has poor hard water resistance, forms flocculent precipitates with calcium and magnesium ions in water and is not beneficial to use; in addition, when the liquid fertilizer is prepared, the liquid fertilizer is unstable after being placed for a long time, and a large amount of colloidal sediment is formed at the bottom of the liquid fertilizer. The ammonium polyphosphate is a nitrogen-phosphorus binary compound fertilizer, can chelate metal ions in soil, is not easily solidified by the soil, and greatly improves the phosphorus utilization rate; in recent years, the application of ammonium polyphosphate is also more and more extensive. However, ammonium polyphosphate has relatively weak calcium and magnesium chelating capacity, so that ammonium orthophosphate in ammonium polyphosphate and calcium and magnesium ions in hard water are easy to separate into flocculent precipitates after entering water, and the ammonium polyphosphate is limited to be used in facility agriculture.
Patent application No. CN201911046274.3 discloses a hard water resistant neutral slightly alkaline macroelement water-soluble fertilizer, and mentions that humic acid and water-soluble ammonium polyphosphate are combined according to a certain proportion to generate self-masking effect on mutual chelation positions, so that flocculation precipitation is not easy to generate, and the problem that both parties are easy to precipitate when meeting hard water is solved; but the effect of hard water resistance is limited, and although no precipitation is generated in 24 hours, the masking effect is extremely unstable, and particularly, the masking effect is more unstable and the precipitation is more easily generated along with the larger dilution time, so that the pipeline is blocked.
Disclosure of Invention
To above-mentioned defect, the application provides a water-soluble fertilizer of anti hard water, and anti hard water effect is stable, and has the fertilizer ratio of broad.
The application utilizes active hydroxyl in the potassium humate to perform condensation reaction with ammonium phosphate (generated by reaction of phosphoric acid and ammonia) to form the polyphosphoric acid ammonium humate potassium, which has better water solubility, is not easy to generate precipitation after being dissolved in hard water, is prepared into the humic acid-containing water-soluble fertilizer, is stable for long-term storage, and can be directly applied or used as a raw material for preparing the humic acid-containing water-soluble fertilizer.
The technical scheme is as follows: a hard water resistant water soluble fertilizer comprising:
polyphosphoric acid ammonium potassium humate; and
a base fertilizer;
wherein, polyphosphoric acid humic acid ammonium potassium: the mass ratio of the basic fertilizer is 1-99: 1-99, the polyphosphoric acid ammonium humate potassium is prepared by reacting phosphoric acid, potassium humate, ammonia and a condensing agent, wherein the phosphoric acid: the mass ratio of the potassium humate is 10: 1-10: 10, phosphoric acid: the ammonia molar ratio is 1: 1-1: 3, phosphoric acid: the mass ratio of the condensing agent is 10: 0.1-10: 5.
optionally, the phosphoric acid: the mass ratio of the potassium humate is 10: 1-10: 5, phosphoric acid: the ammonia molar ratio is 1: 1-1: 2, phosphoric acid: the mass ratio of the condensing agent is 10: 0.3-10: 2.
optionally, the condensing agent is a mixture of urea and ammonium sulfate.
Optionally, the urea: the mass ratio of ammonium sulfate is 50-99: 1-10.
Optionally, the base fertilizer is one or more of potassium nitrate, urea, boric acid, EDTA-Mn, potassium sulfate and ammonium sulfate.
Optionally, the ammonium humic acid polyphosphate potassium is prepared by the following steps:
firstly, uniformly mixing phosphoric acid and potassium humate to obtain mixed slurry;
pressurizing the mixed slurry and ammonia to 0.2-1MPa, feeding the mixture into a reactor for reaction, and spraying out a molten material after the reaction;
thirdly, putting the molten material into a polymerization reaction kettle, and adding a condensing agent;
cooling the reacted materials;
crushing to obtain polyphosphoric acid ammonium humic acid potassium.
Optionally, in the step (ii), the reaction temperature is 120-200 ℃, the reaction time is 5s-2min, and the reactor is a tubular reactor; and thirdly, the reaction temperature is 120-200 ℃, and the reaction time is 60-120 min.
The application also provides application of the water-soluble fertilizer solution for resisting hard water.
The technical scheme is as follows: the hard water resistant water soluble fertilizer is soluble in hard water and is used for agricultural production.
Detailed Description
The present application will be further explained below.
In the following examples 1-8:
the phosphoric acid is: commercially available, 85 wt% technical phosphoric acid;
the potassium humate is as follows: commercially available, humic acid content is more than or equal to 65.0 wt%, potassium oxide content (K)2O)≥10.0wt％。
Example 1
Uniformly mixing 100 kg of phosphoric acid and 10 kg of potassium humate to obtain mixed slurry; pressurizing the mixed slurry and ammonia gas to 0.5mPa, putting the mixed slurry and ammonia gas into a tubular reactor, and controlling the molar ratio of phosphoric acid to ammonia to be 1:1.4 by an adjusting valve; the temperature of the tubular reactor was controlled at 185 ℃ and the reaction time was 10 seconds, and 113.2 kg of the molten material was obtained by blowing out the molten material through the tubular reactor.
The molten material is put into a polymerization reactor, 20 kg of condensing agent (the weight ratio of urea to ammonium sulfate is 95: 5) is added, the temperature of the polymerization reactor is controlled at 185 ℃, and the reaction time is 90 minutes. Then discharging the materials into a mixer through a bottom valve of the polymerization reaction kettle; and 118 kg of polyphosphoric acid ammonium potassium humate is obtained by cold crushing.
Example 2
Uniformly mixing 100 kg of phosphoric acid and 20 kg of potassium humate to obtain mixed slurry; pressurizing the mixed slurry and ammonia gas to 0.5mPa, putting the mixed slurry and ammonia gas into a tubular reactor, and controlling the molar ratio of phosphoric acid to ammonia to be 1:1.4 by an adjusting valve; the temperature of the tubular reactor was controlled at 185 ℃ and the reaction time was 10s, and the molten material was obtained in an amount of 124 kg by spraying through the tubular reactor.
The molten material was put into a polymerization reactor, 24.8 kg of condensing agent (urea: ammonium sulfate ratio: 95:5 by weight) was added, the polymerization reactor temperature was controlled at 185 ℃ and the reaction time was 90 minutes. Then discharging the materials into a mixer through a bottom valve of the polymerization reaction kettle; and cooling and crushing to obtain 128.3 kg of polyphosphoric acid ammonium potassium humate.
Example 3
Uniformly mixing 100 kg of phosphoric acid and 50 kg of potassium humate to obtain mixed slurry; pressurizing the mixed slurry and gas ammonia to 0.5mPa, feeding the mixture into a tubular reactor, and controlling the molar ratio of phosphoric acid to ammonia to be 1:1.4 by using an adjusting valve; the temperature of the tubular reactor was controlled at 185 ℃ and the reaction time was 10 seconds, and 150.5 kg of the molten material was obtained by blowing out the molten material through the tubular reactor.
The molten material was put into a polymerization reactor, 30.1 kg of condensing agent (urea: ammonium sulfate ratio: 95:5 by weight) was added, the polymerization reactor temperature was controlled at 185 ℃ and the reaction time was 90 minutes. Then discharging the materials into a mixer through a bottom valve of the polymerization reaction kettle; 154.1 kg of polyphosphoric acid ammonium humic acid potassium is obtained by cold crushing.
Example 4
Uniformly mixing 100 kg of phosphoric acid and 20 kg of potassium humate to obtain mixed slurry; pressurizing the mixed slurry and ammonia gas to 0.5mPa, putting the mixed slurry and ammonia gas into a tubular reactor, and controlling the molar ratio of phosphoric acid to ammonia to be 1:1.4 by an adjusting valve; the temperature of the tubular reactor was controlled at 185 ℃ and the reaction time was 10s, and 125.7 kg of the molten material was obtained by spraying the molten material through the tubular reactor.
The molten material was placed in a polymerization reactor, 12.57 kg of condensing agent (urea: ammonium sulfate ratio 98:2 by weight) was added, the polymerization reactor temperature was controlled at 185 ℃ and the reaction time was 90 minutes. Then discharging the materials into a mixer through a bottom valve of the polymerization reaction kettle; 127.5 kg of polyphosphoric acid ammonium potassium humate is obtained by cold crushing.
Example 5
Uniformly mixing 100 kg of phosphoric acid and 20 kg of potassium humate to obtain mixed slurry; pressurizing the mixed slurry and gas ammonia to 0.5mPa, feeding the mixture into a tubular reactor, and controlling the molar ratio of phosphoric acid to ammonia to be 1:1.4 by using an adjusting valve; the temperature of the tubular reactor was controlled at 185 ℃ and the reaction time was 10s, and 125.8 kg of the molten material was obtained by blowing out through the tubular reactor.
The molten material was placed in a polymerization reactor, 37.74 kg of condensing agent (urea: ammonium sulfate ratio: 90:10 by weight) was added, the polymerization reactor temperature was controlled at 185 ℃ and the reaction time was 90 minutes. Then discharging the materials into a mixer through a bottom valve of the polymerization reaction kettle; the mixture is cooled and crushed to obtain 131.5 kg of polyphosphoric acid ammonium potassium humate.
Example 6
The physical and chemical indexes of the ammonium humic acid polyphosphate potassium of the examples 1 to 5 are measured, and the results are shown in the following table 1.
TABLE 1
In table 1, water in solubility is pure water (distilled water).
Example 7
The ammonium potassium humate polyphosphate of examples 1-5 was subjected to hard water resistance tests (1:300 fold hard water dilution, water hardness 35 degrees, 1:300 fold, e.g. in kg, 1 kg ammonium potassium humate polyphosphate, 300 kg hard water) and the results are given in table 2 below.
TABLE 2
As can be seen from table 2, example 2 works best, followed by example 3, then example 4, example 1, and finally example 5.
Example 8
200g of the polyphosphoric acid ammonium humic acid potassium product produced in the implementation 2 is taken, 205 g of potassium nitrate and 95g of urea are added to prepare the fertilizer A, wherein the proportion of nitrogen, phosphorus and potassium is 19-19 percent, and the humic acid is more than or equal to 4.0 percent.
Taking 75g of the polyphosphoric acid ammonium humic acid potassium product produced in the implementation 3, adding 100 g of potassium nitrate, 200g of potassium sulfate and 125g of urea to prepare a fertilizer B, wherein the proportion of nitrogen, phosphorus and potassium is 15-6-30, and the humic acid is more than or equal to 3.0%.
130g of polyphosphoric acid ammonium potassium humate product produced in the implementation 3 is taken, 105 g of potassium nitrate and 265g of urea are added to prepare the fertilizer C, wherein the proportion of nitrogen, phosphorus and potassium is 30-10-10, and the humic acid is more than or equal to 5.0%.
Taking 400g of the ammonium potassium humate polyphosphate product produced in the implementation 3, adding 50g of potassium nitrate, 35g of potassium sulfate, 8g of ammonium sulfate, 3.5g of boric acid and 3.5g of EDTA-Mn to prepare a fertilizer D, wherein the proportion of nitrogen, phosphorus and potassium is 10-32-10, and the humic acid is more than or equal to 17.0%.
Taking potassium humate (fertilizer E) and proportioning nitrogen, phosphorus and potassium by 0-0-10.
Taking commercially available water-soluble ammonium polyphosphate (fertilizer F), wherein the nitrogen (N) is more than or equal to 18.0 percent, the phosphorus (P2O5) is more than or equal to 60.0 percent, and the mixture ratio of nitrogen, phosphorus and potassium is 18-60-0.
160G of water-soluble ammonium polyphosphate (sold in the market), 120G of potassium nitrate, 70G of potassium sulfate, 115G of urea and 35G of humic acid potassium are prepared into the fertilizer G, wherein the proportion of nitrogen, phosphorus and potassium is 19-19 percent, and the humic acid is more than or equal to 4.0 percent.
Preparing a fertilizer H from 250g (commercially available) of water-soluble ammonium polyphosphate, 150g of potassium humate, 50g of potassium nitrate, 35g of potassium sulfate, 8g of ammonium sulfate, 3.5g of boric acid and EDTA-Mn3.5g, wherein the proportion of nitrogen, phosphorus and potassium is 10-30-11, and the humic acid is more than or equal to 19.0%.
The fertilizers A-H were subjected to hard water resistance tests, and the results are shown in Table 3 below.
TABLE 3
The results in Table 3 show that the hard water resistance of the fertilizers A-D is better than that of the fertilizers E-H, which indicates that the polyphosphoric acid ammonium humic acid potassium prepared by the application has better hard water resistance when being used as a water-soluble fertilizer by being matched with other fertilizers.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (8)
1. A hard water resistant water soluble fertilizer comprising:
polyphosphoric acid ammonium potassium humate; and
a base fertilizer;
wherein, the polyphosphoric acid humic acid ammonium potassium: the mass ratio of the basic fertilizer is 1-99: 1-99, the polyphosphoric acid ammonium humate potassium is prepared by reacting phosphoric acid, potassium humate, ammonia and a condensing agent, wherein the phosphoric acid: the mass ratio of the potassium humate is 10: 1-10: 10, phosphoric acid: the ammonia molar ratio is 1: 1-1: 3, phosphoric acid: the mass ratio of the condensing agent is 10: 0.1-10: 5.
2. the hard water resistant water soluble fertilizer of claim 1, wherein the phosphoric acid: the mass ratio of the potassium humate is 10: 1-10: 5, phosphoric acid: the ammonia molar ratio is 1: 1-1: 2, phosphoric acid: the mass ratio of the condensing agent is 10: 0.3-10: 2.
3. the hard water resistant water soluble fertilizer according to claims 1-2, wherein said condensing agent is a mixture of urea and ammonium sulfate.
4. The hard water resistant water soluble fertilizer according to claim 3, wherein the urea: the mass ratio of ammonium sulfate is 50-99: 1-10.
5. The hard water resistant water soluble fertilizer according to any one of claims 1 to 4, wherein the base fertilizer is one or more of potassium nitrate, urea, boric acid, EDTA-Mn, potassium sulfate, ammonium sulfate.
6. The hard water resistant water soluble fertilizer according to any one of claims 1-5, wherein the ammonium humic acid polyphosphate potassium is prepared by the following steps:
firstly, uniformly mixing phosphoric acid and potassium humate to obtain mixed slurry;
pressurizing the mixed slurry and ammonia to 0.2-1MPa, feeding the mixture into a reactor for reaction, and spraying out a molten material after the reaction;
thirdly, putting the molten material into a polymerization reaction kettle, and adding a condensing agent;
fourthly, cooling the material after the reaction in the third step;
crushing to obtain polyphosphoric acid ammonium humic acid potassium.
7. The hard water resistant water-soluble fertilizer as claimed in claim 6, wherein the reaction temperature is 120-200 ℃, the reaction time is 5s-2min, and the reactor is a tubular reactor; and thirdly, the reaction temperature is 120-200 ℃, and the reaction time is 60-120 min.
8. A hard water resistant water soluble fertilizer as claimed in any one of claims 1 to 7 which is soluble in hard water for use in agricultural operations.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210439277.9A CN114773129B (en) | 2022-04-25 | 2022-04-25 | Hard water resistant water-soluble fertilizer and application thereof |
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| CN202210439277.9A CN114773129B (en) | 2022-04-25 | 2022-04-25 | Hard water resistant water-soluble fertilizer and application thereof |
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| CN114773129B CN114773129B (en) | 2023-08-11 |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3713802A (en) * | 1970-01-09 | 1973-01-30 | Ugine Kuhlmann | Reaction of phosphoric acid, urea, and ammonia |
| US4440560A (en) * | 1979-12-13 | 1984-04-03 | Japan Metals And Chemicals Co., Ltd. | Mixed phosphatic fertilizer and process for producing the same |
| CN1651488A (en) * | 2004-12-23 | 2005-08-10 | 云南省化工研究院 | Production method of poly ammonium phosphate |
| CN106348271A (en) * | 2016-08-31 | 2017-01-25 | 广西越洋科技股份有限公司 | Production method for preparing ammonium polyphosphate from wet-process phosphoric acid serving as raw material |
| CN108002357A (en) * | 2017-12-10 | 2018-05-08 | 什邡市长丰化工有限公司 | A kind of production method of highly-water-soluble ammonium polyphosphate solid |
| CN110724005A (en) * | 2019-10-30 | 2020-01-24 | 什邡市长丰化工有限公司 | Hard water-resistant neutral slightly-alkaline macroelement water-soluble fertilizer |
| CN111205134A (en) * | 2020-01-16 | 2020-05-29 | 三峡大学 | Preparation method of modified poly-humic acid ammonium phosphate |
-
2022
- 2022-04-25 CN CN202210439277.9A patent/CN114773129B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3713802A (en) * | 1970-01-09 | 1973-01-30 | Ugine Kuhlmann | Reaction of phosphoric acid, urea, and ammonia |
| US4440560A (en) * | 1979-12-13 | 1984-04-03 | Japan Metals And Chemicals Co., Ltd. | Mixed phosphatic fertilizer and process for producing the same |
| CN1651488A (en) * | 2004-12-23 | 2005-08-10 | 云南省化工研究院 | Production method of poly ammonium phosphate |
| CN106348271A (en) * | 2016-08-31 | 2017-01-25 | 广西越洋科技股份有限公司 | Production method for preparing ammonium polyphosphate from wet-process phosphoric acid serving as raw material |
| CN108002357A (en) * | 2017-12-10 | 2018-05-08 | 什邡市长丰化工有限公司 | A kind of production method of highly-water-soluble ammonium polyphosphate solid |
| CN110724005A (en) * | 2019-10-30 | 2020-01-24 | 什邡市长丰化工有限公司 | Hard water-resistant neutral slightly-alkaline macroelement water-soluble fertilizer |
| CN111205134A (en) * | 2020-01-16 | 2020-05-29 | 三峡大学 | Preparation method of modified poly-humic acid ammonium phosphate |
Non-Patent Citations (1)
| Title |
|---|
| 王正银, vol. 2, 中国农业大学出版社, pages: 244 * |
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