CN1190413C - Production method of EDTA complex metal salt - Google Patents
Production method of EDTA complex metal salt Download PDFInfo
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- CN1190413C CN1190413C CNB011337079A CN01133707A CN1190413C CN 1190413 C CN1190413 C CN 1190413C CN B011337079 A CNB011337079 A CN B011337079A CN 01133707 A CN01133707 A CN 01133707A CN 1190413 C CN1190413 C CN 1190413C
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- edta
- metal salt
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- sodium hydroxide
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Abstract
The present invention relates to a preparation method of complex metal salt of ethylenediaminetetraacetic acid, particularly to a preparation method of microelement fertilizer, which aims to provide a preparation method of single high-purity complex metal salt of ethylenediaminetetraacetic acid. In the method, ethylenediaminetetraacetic acid and sodium hydroxide are added to water and stirred to acquire sodium salt of the ethylenediaminetetraacetic acid; then, metal salt is added; the mole proportion of the ethylenediaminetetraacetic acid: the sodium hydroxide: the metal salt: the water is 1:1.5 to 5.0:0.1 to 1.1:10 to 200; a product is acquired by reaction at 70 to 150 DEG C for 0.5 to 5 hours. The metal salt is one of ferric trichloride, ferric sulfate, manganese carbonate, basic copper carbonate, zinc oxide, basic zinc carbonate, magnesium oxide and basic magnesium carbonate. The method of the present invention is suitable for preparing various kinds of single-element high-purity organic complex microelement fertilizer.
Description
Technical field:
The present invention relates to the manufacture method of chemical fertilizer, the Medium Trace Element Fertilizer method of particularly highly purified single EDTA complexing metal salt
Background technology:
Existing trace element fertilizer has two kinds, and a kind of is vitriol, as CuSO
4, MnSO
4, ZnSO
4, MgSO
4Another kind is that the upgraded product of vitriol is vitriol+EDTA2Na+ (a stablizer urea), and the principle of its production method institute foundation is:
About vitriol+EDTA2Na+ (stablizer urea) existing introduction in Chinese patent bulletin CN1102298, CN1103393, documents such as CN1064670, CN1074431, its method is with vitriol CuSO
4, MnSO
4, ZnSO
4, MgSO
4The middle EDTA2Na that adds makes, and when making solid phase prod, only is a kind of simple mixed thing in fact; When making liquid product, wherein EDTA complexing salt concentration is quite low, has only 1～10% usually, and all the other are inorganic salt composition and water.
The preparation method of existing vitriol+EDTA2Na+ (stablizer urea) is:
With vitriol CuSO
4, MnSO
4, ZnSO
4, MgSO
4In 70 ℃ with interior all be dissolved in the water solution A, with EDTA2Na in 70 ℃ in interior whole dissolving water solution B, solution A, B are pressed EDTA2Na: vitriol: the mixed of water (mole proportioning)=1: 0.1～0.5: 300～2500 stirred 0.5 hour, regulate the pH value with NaOH, filter and obtain finished product.
This production method exists a lot of not enough:
1, raw material adopts vitriol in the technology, makes to contain a large amount of inorganic salt (Na in the finished product
2SO
4).
2, make complexing agent with EDTA2Na in the technology, must be in excess in vitriol greatly, make cost up according to above proportioning EDTA2Na.
3, the proportioning amount of water is too big in the technology, make that finished product can only be a liquid form, and EDTA complexing metal salts contg is very low, only is 1～10%.
4, can adopt single vitriol+EDTA2Na through reaction, the concentrated solid finished product that obtains in the technology, but moisture content is too many in the reaction solution, power consumption is too many, makes cost too high, and does not have actual use value.Even moreover wherein the complexing metal salts contg is also very low to make solid finished product, only is 25～40%, does not more have actual use value.
5, the poor product quality that adopts this technology to obtain shows through for many years production application, all has a lot of problems and defective:
(1) makes salting of soil.Because the existence of a large amount of sulfate radicals makes salting of soil easily, reduce fertilizer efficiency.
(2) easily from falling, applicable pH range is narrow.Can only be used for neutral soil, in sour environment, make the EDTA precipitation easily, in alkaline environment, become precipitated metal easily, as Zn (OH)
2, Cu (OH)
2, in soil, be easy to disassociation, thereby make trace element fertilizer function complete failure.In fact based on meta-alkalescence soil, often effect is quite low in use in China.
(3) poor stability.In the efficient composite liquid fertilizer of actual production, often there are ionic equilibrium in vitriol and EDTA2Na, when phosphate radical and borate, molybdate, put the insoluble metal precipitation (Zn, Mn, Cu) that them can occur for a long time, cause the trace element fertilizer instability, effective constituent reduces, and quality product descends, and stops up the equipment that sprays.
(4) range of application is narrow.Neutral lower concentration composite liquid fertilizer can only be used to produce, production high density liquid fertilizer, particularly P can not be used for
2O
5During for the phosphorus ammonium, some metallic element (as Zn) can add at all, a large amount of precipitations can occur.And because the redox reaction between the element causes all vitriol simultaneously and not to be stored in the same solution system, thereby greatly reduce range of application.
(5) use inconvenience.All vitriol+EDTA2Na+ (stablizer urea) all exist with mixed state, can not use single EDTA complexing trace element fertilizer, can not play the effect of a certain element of independent enhancing when using.
(6) specific absorption is not only low, and absorbs slowly, and nutrient runs off easily.
Summary of the invention:
Given this, the object of the present invention is to provide a kind of production method of highly purified EDTA complex metal salt.
The production method of EDTA complex metal salt of the present invention is, ethylenediamine tetraacetic acid (EDTA), sodium hydroxide are added in the entry, stirring reaction, obtain disodium edta, add a kind of metallic compound in manganous carbonate, ventilation breather, zinc oxide, zinc subcarbonate, magnesium oxide, the magnesium basic carbonate again, ethylenediamine tetraacetic acid (EDTA): sodium hydroxide: metallic compound: the mole proportioning of water is 1: 1.5～5.0: 0.1～1.1: 10～200, under 70～150 ℃, reacted 0.5～5 hour, and obtained product.
Above-mentioned metallic compound is manganous carbonate (MuCO
3), ventilation breather (CuCO
3Cu (OH)
2), zinc oxide (ZnO), zinc subcarbonate (ZnCO
32Zn (OH)
2), magnesium oxide (MgO), magnesium basic carbonate (4MgCO
3Mg (OH)
2) in a kind of.
Above-mentioned product drying obtains solid phase prod.
Ethylenediamine tetraacetic acid (EDTA) among the present invention is EDTA, is a kind of complexing agent.Ethylenediamine tetraacetic acid (EDTA) and sodium hydroxide reaction obtain disodium edta, its chemical reaction mechanism:
Disodium edta again with manganous carbonate, ventilation breather, zinc oxide, zinc subcarbonate, magnesium oxide, magnesium basic carbonate in the reaction of a kind of metallic compound obtain ethylenediamine tetraacetic acid (EDTA) metal salt.As EDTA complex manganese salt (EDTA2NaMn), EDTA complex mantoquita (EDTA2NaCu), EDTA complex zinc salt (EDTA2NaZn), EDTA complex magnesium salts (EDTA2NaMg).Its chemistry answers formula as follows:
The proportioning of each component, temperature of reaction, reaction times are determined according to selected metallic compound and dosage thereof in the production method of the present invention.
When using present method to manufacture a product, select following raw material and proportioning thereof for use, the purity of the product that is obtained is higher.
Ethylenediamine tetraacetic acid (EDTA): sodium hydroxide: manganous carbonate: water=1: 1.6～2.6: 0.9～1.1: 15～200
Ethylenediamine tetraacetic acid (EDTA): sodium hydroxide: ventilation breather: water=1: 1.6～2.6: 0.4～0.6: 15～200
Ethylenediamine tetraacetic acid (EDTA): sodium hydroxide: zinc oxide: water=1: 1.6～2.6: 0.9～1.1: 15～200
Ethylenediamine tetraacetic acid (EDTA): sodium hydroxide: zinc subcarbonate: water=1: 1.6～2.6: 0.2～0.4: 15～200
Ethylenediamine tetraacetic acid (EDTA): sodium hydroxide: magnesium oxide: water=1: 1.6～2.6: 0.9～1.1: 15～200
Ethylenediamine tetraacetic acid (EDTA): sodium hydroxide: magnesium basic carbonate: water=1: 1.6～2.6: 0.1～0.3: 15～200
The present invention compares with the production method of vitriol+EDTA2Na+ (stablizer urea) with existing vitriol trace element fertilizer, has overcome their shortcoming fully, and has had following significant advantage and obvious effects:
One, in the production method of the present invention when adopting clean, pure raw material, have only purified EDTA complex metal salt in the reaction product, water and carbonic acid gas do not contain or seldom contain inorganic salt.
Two, the production method of the present invention EDTA2Na that adopts EDTA to replace prior art makes complexing agent, and the consumption of EDTA only is the about 78% of existing methods EDTA2Na under the same conditions, so production cost can reduce about 20%.
Three, production method of the present invention adopts the EDTA2Na of EDTA replacement prior art to make complexing agent, can reduce the consumption of EDTA significantly, thereby reduce production costs significantly.
Four, production method of the present invention is particularly when adopting complexing agent EDTA, NaOH, manganous carbonate, ventilation breather, zinc oxide, zinc subcarbonate, magnesium oxide, magnesium basic carbonate as raw material, when reducing amount of water significantly, EDTA complexing metal salts contg in the liquid product is improved greatly, EDTA complex metal content in the liquid product that can make can be up to 60%, do not contain or seldom contain by product, thereby improved economic and practical, helped making highly purified solid phase prod.
Five, the water content in the liquid product of production method manufacturing of the present invention is low, adopts common concentrating and drying mode, just can obtain the solid EDTA complex metal salt product of content 〉=95%, has advantage of low energy consumption.
Six, the EDTA complex metal salt of content 〉=95% that obtains of production method of the present invention has changed the characteristic as trace element fertilizer of vitriol+ETDA2NA+ (stablizer urea), has quite excellent performance and effect, shows:
(1) the purity height of the EDTA complex metal salt of use the inventive method acquisition, purity can reach more than 95%, do not contain or seldom contain any inorganic salt, do not contain the sulfate radical that makes soil compaction, therefore can be used for soilless culture nutrient fluid, also can directly add in the efficient compound fertilizer, can guarantee that each nutrient of whole compound manure is all useful to soil, the existence of no harmful element reaches real nuisanceless.
(2) EDTA complex metal salt of using the inventive method to obtain is not dissociated by soil, it is a kind of pure compound of single metal, at pH value is in 9 the time, EDTA complex metal salt has very high stability constant, and in this scope, ethylenediamine tetraacetic acid (EDTA) formula salt metal-salt is not decomposed, can not produce any precipitation, therefore do not dissociated, be applicable to any soil of PH≤9, enlarged range of application by soil.
(3) stability of the EDTA complex metal salt of use the inventive method acquisition is high.Obtain EDTA complexing metal salt in the solution system of PH≤9 with the present invention, owing to have very high stability constant, so chemical reaction can not take place between the metallic element, can make several metallic elements and be stored in the liquid, and do not have any precipitation.Metallic element can not produce precipitation with phosphoric acid, boric acid, molybdenum acid ion reaction yet simultaneously.The production of efficient compound fertilizer and high density liquid fertilizer can be used for, and low active compound fertilizer and lower concentration liquid fertilizer can be replaced.
(4) use of the EDTA complex metal salt of use the inventive method acquisition and accumulating are convenient.Quadrol amine tetraacethyl complexing metal salt can be made single trace element fertilizer and spray, and can reach the effect of a certain element of independent enhancing.EDTA complexing metal salt also can be directly and agricultural chemicals, nitrogen phosphorus potassium (N-P-K) fertilizer use with, make make composite fertilizer, efficient liquid fertilizer becomes very simple, need not consider antagonism mutual between composition, the problem of destroying, using fully.
(5) product that uses the present invention to obtain makes inorganic salt be converted into organic by EDTA, and solid phase prod energy 100% is water-soluble fully, can make complexing metal very fast by plant absorbing, the specific absorption height.And because the complexing action of EDTA, can fixing soil in benefit materials, as Fe, Cu, Mn, Zn etc., prevent to run off, strengthened validity.
The inventive method is applicable to the high purity organic complex attitude trace element fertilizer of making various single-elements.
Below, with embodiment the present invention is further described again.
Embodiment:
Embodiment
In 2000 liters reactor, the according to the form below dosage, ethylenediamine tetraacetic acid (EDTA), sodium hydroxide are added in the entry, stirring reaction, obtain disodium edta, add a kind of metallic compound in manganous carbonate, ventilation breather, zinc oxide, zinc subcarbonate, magnesium oxide, the magnesium basic carbonate again, according to the form below controlled temperature, time react, and obtain product.With liquid product through concentrate, after the drying, the solid phase prod that obtains is respectively the EDTA complex mantoquita (EDTA2NaCu) that is blue solid, is the EDTA complex zinc salt (EDTA2NaZn) of the EDTA complex manganese salt (EDTA2NaCu) of light red powder, the powder that is white in color, the EDTA complex magnesium salts (EDTA2NaMg) of white solid.
In the following table, A is that ethylenediamine tetraacetic acid (EDTA), B are that NaOH, C are that metallic compound, D are water.
| Embodiment | A | B | C | D | A∶B∶C∶D | Temperature of reaction (℃) | Reaction times (h) | Purity (%) | Name of product | |
| Dosage (kg) | Dosage (kg) | Title | Dosage (kg) | Dosage (kg) | ||||||
| 1 | 117 | 26 | Manganous carbonate | 42 | 1152 | 1∶1.6∶0.9∶160 | 95 | 4.5 | 96. 5 | Disodium ethylene diamine tetraacetate manganese |
| 2 | 204 | 67 | 81 | 1512 | 1∶2.4∶1.0∶120 | 75 | 5.0 | 97. 0 | ||
| 3 | 248 | 65 | 103 | 1377 | 1∶1.9∶1.05∶90 | 110 | 3.5 | 98. 1 | ||
| 4 | 526 | 151 | 229 | 810 | 1∶2.4∶1.1∶5 | 140 | 1.5 | 97. 8 | ||
| 5 | 234 | 80 | Ventilation breather | 70 | 504 | 1∶2.5∶0.4∶35 | 102 | 3.5 | 98. 0 | Disodium ethylene diamine tetraacetate copper |
| 6 | 146 | 34 | 56 | 1035 | 11.7∶0.5∶115 | 110 | 1.0 | 98. 3 | ||
| 7 | 336 | 101 | 140 | 1656 | 1∶2.2∶0.55∶80 | 135 | 4.0 | 97. 6 | ||
| 8 | 88 | 24 | 40 | 945 | 1∶2.0∶0.6∶175 | 70 | 5.0 | 97. 2 | ||
| 9 | 219 | 48 | Zinc oxide | 61 | 1350 | 1∶1.6∶1.0∶100 | 76 | 2.0 | 98. 0 | Ethylenediamine tetraacetic acid disodium zinc salt |
| 1 0 | 380 | 94 | 111 | 1105 | 1∶1.8∶1.05∶45 | 98 | 3.0 | 97. 3 | ||
| 11 | 131 | 38 | 33 | 1337 | 1∶2.1∶0.9∶165 | 112 | 1.0 | 96. 8 | ||
| 1 2 | 642 | 220 | 169 | 594 | 1∶2.5∶0.95∶15 | 138 | 4.0 | 97. 3 | ||
| 1 3 | 277 | 76 | Zinc subcarbonate | 65 | 513 | 1∶2.0∶0.2∶30 | 85 | 4.0 | 98. 0 | Ethylenediamine tetraacetic acid disodium zinc salt |
| 1 4 | 102 | 36 | 48 | 1166 | 1∶2.6∶0.4∶185 | 130 | 4.5 | 97. 8 | ||
| 1 5 | 409 | 101 | 168 | 1386 | 1∶1.8∶0.35∶55 | 145 | 3.0 | 98. 5 | ||
| 1 6 | 161 | 51 | 57 | 941 | 1∶2.3∶0.3∶95 | 105 | 1.0 | 97. 6 | ||
| 1 7 | 228 | 50 | Magnesium oxide | 34 | 1474 | 1∶1.6∶1.1∶05 | 90 | 3.5 | 97. 6 | Ethylenediamine tetraacetic acid disodium magnesium salt |
| 1 8 | 876 | 240 | 126 | 1080 | 1∶2.0∶1.05∶20 | 136 | 2.5 | 97. 3 | ||
| 1 9 | 152 | 44 | 21 | 1572 | 1∶2.1∶1.0∶168 | 95 | 4.5 | 96. 6 | ||
| 2 0 | 467 | 166 | 61 | 1584 | 1∶2.6∶0.95∶55 | 82 | 1.0 | 98. 1 | ||
| 2 1 | 190 | 52 | Magnesium basic carbonate | 25 | 1463 | 1∶2.0∶0.1∶125 | 97 | 3.5 | 97. 0 | Ethylenediamine tetraacetic acid disodium magnesium salt |
| 2 2 | 307 | 109 | 62 | 529 | 1∶2.6∶0.15∶28 | 132 | 2.0 | 98. 2 | ||
| 2 3 | 152 | 40 | 41 | 1591 | 1∶1.9∶032∶17 0 | 105 | 0.5 | 96. 8 | ||
| 2 4 | 292 | 68 | 99 | 1548 | 1∶1.7∶0.25∶86 | 78 | 4.5 | 98. 6 |
The above embodiment does not limit the present invention just to further elaboration of the present invention.In addition, still can in the scope of technical solution of the present invention, change enforcement.
Claims (8)
1, a kind of production method of EDTA complex metal salt, it is characterized in that ethylenediamine tetraacetic acid (EDTA), sodium hydroxide are added in the entry, stirring reaction, obtain disodium edta, add a kind of metallic compound in manganous carbonate, ventilation breather, zinc oxide, zinc subcarbonate, magnesium oxide, the magnesium basic carbonate again, ethylenediamine tetraacetic acid (EDTA): sodium hydroxide: metallic compound: the mole proportioning of water is 1: 1.5～5.0: 0.1～1.1: 10～200, under 70～150 ℃, reacted 0.5～5 hour, and obtained product.
2, the production method of EDTA complex metal salt according to claim 1 is characterized in that said ethylenediamine tetraacetic acid (EDTA): sodium hydroxide: manganous carbonate: the mole proportioning of water is 1: 1.6～2.6: 0.9～1.1: 15～200.
3, the production method of EDTA complex metal salt according to claim 1 is characterized in that said ethylenediamine tetraacetic acid (EDTA): sodium hydroxide: ventilation breather: the mole proportioning of water is 1: 1.6～2.6: 0.4～0.6: 15～200.
4, the production method of EDTA complex metal salt according to claim 1 is characterized in that said ethylenediamine tetraacetic acid (EDTA): sodium hydroxide: zinc oxide: the mole proportioning of water is 1: 1.6～2.6: 0.9～1.1: 15～200.
5, the production method of EDTA complex metal salt according to claim 1 is characterized in that said ethylenediamine tetraacetic acid (EDTA): sodium hydroxide: carbon formula zinc carbonate: the mole proportioning of water is 1: 1.6～2.6: 0.2～0.4: 15～200.
6, the production method of EDTA complex metal salt according to claim 1 is characterized in that said ethylenediamine tetraacetic acid (EDTA): sodium hydroxide: magnesium oxide: the mole proportioning of water is 1: 1.6～2.6: 0.9～1.1: 15～200.
7, the production method of EDTA complex metal salt according to claim 1 is characterized in that said ethylenediamine tetraacetic acid (EDTA): sodium hydroxide: magnesium basic carbonate: the mole proportioning of water is 1: 1.6～2.6: 0.1～0.3: 15～200.
8,, it is characterized in that said product obtains solid phase prod through dense place, drying according to the production method of any described EDTA complex metal salt among the claim 1-7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011337079A CN1190413C (en) | 2001-12-19 | 2001-12-19 | Production method of EDTA complex metal salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011337079A CN1190413C (en) | 2001-12-19 | 2001-12-19 | Production method of EDTA complex metal salt |
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| Publication Number | Publication Date |
|---|---|
| CN1426998A CN1426998A (en) | 2003-07-02 |
| CN1190413C true CN1190413C (en) | 2005-02-23 |
Family
ID=4672040
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011337079A Expired - Fee Related CN1190413C (en) | 2001-12-19 | 2001-12-19 | Production method of EDTA complex metal salt |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1190413C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102001880A (en) * | 2010-05-11 | 2011-04-06 | 苏州联胜化学有限公司 | Process for producing microelement complex fertilizer |
| CN103172532B (en) * | 2011-12-02 | 2016-10-12 | 扬子江药业集团江苏海慈生物药业有限公司 | A kind of preparation method of ethylenediaminetetraacidic acidic calcium disodium salt |
| CN104086453A (en) * | 2014-06-11 | 2014-10-08 | 南通昊友食品添加剂有限公司 | Production method of nutrition enhancer ferric sodium ethylenediamine tetraacetate |
| CN106831440A (en) * | 2017-01-20 | 2017-06-13 | 四川隆桥化工集团有限公司 | The preparation method of the ferrisodium of ethylenediamine two |
| PT115056B (en) * | 2018-10-04 | 2021-12-10 | Hovione Farm Sa | Amorphous forms of chelating agents and their preparation methods |
| CN109369426A (en) * | 2018-12-06 | 2019-02-22 | 郑州瑞普生物工程有限公司 | A kind of preparation method of high-quality ethylenediamine tetra-acetic acid zinc sodium |
| CN109651180B (en) * | 2019-01-22 | 2021-07-30 | 北京海德恒生科技发展有限公司 | Production method of sodium iron ethylene diamine tetraacetate |
| CN114685141A (en) * | 2022-05-05 | 2022-07-01 | 董坤 | Iron-removing whitening method for ceramic raw material |
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2001
- 2001-12-19 CN CNB011337079A patent/CN1190413C/en not_active Expired - Fee Related
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