CN101050134A - Fertilizer of chelated calcium, and preparation method - Google Patents
Fertilizer of chelated calcium, and preparation method Download PDFInfo
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- CN101050134A CN101050134A CN 200710107077 CN200710107077A CN101050134A CN 101050134 A CN101050134 A CN 101050134A CN 200710107077 CN200710107077 CN 200710107077 CN 200710107077 A CN200710107077 A CN 200710107077A CN 101050134 A CN101050134 A CN 101050134A
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Abstract
This invention relates to a chelated calcium fertilizer, which is prepared from: catalyst 1-2 wt. %, inorganic calcium raw material 58-69 wt. %, and chelating agent 30-40 wt. %. The chelating agent is composed of: oxalic acid 5-10 wt.%, malic acid 8-20 wt.%, citric acid 15-25 wt.%, maleic acid 10-25 wt.%, sorbitol 3-8 wt.%, gallic acid 8-10 wt.%, and lactic acid 2-8 wt.%. The catalyst is composed of: gadolinium chloride 0.1-0.35 wt.%, selenium dioxide 0.1-0.2 wt.%, chalcanthite 0.05-0.1 wt.%, KOH 0.05-0.1 wt.%, potash 0.1-0.2 wt.%, and palladium carbonate 0.05-0.2 wt.%. The chelating agent has appropriate stability and low cost, and can chelate with calcium in solid state. Besides, the chelating agent cannot be deactivated in plants by hydrolysis or reacting with phosphate, sulfate and oxalic acid. This invention also relates to a method for preparing the chelated calcium fertilizer, which specifies the production process, process parameters, and chelating agent and high-efficiency catalyst needed.
Description
Technical field
The present invention relates to the chemical fertilizer field in the agricultural cience and farming techniques, particularly a kind of fertilizer of chelated calcium and preparation method thereof.
Background technology
The crop calcium deficiency is cumbersome thing in present plant nutrition and the fertilising field, the a large amount of leaching losses of calcium in China's soils in south china, the active calcium ion content is low in the soil, the crop calcium deficiency is normal, yet the crop calcium deficiency is not that effective calcium deficiency causes in the soil on the northern calcareous soil, so the soil application calcareous fertilisers are difficult to solve the problem of plant calcium deficiency.Traditional calcareous fertilisers (using nitrocalcite usually) are carried out foliage-spray certain effect is arranged, even but also still there is the defective of self in traditional calcareous fertilisers by plant absorbing, calcium forms the compound of insoluble and calcium was lost efficacy in plant materials with a lot of negatively charged ion in plant materials, wherein topmost negatively charged ion has phosphate radical, sulfate radical, oxalic acid etc.Therefore have a lot of the time, though the very high calcium of content in the leaf of plant, but the newborn position of crop particularly fruit still produce tangible calcium deficiency symptom, as apple, tomato, citrus, peanut, soybean etc.The newborn position of plant and another reason of fruit calcium deficiency are that calcium is in the intravital assignment problem of plant.The key that therefore will solve the newborn position of plant and fruit calcium deficiency be prevent calcium in plant materials inactivation and artificial adjustment calcium in intravital transportation of plant and distribution.
Prevent that calcium way of inactivation in plant materials from being with a kind of specific organic compound calcium to be protected, promptly so-called chelating calcium.The way of artificial adjustment calcium is to use some that the material of regulating the plant metabolism function is arranged, and strengthens the storehouse intensity of newborn position and fruit, more calcium is assigned in newborn position of plant and the fruit goes.
The chelating calcium of Shi Yonging has EDTA-Ca traditionally, and citrate of lime and amino-acid zinc, traditional EDTA-Ca and citrate of lime also have problems such as detrimentally affect that EDTA exists plant-growth and citrate of lime poorly water-soluble except costing an arm and a leg.Though amino acid calcium can not produce detrimentally affect to plant, the stability constant of amino acid calcium is too low, cannot stop interior generation hydrolysis of calcium plant materials and negatively charged ion a little with it to react and the problem of inactivation.
Summary of the invention
The technical problem to be solved in the present invention is intended to overcome the deficiency of above-mentioned prior art, and a kind of fertilizer of chelated calcium is provided, and the sequestrant stability in described fertilizer of chelated calcium is moderate, and cost is low and can carry out chelatropic reaction with calcium under solid state shape.
The technical solution used in the present invention is:
Fertilizer of chelated calcium, described fertilizer of chelated calcium are under the catalyst action of 1-2% (quality percentage composition), make behind the sequestrant generation chelatropic reaction by the inorganic calcium raw material of 58-69% and 30-40%; Wherein, described sequestrant comprises the component of following mass ratio:
Oxalic acid: 5-10; Oxysuccinic acid: 8-20; Citric acid: 15-25;
Toxilic acid: 10-25; Sorbitol Powder: 3-8; Gallic acid: 8-10; Lactic acid: 2-8;
And described catalyzer comprises the component of following mass ratio:
Gadolinium trichloride: 0.1-0.35; Tin anhydride: 0.1-0.2; Blue stone: 0.05-0.1;
Potassium hydroxide: 0.05-0.1; Potash: 0.1-0.2; Carbonate palladium: 0.05-0.2.
Compared with the prior art fertilizer of chelated calcium of the present invention has following positively effect: sequestrant is wherein compared with traditional sequestrant, and stability is moderate, and crop is not only had detrimentally affect, but also the growth of crop has certain useful influence; The technology of chelatropic reaction fully breaks traditions, under the condition of solid phase, carry out chelating with sequestrant, reduce the cost of product chelating process greatly, its production cost approximately has only tradition chelated calcium 1/1/3rd, so just makes to be widely used in agriculture production with chelating calcium and to become possibility; Therefore the molecular weight of sequestrant is low, makes the content of chelating calcium product calcium far above traditional chelating calcium.The chelating calcium product that utilizes this new sequestrant and novel process to produce, in plant materials, can not take place hydrolysis or and phosphate radical, sulfate radical, oxalic acid etc. react and inactivation, and cost is low, effective, show that through a large amount of field test results this novel chelating iron fertilizer has good effect, through lab scale, pilot scale and small-scale production prove that this technology and production technique are feasible.
Another technical problem that the present invention will solve provides a kind of preparation method of fertilizer of chelated calcium, includes following step: each component of inorganic calcium raw material, sequestrant and catalyzer mixes; Under 30-80 ℃, carried out the first solid state reaction 7-15 hour, and stirred reactant; Adjust the temperature to 50-180 ℃, carried out again the second solid state reaction 10-25 hour, can obtain fertilizer of chelated calcium.
The preparation method of the fertilizer of chelated calcium that the present invention relates to, the clear and definite production process of fertilizer of chelated calcium, processing parameter and produce in required sequestrant, effective catalyst.
Embodiment
Below will be described in detail the specific embodiment of the present invention.
After taking off the mutual thorough mixing of inorganic calcium raw material, sequestrant and catalyzer of stating the percentage composition of quality shown in the table 1, carry out first solid state reaction and second solid state reaction according to the operating parameters shown in the following table 1, and the fertilizer of chelated calcium that must the present invention relates to.
Table 1
| The quality of material percentage composition | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Inorganic calcium amounts to | 58 | 60 | 62 | 64 | 66 | 69 |
| Sequestrant amounts to | 34 | 32 | 30 | 40 | 38 | 36 |
| Catalyzer amounts to | 1.8 | 2 | 1.6 | 1.2 | 1.4 | 1.0 |
| The first solid state reaction time (hour) | 7 | 8 | 10 | 12 | 14 | 15 |
| The first solid state reaction temperature (℃) | 80 | 70 | 60 | 50 | 40 | 30 |
| The second solid state reaction time (hour) | 25 | 19 | 22 | 16 | 10 | 13 |
| The second solid state reaction temperature (℃) | 50 | 100 | 80 | 130 | 180 | 150 |
Wherein as shown in table 2, comprise each component of following mass ratio described in the foregoing description 1-6 in the inorganic calcium raw material respectively.
Table 2
| Nitrocalcite | 5 | 6 | 7 | 8 | 9 | 10 |
| Calcium chloride | 50 | 45 | 40 | 30 | 20 | 10 |
| Calcium oxide | 30 | 20 | 10 | 60 | 50 | 40 |
| Calcium sulfate | 0 | 0 | 0 | 1 | 1.5 | 2 |
| Losantin | 0 | 0 | 0 | 3 | 5 | 1 |
Wherein as shown in table 3, comprise each component of following mass ratio described in the foregoing description 1-6 in the sequestrant respectively.
Table 3
| Oxalic acid | 5 | 6 | 7 | 8 | 9 | 10 |
| Oxysuccinic acid | 20 | 18 | 15 | 12 | 10 | 8 |
| Citric acid | 21 | 23 | 25 | 15 | 17 | 19 |
| Toxilic acid | 13 | 25 | 19 | 22 | 16 | 10 |
| Sorbitol Powder | 3 | 5 | 7 | 6 | 8 | 4 |
| Gallic acid | 8 | 10 | 9.6 | 9.2 | 8.8 | 8.4 |
| Lactic acid | 3 | 2 | 5 | 4 | 8 | 7 |
Wherein as shown in table 4, comprise each component of following mass ratio described in the foregoing description 1-6 in the catalyzer respectively.
Table 4
| Gadolinium trichloride | 0.10 | 0.15 | 0.20 | 0.25 | 0.30 | 0.35 |
| Tin anhydride | 0.20 | 0.18 | 0.16 | 0.14 | 0.12 | 0.10 |
| Blue stone | 0.08 | 0.09 | 0.10 | 0.05 | 0.06 | 0.07 |
| Potassium hydroxide | 0.06 | 0.10 | 0.08 | 0.09 | 0.07 | 0.05 |
| Potash | 0.10 | 0.14 | 0.18 | 0.16 | 0.20 | 0.12 |
| Carbonate palladium | 0.08 | 0.05 | 0.14 | 0.11 | 0.20 | 0.17 |
In embodiment 1-6, each component of inorganic calcium raw material, sequestrant and catalyzer shown in table 2,3 and 4, can be in each table equal picked at random one row component concentration ratios, thereby can form the combination of multiple content ratio of above-mentioned three kinds of compositions of embodiment 1-6.
Behind the fertilizer of chelated calcium of finishing above-mentioned first solid state reaction and second solid state reaction and must the present invention relates to,, and pulverize preferably with fertilizer of chelated calcium cool to room temperature under dry environment.Wherein, preferred described crushing operation be earlier through put into again after the coarse reduction micronizer mill be crushed to 200 orders or more than, the granularity of the fertilizer of chelated calcium after the pulverizing is suitable for the plant absorbing nutrient.
Further, preferred described first solid state reaction and second solid state reaction are all carried out in reaction box, and its temperature rise rate is 30 ℃/10 minutes, and the inside and outside temperature head of case is≤2 ℃.
Claims (10)
1, fertilizer of chelated calcium is characterized in that described fertilizer of chelated calcium under the catalyst action of 1-2% (quality percentage composition), makes behind the sequestrant generation chelatropic reaction by the inorganic calcium raw material of 58-69% and 30-40%; Wherein, described sequestrant comprises the component of following mass ratio:
Oxalic acid: 5-10; Oxysuccinic acid: 8-20; Citric acid: 15-25;
Toxilic acid: 10-25; Sorbitol Powder: 3-8; Gallic acid: 8-10; Lactic acid: 2-8;
And described catalyzer comprises the component of following mass ratio:
Gadolinium trichloride: 0.1-0.35; Tin anhydride: 0.1-0.2; Blue stone: 0.05-0.1;
Potassium hydroxide: 0.05-0.1; Potash: 0.1-0.2; Carbonate palladium: 0.05-0.2.
2, fertilizer of chelated calcium according to claim 1 is characterized in that described inorganic calcium raw material comprises the component of following mass ratio:
Nitrocalcite: 5-10; Calcium chloride: 10-50; Calcium oxide: 10-60.
3, fertilizer of chelated calcium according to claim 2 is characterized in that described inorganic calcium raw material comprises the component of following mass ratio:
Calcium sulfate: 1-2; Losantin: 1-5.
4,, it is characterized in that described fertilizer of chelated calcium is got by following method preparation according to the described fertilizer of chelated calcium of the arbitrary claim of claim 1-3:
1) each component of inorganic calcium raw material, sequestrant and catalyzer mixes;
2) under 30-80 ℃, carry out the first solid state reaction 7-15 hour, stir reactant;
3) adjust the temperature to 50-180 ℃, carried out again the second solid state reaction 10-25 hour, can obtain fertilizer of chelated calcium.
5, fertilizer of chelated calcium according to claim 4 is characterized in that described fertilizer of chelated calcium after step 3 reaction is finished, cool to room temperature under dry environment, and pulverize.
6, fertilizer of chelated calcium according to claim 5, it is characterized in that described crushing operation be earlier through put into again after the coarse reduction micronizer mill be crushed to 200 orders or more than.
7, a kind of preparation includes following step as the method for fertilizer of chelated calcium as described in the arbitrary claim of claim 1-3:
1) each component of inorganic calcium raw material, sequestrant and catalyzer mixes;
2) under 30-80 ℃, carry out the first solid state reaction 7-15 hour, stir reactant;
3) adjust the temperature to 50-180 ℃, carried out again the second solid state reaction 10-25 hour, can obtain fertilizer of chelated calcium.
8, according to the preparation method of the described fertilizer of chelated calcium of claim 7, it is characterized in that described fertilizer of chelated calcium after step 3 reaction is finished, cool to room temperature under dry environment, and pulverize.
9, the preparation method of described fertilizer of chelated calcium according to Claim 8, it is characterized in that described crushing operation be earlier through put into again after the coarse reduction micronizer mill be crushed to 200 orders or more than.
10, the preparation method of described fertilizer of chelated calcium according to Claim 8 is characterized in that described first solid state reaction and second solid state reaction all carry out in reaction box, its temperature rise rate is 30 ℃/10 minutes, and the inside and outside temperature head of case is≤2 ℃.
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Cited By (18)
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| CN102731199A (en) * | 2012-06-06 | 2012-10-17 | 苏州安德鲁尹生物技术咨询有限公司 | Particulate sustained-release calcium fertilizer and preparation method thereof |
| CN102887795A (en) * | 2012-11-08 | 2013-01-23 | 广西新方向化学工业有限公司 | Surfactant-containing chelation powdery water-soluble fertilizer and preparation method thereof |
| CN103483044A (en) * | 2013-09-18 | 2014-01-01 | 句容市植保植检站 | Calcium-rich organic liquid fertilizer and preparation method thereof |
| CN103588564A (en) * | 2013-11-07 | 2014-02-19 | 华南农业大学 | Sugar alcohol calcium magnesium zinc boron compound liquid fertilizer and preparation method and applications thereof |
| CN103739404A (en) * | 2014-01-23 | 2014-04-23 | 佛山市植宝化工有限公司 | Nucleotide-added water soluble fertilizer containing amino acid and preparation method thereof |
| CN103771974A (en) * | 2014-01-17 | 2014-05-07 | 陕西鼎天济农腐殖酸制品有限公司 | Multifunctional liquid calcium fertilizer and production method thereof |
| CN104030831A (en) * | 2014-06-24 | 2014-09-10 | 合肥路飞农业科技有限公司 | Acidotrophic fertilizer |
| CN104030758A (en) * | 2014-06-23 | 2014-09-10 | 合肥路飞农业科技有限公司 | Complex calcium fertilizer |
| CN104447286A (en) * | 2014-11-07 | 2015-03-25 | 李玉成 | Soluble selenium/calcium citrate and preparation method thereof |
| CN104692937A (en) * | 2015-02-16 | 2015-06-10 | 鲁西化工集团股份有限公司 | Double-chelate liquid fertilizer and preparation method thereof |
| CN104961587A (en) * | 2015-07-06 | 2015-10-07 | 汤在英 | China rose soilless culture nutrient formula and application thereof |
| CN105084944A (en) * | 2015-08-21 | 2015-11-25 | 南宁汉和生物科技有限公司 | Chelated calcium fertilizer prepared by utilizing shells as well as preparation method and application thereof |
| CN105085051A (en) * | 2015-08-21 | 2015-11-25 | 南宁汉和生物科技有限公司 | Chelated calcium fertilizer prepared from oyster shell, and preparation method and application thereof |
| CN106699344A (en) * | 2016-11-25 | 2017-05-24 | 深圳市芭田生态工程股份有限公司 | Chelated calcium synthesized by taking oyster shells and alcohol slops as raw materials and preparation method thereof |
| CN107311800A (en) * | 2017-06-27 | 2017-11-03 | 青岛大学 | A kind of special fertilizer of chelated calcium of celery |
| CN109232102A (en) * | 2018-11-09 | 2019-01-18 | 中国农业科学院农业资源与农业区划研究所 | Nutrient calcium chelating carrier and application thereof is measured in one kind |
| CN114349566A (en) * | 2021-12-30 | 2022-04-15 | 江西科农沃科技有限责任公司 | Calcium fertilizer and preparation method thereof |
| CN114573391A (en) * | 2022-03-01 | 2022-06-03 | 青岛大学 | Sugar alcohol chelated calcium fertilizer special for peanuts and preparation method thereof |
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2007
- 2007-05-18 CN CN 200710107077 patent/CN101050134A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731199B (en) * | 2012-06-06 | 2014-08-27 | 苏州安德鲁尹生物技术咨询有限公司 | Particulate sustained-release calcium fertilizer and preparation method thereof |
| CN102731199A (en) * | 2012-06-06 | 2012-10-17 | 苏州安德鲁尹生物技术咨询有限公司 | Particulate sustained-release calcium fertilizer and preparation method thereof |
| CN102887795A (en) * | 2012-11-08 | 2013-01-23 | 广西新方向化学工业有限公司 | Surfactant-containing chelation powdery water-soluble fertilizer and preparation method thereof |
| CN103483044A (en) * | 2013-09-18 | 2014-01-01 | 句容市植保植检站 | Calcium-rich organic liquid fertilizer and preparation method thereof |
| CN103588564A (en) * | 2013-11-07 | 2014-02-19 | 华南农业大学 | Sugar alcohol calcium magnesium zinc boron compound liquid fertilizer and preparation method and applications thereof |
| CN103771974B (en) * | 2014-01-17 | 2015-04-08 | 陕西鼎天济农腐殖酸制品有限公司 | Multifunctional liquid calcium fertilizer and production method thereof |
| CN103771974A (en) * | 2014-01-17 | 2014-05-07 | 陕西鼎天济农腐殖酸制品有限公司 | Multifunctional liquid calcium fertilizer and production method thereof |
| CN103739404A (en) * | 2014-01-23 | 2014-04-23 | 佛山市植宝化工有限公司 | Nucleotide-added water soluble fertilizer containing amino acid and preparation method thereof |
| CN103739404B (en) * | 2014-01-23 | 2015-11-18 | 佛山市植宝化工有限公司 | A kind of add Nucleotide containing amino acid water-soluble fertilizer and preparation method thereof |
| CN104030758A (en) * | 2014-06-23 | 2014-09-10 | 合肥路飞农业科技有限公司 | Complex calcium fertilizer |
| CN104030831A (en) * | 2014-06-24 | 2014-09-10 | 合肥路飞农业科技有限公司 | Acidotrophic fertilizer |
| CN104447286A (en) * | 2014-11-07 | 2015-03-25 | 李玉成 | Soluble selenium/calcium citrate and preparation method thereof |
| CN104692937B (en) * | 2015-02-16 | 2017-06-13 | 鲁西化工集团股份有限公司 | A kind of double chelating liquid fertilizer and preparation methods |
| CN104692937A (en) * | 2015-02-16 | 2015-06-10 | 鲁西化工集团股份有限公司 | Double-chelate liquid fertilizer and preparation method thereof |
| CN104961587A (en) * | 2015-07-06 | 2015-10-07 | 汤在英 | China rose soilless culture nutrient formula and application thereof |
| CN105084944A (en) * | 2015-08-21 | 2015-11-25 | 南宁汉和生物科技有限公司 | Chelated calcium fertilizer prepared by utilizing shells as well as preparation method and application thereof |
| CN105085051A (en) * | 2015-08-21 | 2015-11-25 | 南宁汉和生物科技有限公司 | Chelated calcium fertilizer prepared from oyster shell, and preparation method and application thereof |
| CN106699344A (en) * | 2016-11-25 | 2017-05-24 | 深圳市芭田生态工程股份有限公司 | Chelated calcium synthesized by taking oyster shells and alcohol slops as raw materials and preparation method thereof |
| CN107311800A (en) * | 2017-06-27 | 2017-11-03 | 青岛大学 | A kind of special fertilizer of chelated calcium of celery |
| CN109232102A (en) * | 2018-11-09 | 2019-01-18 | 中国农业科学院农业资源与农业区划研究所 | Nutrient calcium chelating carrier and application thereof is measured in one kind |
| CN114349566A (en) * | 2021-12-30 | 2022-04-15 | 江西科农沃科技有限责任公司 | Calcium fertilizer and preparation method thereof |
| CN114573391A (en) * | 2022-03-01 | 2022-06-03 | 青岛大学 | Sugar alcohol chelated calcium fertilizer special for peanuts and preparation method thereof |
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