CN102504253A - Environmental-protection preparation method for calcium polyaspartate as agricultural calcium supplement - Google Patents
Environmental-protection preparation method for calcium polyaspartate as agricultural calcium supplement Download PDFInfo
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- CN102504253A CN102504253A CN2011103266075A CN201110326607A CN102504253A CN 102504253 A CN102504253 A CN 102504253A CN 2011103266075 A CN2011103266075 A CN 2011103266075A CN 201110326607 A CN201110326607 A CN 201110326607A CN 102504253 A CN102504253 A CN 102504253A
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Abstract
The invention discloses an environmental-protection preparation method for calcium polyaspartate as an agricultural calcium supplement, which comprises the following steps: reacting polysuccinimide with calcium hydroxide under the existence of water to obtain turbid liquid containing the calcium polyaspartate; adding an acid to the turbid liquid for reaction to obtain a solution containing the calcium polyaspartate; and performing split charging the solution to obtain the agricultural calcium supplement. The preparation method disclosed by the invention is simple and convenient and environmentally friendly and has low cost and stability in effect, and the obtained calcium polyaspartate has good dissolvability.
Description
Technical field
The invention belongs to the preparation field of high molecular polymer, particularly a kind of agricultural is with the environment-friendly preparation method of calsium supplement calcium polyaspartate.
Background technology
Research for many years according to domestic proves that there is the calcium constituent disappearance in the farm crop more than 80%, has had a strong impact on output and the quality of farm crop.Enrich calcium constituent though exist in the soil, it mainly is to exist with insoluble inorganic salt forms such as lime carbonate, calcium phosphate more than 99%, and its solubleness is low, is difficult to by plant absorbing and utilization, causes plant big area ubiquity calcium deficiency.
Current agriculture calsium supplement is main with inorganic calcium (like calcium chloride) and organic calcium (like calcium formiate) etc. mainly.When being calsium supplement with calcium chloride, the content of its cl ions is higher than the permissible scope of plant far away, causes symptoms such as plant chlorine poisoning easily; And when being calsium supplement with the calcium formiate, solubleness is lower, has hindered effective absorption of calcium constituent.
Calcium polyaspartate is a kind of novel efficient organic calsium supplement, and degraded easily in soil is prone to by plant absorbing, is a kind of nontoxic, free of contamination environmentally friendly plant calsium supplement.Calcium polyaspartate is solvable under neutral environment, and solubleness increases in the sour environment.In addition, SAP 73 acid also has the effect that the enhancement of plant nutritive element absorbs, supplementing calcium element better.
Polysuccinimide is called for short PSI, is the macromolecular compound that is aggregated into by aspartic acid.The PSI hydrolysis can generate SAP 73.At present, PSI has extensively realized industrialized production, has various different molecular weight specifications.
Chinese patent CN101100510A discloses a kind of compound method of calcium polyaspartate, is raw material with the SAP 73, adds excessive calcium hydroxide, reacting by heating; The reaction after-filtration that finishes obtains containing the mixing solutions of calcium polyaspartate; In mixing solutions, add hydrochloric acid conditioning solution to neutral, the excessive calcium hydroxide that neutralizes adds ethanol calcium polyaspartate is separated out, and filters and obtains the calcium polyaspartate solid.
Synthesizing of existing calcium polyaspartate, adopt the neutral method, consume a large amount of calcium hydroxide, reaction process needs heating, consumes energy; The mixing solutions that obtains of reaction adopt in the hydrochloric acid with the time introduce cl ions, excessive cl ions produces detrimentally affect to plant-growth easily.
Summary of the invention
The technical issues that need to address of the present invention provide the environment-friendly preparation method of a kind of agricultural with the calsium supplement calcium polyaspartate, and it is easy, cost is low, effect stability, environmental friendliness, and the calcium polyaspartate solvability that obtains is good.
For solving the problems of the technologies described above, the technical scheme that the present invention adopted is:
Agricultural may further comprise the steps with the environment-friendly preparation method of calsium supplement calcium polyaspartate:
A, with polysuccinimide and calcium hydroxide under the condition that has water to exist, reaction obtains containing the suspension liquid of calcium polyaspartate;
B, adding acid in suspension liquid, reaction obtains the SAP 73 calcium solution, the solution packing is obtained agricultural use the calsium supplement calcium polyaspartate.
Improvement of the present invention is: the molecular weight of said calcium polyaspartate is 5000 ~ 50000.
Further improvement of the present invention is: the mass ratio of said polysuccinimide and calcium hydroxide is 100: 35 ~ 45.
Further improvement of the present invention is: among the said step a, temperature of reaction is 20 ~ 35 ℃, and the reaction times is 1 ~ 3h.
Further improvement of the present invention is: the acid among the said step b is any one in formic acid, acetate, nitric acid, the phosphoric acid, and the pH value of step b gained solution is 4 ~ 5.
Further improvement of the present invention is: the mass ratio of said polysuccinimide and formic acid is 100: 10 ~ 30.
Further improvement of the present invention is: the quality percentage composition of solid substance is 30% ~ 40% in the said step b gained solution, and the quality percentage composition of calcium constituent is 12% ~ 18% in the solid substance.
Further improvement of the present invention is: among the said step b, the solution feeding spray drying device that reaction is obtained carries out drying treatment, obtains containing the powder of calcium polyaspartate, the powder packing is obtained agricultural use the calsium supplement calcium polyaspartate.
Because the technical progress of having adopted technique scheme, the present invention to obtain is:
Technical scheme of the present invention adopts at present extensively, and the polysuccinimide of industrialized production is a raw material; Add calcium hydroxide and make hydrolysis of polysuccinimide, obtain containing the suspension liquid of calcium polyaspartate, add formic acid again; Strengthen the solvability of calcium polyaspartate; And remaining a small amount of calcium hydroxide reaction generation calcium formiate is dissolved in the water, and obtain containing the solution of calcium polyaspartate, can directly use calsium supplement after this solution packing as agricultural; Or this solution processed powder after spray-dried, add water-dispersion during use and get final product.Adopt technical scheme preparation agricultural of the present invention to use the calsium supplement calcium polyaspartate, under lower temperature and room temperature condition, all can react save energy; Production process does not have the three wastes and produces economic environmental protection; Hydrolysis of polysuccinimide is thorough, and reactant hydrogen quicklime consumption is few, cost is low; Select for use calcium hydroxide to come the advantage of hydrolysis to be: when ensureing hydrolysis of polysuccinimide, can introduce calcium ion again as alkali.The calcium hydroxide low in raw material cost is easy to get simultaneously, is fit to industrialized production.Adopting method of the present invention, guaranteeing that product under the prerequisite of result of use on the agricultural, optimized production technique, shortened Production Flow Chart, improved production efficiency, reduced production cost, is a kind of preparation method of calcium polyaspartate of efficient, environmental protection.
The molecular weight of product calcium polyaspartate of the present invention is 5000 ~ 50000, and the calcium polyaspartate solvability of above-mentioned molecular weight ranges is good, and the SAP 73 acid ion can play and strengthen the effect that crop nutrient elements absorbs.The mass ratio of polysuccinimide and calcium hydroxide is 100: 35 ~ 45 o'clock, and the hydrolysis reaction of polysuccinimide carries out fully, can avoid a large amount of calcium hydroxide of residue in the product simultaneously.Polysuccinimide and calcium hydroxide are under 20 ~ 35 ℃ condition, and 1 ~ 3h reaction gets final product complete reaction.Adopting the pH of formic acid regulator solution is 4 ~ 5, has strengthened the water-soluble of calcium polyaspartate, makes that solid content reaches 40% in the solution, has practiced thrift the transportation cost of product.Formic acid, acetate, nitric acid, phosphoric acid have advantage cheap and easy to get as organic acid or mineral acid commonly used.In the contained solid substance of reaction product solution, the content of calcium constituent can play good calcium supplementing effect to farm crop up to 12 ~ 18%.
The aqueous solution that contains calcium polyaspartate that above-mentioned reaction obtains, be prepared into powder through spray-dired method after, in water, can disperse rapidly, have good solubility.Be prepared into pulverous calcium polyaspartate, be convenient to store and transportation, help prolonging the quality guaranteed period of product.
Embodiment
Below in conjunction with specific embodiments the present invention is explained further details:
Embodiment 1
The raw material polysuccinimide, calcium hydroxide, the formic acid that are adopted in the present embodiment are technical grade.
Adopt following method preparation agricultural to use the calsium supplement calcium polyaspartate:
A, be that 5000 polysuccinimide and the water of 560kg join in the reaction kettle with the 280kg molecular weight; Stir, divide the calcium hydroxide that in reaction kettle, adds 108kg for three times again, keeping the temperature of reaction kettle is 25 ℃; Stir 2h, reaction obtains containing the suspension liquid of calcium polyaspartate;
B, in suspension liquid, add formic acid, reaction obtains containing the solution of calcium polyaspartate, and the pH value of solution is 4.5, and the amount of adding formic acid is 68kg.With the packing of gained solution, obtain agricultural with calsium supplement SAP 73 calcium product.
With said product evaporate to dryness, measure the quality percentage composition of solid substance, the result is 40%.Measure the quality percentage composition of calcium constituent in the solid substance, the result is 15%, measures the molecular weight of product calcium polyaspartate, and the result is 7100 dalton.
Embodiment 2
The difference of present embodiment and embodiment 1 is:
The add-on of water is 600kg, and the add-on of calcium hydroxide is 98kg, and the temperature of reaction kettle is 20 ℃; The reaction times of step a is 1h; The pH value of gained solution is 5 among the step b, and the amount that adds formic acid is 28kg, and the quality percentage composition of solid substance is 35% in the product; The quality percentage composition of calcium constituent is 12% in the solid substance, and the molecular weight of product calcium polyaspartate is 5000 dalton.
Embodiment 3
The difference of present embodiment and embodiment 1 is:
The add-on of water is 600kg, and the add-on of calcium hydroxide is 126kg, and the temperature of reaction kettle is 35 ℃; The reaction times of step a is 3h; The pH value of gained solution is 4 among the step b, and the amount that adds formic acid is 84kg, and the quality percentage composition of solid substance is 38% in the product; The quality percentage composition of calcium constituent is 18% in the solid substance, and the molecular weight of product calcium polyaspartate is 50000 dalton.
Embodiment 4
The difference of present embodiment and embodiment 1 is:
The add-on of water is 1000kg, and the add-on of calcium hydroxide is 108kg, and the temperature of reaction kettle is 25 ℃; The reaction times of step a is 2.5h; The pH value of gained solution is 4.5 among the step b, and the amount that adds formic acid is 68kg, and the quality percentage composition of solid substance is 30% in the product; The quality percentage composition of calcium constituent is 15% in the solid substance, and the molecular weight of product calcium polyaspartate is 14200 dalton.
Embodiment 5
The difference of present embodiment and embodiment 1 is:
The solution that contains calcium polyaspartate of reaction gained is carried out spray drying treatment, and step is following:
Air after air filter filters is sent into well heater by fan and is heated, and the air after the heating feeds spray-dryer and carries out thermal pretreatment; The EAT of setting spray-dryer is 260 ℃; Air outlet temperature is 130 ℃, treat temperature-stable after, get the above-mentioned solution that contains calcium polyaspartate; Through the flow velocity of charging pump with 1500kg/h; Pump in the spray-dryer after the above-mentioned preheating, collect the powder of spray-dryer bottom, packing obtains agricultural and uses the calsium supplement calcium polyaspartate.
The SAP 73 calcium powder outward appearance of spray drying method for preparation is evenly fine and smooth, and solvability is good.Measure the content of calcium constituent in the powder, the result is 15%; Measure the molecular weight of calcium polyaspartate, the result is 7100 dalton.
Formic acid in the foregoing description can replace to other organic acids such as other mineral acid such as nitric acid, phosphoric acid or acetate.
Claims (8)
1. agricultural is characterized in that may further comprise the steps with the environment-friendly preparation method of calsium supplement calcium polyaspartate:
A, with polysuccinimide and calcium hydroxide under the condition that has water to exist, reaction obtains containing the suspension liquid of calcium polyaspartate;
B, adding acid in suspension liquid, reaction obtains the SAP 73 calcium solution, the solution packing is obtained agricultural use the calsium supplement calcium polyaspartate.
2. agricultural according to claim 1 is with the environment-friendly preparation method of calsium supplement calcium polyaspartate, and it is characterized in that: the molecular weight of said calcium polyaspartate is 5000 ~ 50000.
3. agricultural according to claim 2 is with the environment-friendly preparation method of calsium supplement calcium polyaspartate, and it is characterized in that: the mass ratio of said polysuccinimide and calcium hydroxide is 100: 35 ~ 45.
4. agricultural according to claim 3 is with the environment-friendly preparation method of calsium supplement calcium polyaspartate, and it is characterized in that: among the said step a, temperature of reaction is 20 ~ 35 ℃, and the reaction times is 1 ~ 3h.
5. agricultural according to claim 4 is with the environment-friendly preparation method of calsium supplement calcium polyaspartate, and it is characterized in that: the acid among the said step b is any one in formic acid, acetate, nitric acid, the phosphoric acid, and the pH value of step b gained solution is 4 ~ 5.
6. agricultural according to claim 5 is with the environment-friendly preparation method of calsium supplement calcium polyaspartate, and it is characterized in that: the mass ratio of said polysuccinimide and formic acid is 100: 10 ~ 30.
7. according to the environment-friendly preparation method of each described agricultural of claim 1 ~ 6 with the calsium supplement calcium polyaspartate; It is characterized in that: the quality percentage composition of solid substance is 30% ~ 40% in the said step b gained solution, and the quality percentage composition of calcium constituent is 12% ~ 18% in the solid substance.
8. agricultural according to claim 7 is with the environment-friendly preparation method of calsium supplement calcium polyaspartate; It is characterized in that: among the said step b; The solution feeding spray drying device that reaction is obtained carries out drying treatment; Obtain containing the powder of calcium polyaspartate, the powder packing is obtained agricultural use the calsium supplement calcium polyaspartate.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275318A (en) * | 2013-05-24 | 2013-09-04 | 石家庄中农兴泰生物科技有限公司 | Production method of selenium-enriched polyaspartic acid calcium salt |
| CN105565910A (en) * | 2015-12-16 | 2016-05-11 | 山东远联化工有限公司 | Preparation method of bioactive polypeptide calcium fertilizer |
| CN108739836A (en) * | 2018-06-21 | 2018-11-06 | 山东省农业科学院植物保护研究所 | A kind of composition pesticide of prevention Virus Diseases of Sweet Potato |
| CN113896601A (en) * | 2021-10-14 | 2022-01-07 | 河北协同化学有限公司 | Polyaspartic acid chelated calcium magnesium fertilizer for preventing and treating physiological diseases of potatoes in storage period and preparation method thereof |
| CN117342896A (en) * | 2023-12-04 | 2024-01-05 | 烟台凡西农业科技有限公司 | Preparation method of marine mineral source silicon-calcium-magnesium fertilizer with soil anti-caking effect |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107903395B (en) * | 2017-11-27 | 2020-06-05 | 山东远联化工股份有限公司 | Method for preparing polyaspartic acid by catalytic hydrolysis |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1146210A (en) * | 1994-12-21 | 1997-03-26 | 三菱化学株式会社 | Polyaspartic acid or salt thereof and process for producing the same |
| CN101100510A (en) * | 2006-07-04 | 2008-01-09 | 北京联合大学 | Calcium polyaspartate |
-
2011
- 2011-10-25 CN CN 201110326607 patent/CN102504253B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1146210A (en) * | 1994-12-21 | 1997-03-26 | 三菱化学株式会社 | Polyaspartic acid or salt thereof and process for producing the same |
| CN101100510A (en) * | 2006-07-04 | 2008-01-09 | 北京联合大学 | Calcium polyaspartate |
Non-Patent Citations (1)
| Title |
|---|
| 李金: "聚天冬氨酸钙的合成与表征", 《化学研究与应用》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275318A (en) * | 2013-05-24 | 2013-09-04 | 石家庄中农兴泰生物科技有限公司 | Production method of selenium-enriched polyaspartic acid calcium salt |
| CN103275318B (en) * | 2013-05-24 | 2016-01-20 | 石家庄中农兴泰生物科技有限公司 | A kind of production method of rich selenium polyaspartic acid calcium salt |
| CN105565910A (en) * | 2015-12-16 | 2016-05-11 | 山东远联化工有限公司 | Preparation method of bioactive polypeptide calcium fertilizer |
| CN105565910B (en) * | 2015-12-16 | 2017-03-08 | 山东远联化工有限公司 | The preparation method of biologically active polypeptide calcareous fertilisers |
| CN108739836A (en) * | 2018-06-21 | 2018-11-06 | 山东省农业科学院植物保护研究所 | A kind of composition pesticide of prevention Virus Diseases of Sweet Potato |
| CN113896601A (en) * | 2021-10-14 | 2022-01-07 | 河北协同化学有限公司 | Polyaspartic acid chelated calcium magnesium fertilizer for preventing and treating physiological diseases of potatoes in storage period and preparation method thereof |
| CN117342896A (en) * | 2023-12-04 | 2024-01-05 | 烟台凡西农业科技有限公司 | Preparation method of marine mineral source silicon-calcium-magnesium fertilizer with soil anti-caking effect |
| CN117342896B (en) * | 2023-12-04 | 2024-02-02 | 烟台凡西农业科技有限公司 | Preparation method of marine mineral source silicon-calcium-magnesium fertilizer with soil anti-caking effect |
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Inventor after: Zhang Jiechun Inventor after: Dong Zhiqiang Inventor after: Tian Liying Inventor before: Zhang Jiechun Inventor before: Tian Liying |
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Address after: 050099 No. 6, middle Mill Road, circular chemical industry park, Hebei, Shijiazhuang Patentee after: HEBEI XIETONG ENVIRONMENTAL PROTECTION TECHNOLOGY CO., LTD. Address before: 050035 No. 55 Kunlun street, hi tech Development Zone, Hebei, Shijiazhuang Patentee before: Shijiazhuang Development Zone Desai Chemical Technology Co., Ltd. |
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Application publication date: 20120620 Assignee: Hebei Xieli Chemical Co.,Ltd. Assignor: HEBEI XIETONG ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Contract record no.: X2021130000017 Denomination of invention: Environmental protection preparation method of agricultural calcium supplement polyaspartic acid calcium Granted publication date: 20130515 License type: Common License Record date: 20210914 |