CN109608249A - Divalent iron supply liquid and its application - Google Patents
Divalent iron supply liquid and its application Download PDFInfo
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- CN109608249A CN109608249A CN201910106700.1A CN201910106700A CN109608249A CN 109608249 A CN109608249 A CN 109608249A CN 201910106700 A CN201910106700 A CN 201910106700A CN 109608249 A CN109608249 A CN 109608249A
- Authority
- CN
- China
- Prior art keywords
- supply liquid
- divalent iron
- ferrous
- iron supply
- iron
- Prior art date
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 183
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 92
- 239000007788 liquid Substances 0.000 title claims abstract description 67
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 30
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 23
- 239000011640 ferrous citrate Substances 0.000 claims abstract description 20
- 235000019850 ferrous citrate Nutrition 0.000 claims abstract description 20
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 20
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 20
- APVZWAOKZPNDNR-UHFFFAOYSA-L iron(ii) citrate Chemical compound [Fe+2].OC(=O)CC(O)(C([O-])=O)CC([O-])=O APVZWAOKZPNDNR-UHFFFAOYSA-L 0.000 claims abstract description 20
- PRZPUYBFEJPNPF-UHFFFAOYSA-J tetrasodium 3-carboxy-3,5-dihydroxy-5-oxopentanoate 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Na+].C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].[Na+].[Na+].[Na+].C(CC(O)(C(=O)O)CC(=O)O)(=O)[O-] PRZPUYBFEJPNPF-UHFFFAOYSA-J 0.000 claims abstract description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 48
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 29
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- 238000010792 warming Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000002955 isolation Methods 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 230000008635 plant growth Effects 0.000 claims description 4
- 230000001737 promoting effect Effects 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 abstract 2
- 241000196324 Embryophyta Species 0.000 description 19
- 239000003337 fertilizer Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 12
- 241000219315 Spinacia Species 0.000 description 9
- 235000009337 Spinacia oleracea Nutrition 0.000 description 9
- 238000010790 dilution Methods 0.000 description 9
- 239000012895 dilution Substances 0.000 description 9
- 239000002689 soil Substances 0.000 description 9
- 240000006108 Allium ampeloprasum Species 0.000 description 8
- 235000005254 Allium ampeloprasum Nutrition 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 230000012010 growth Effects 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PUKLDDOGISCFCP-JSQCKWNTSA-N 21-Deoxycortisone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2=O PUKLDDOGISCFCP-JSQCKWNTSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- FCYKAQOGGFGCMD-UHFFFAOYSA-N Fulvic acid Natural products O1C2=CC(O)=C(O)C(C(O)=O)=C2C(=O)C2=C1CC(C)(O)OC2 FCYKAQOGGFGCMD-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000002509 fulvic acid Substances 0.000 description 3
- 229940095100 fulvic acid Drugs 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- 102000018832 Cytochromes Human genes 0.000 description 2
- 108010052832 Cytochromes Proteins 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 230000035784 germination Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- -1 iron ion Chemical class 0.000 description 2
- 235000019691 monocalcium phosphate Nutrition 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000035806 respiratory chain Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 238000009333 weeding Methods 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 108091006149 Electron carriers Proteins 0.000 description 1
- 102000008857 Ferritin Human genes 0.000 description 1
- 108050000784 Ferritin Proteins 0.000 description 1
- 238000008416 Ferritin Methods 0.000 description 1
- 239000004277 Ferrous carbonate Substances 0.000 description 1
- 206010022971 Iron Deficiencies Diseases 0.000 description 1
- 108010063653 Leghemoglobin Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KVCWSJZUKMSPLM-UHFFFAOYSA-N O.O[PH2]=O Chemical compound O.O[PH2]=O KVCWSJZUKMSPLM-UHFFFAOYSA-N 0.000 description 1
- 102000003992 Peroxidases Human genes 0.000 description 1
- ZLXPLDLEBORRPT-UHFFFAOYSA-M [NH4+].[Fe+].[O-]S([O-])(=O)=O Chemical compound [NH4+].[Fe+].[O-]S([O-])(=O)=O ZLXPLDLEBORRPT-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 1
- 235000019268 ferrous carbonate Nutrition 0.000 description 1
- 229960004652 ferrous carbonate Drugs 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- 208000006278 hypochromic anemia Diseases 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000015 iron(II) carbonate Inorganic materials 0.000 description 1
- MVZXTUSAYBWAAM-UHFFFAOYSA-N iron;sulfuric acid Chemical compound [Fe].OS(O)(=O)=O MVZXTUSAYBWAAM-UHFFFAOYSA-N 0.000 description 1
- YDCPQRQGABOSRY-UHFFFAOYSA-N iron;urea Chemical compound [Fe].NC(N)=O YDCPQRQGABOSRY-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003895 organic fertilizer Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 108040007629 peroxidase activity proteins Proteins 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 230000008654 plant damage Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- MKWYFZFMAMBPQK-UHFFFAOYSA-J sodium feredetate Chemical compound [Na+].[Fe+3].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O MKWYFZFMAMBPQK-UHFFFAOYSA-J 0.000 description 1
- 239000004016 soil organic matter Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Classifications
-
- 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
- C05G5/00—Fertilisers characterised by their form
- C05G5/20—Liquid fertilisers
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D9/00—Other inorganic fertilisers
- C05D9/02—Other inorganic fertilisers containing trace elements
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses a kind of divalent iron supply liquid, it is characterized in that the divalent iron supply liquid is a kind of mixed liquor containing ferrous ion, the mixed liquor includes tetrasodium biscitrate ferrate, ferrous sulfate, ferrous citrate, the molal weight ratio of tetrasodium biscitrate ferrate, ferrous sulfate, ferrous citrate in mixed liquor are as follows: 1:0.28~0.38:0.17~0.23, the pH of the divalent iron supply liquid are 4.5~5.5.Divalent iron supply liquid of the invention can to plant stability provide divalent ferro element, it is promoted to germinate and grow.
Description
Technical field
The invention belongs to technical field of land improvement, and in particular to a kind of divalent iron supply liquid and its application.
Background technique
Organism usually converts ferrous ion for iron ion, be incorporated into organism as complexing iron, as fulvic acid iron,
Ferrous citrate etc..Ferrous ion plays a significant role in the respiratory chain complex of organism as electron carrier, although
Its content is micro, but when lacking, will limit entire respiratory chain and be related to organism vital movement.Even for such as plant
The photosynthesis such as object biology, as the cytochromes (hemoprotein) in photosynthetic electron transport system, lacks ferrous ion
Also it will limit entire vital movement.The content of iron is quite high in soil, but because being oxidized to Fe (OH)3And precipitate, in water
It is insoluble.Ferric iron in soil is reduced into ferrous iron in the outer surface of plant root cells film and is absorbed by plants.But cause to plant
The reason of object iron deficiency, is pH value i.e. pH value and oxidation-reduction potential of edaphic condition such as soil etc..Therefore the prior art is utilized
Ferric iron using the ferrous iron being easily oxidized or is directly used for plant culture additive, efficiency is extremely low, and is not easy to be inhaled by plant
It receives.
Iron generates ferritin: cytochromes, peroxidase, legh emoglobin, iron with various forms in conjunction with protein
Oxygen also albumen.Iron fertilizer has certain effect to fruit tree chlorosis is rescued.Common iron fertilizer can be divided into inorganic iron fertilizer such as ferrous sulfate, sulfuric acid
Iron, iron oxide, iron ammonium sulfate, ferrous carbonate and a hypophosphite monohydrate ferrous ammonium, organic iron fertilizer such as urea iron complex (three nitric acid
Six urea close iron), fulvic acid diamines iron (urea, ferrous sulfate and fulvic acid are made), and chelating iron fertilizer such as NaFeEDTA,
NaFeEDDHA and NaFeDTPA.But these iron fertilizers usually have various disadvantages, although as inorganic iron fertilizer effect is fast, it is cheap,
But it is easily oxidized the ferric iron precipitating for generating and not absorbed by plant, and is difficult to be continued to decompose by microorganism, pollutes environment；
Chelating iron fertilizer price itself is very expensive, and in addition the toxicology of chelating agent is also less clear at present in chelated iron, there is carcinogenic possibility
Property, while chelating agent is easy to combine heavy metal ion, and heavy metallic salt not soluble in water original in soil is become the weight for being dissolved in water
Metal ion causes heavy metal in soil exceeded.Although common are machine iron fertilizer with certain inoxidizability, price also compared with
Inorganic iron fertilizer is high, in addition organic iron fertilizer due to solubility it is lower, so plant absorption is slow, being sprayed on plant leaf surface be will lead to
Plant damage, easily precipitating mildew.
Summary of the invention
Therefore, the shortcomings that present invention is for different type iron fertilizer in the prior art, it is therefore intended that it is easy to solve inorganic iron fertilizer
The shortcomings that oxidation, in combination with the strong feature of organic iron fertilizer inoxidizability, provide it is a kind of it is new stablize release ferrous iron from
The divalent iron supply liquid of son.
One of the objects of the present invention is to provide a kind of divalent iron supply liquid, the divalent iron supply liquid contains for one kind
There is a mixed liquor of ferrous ion, the mixed liquor includes tetrasodium biscitrate ferrate, ferrous sulfate, ferrous citrate, in mixed liquor
Tetrasodium biscitrate ferrate, ferrous sulfate, ferrous citrate molal weight ratio are as follows: 1:0.28~0.38:0.17~0.23, the divalent
The pH of iron supply liquid is 4.5~5.5.Tetrasodium biscitrate ferrate, ferrous sulfate, lemon in divalent iron supply liquid of the invention
Sour these three substances of ferrous iron play the role of stable supplying ferrous iron.
The mixed liquor also includes impurity: citric acid, sodium citrate and sodium sulphate.
The total concentration of the mixed liquor ferrous ions is 0.09mol/L~0.1mol/L, the divalent iron supply liquid
PH is 5.0.
Another object of the present invention is to provide a kind of method for preparing divalent iron supply liquid of the invention, the methods
Include:
Step 1) after Citric Acid Mono powder is dissolved in water, is warming up to 50~60 DEG C, is slowly added to carbon in batches with stirring
It is reacted at sour sodium powder end；
Step 2) after being warming up to 70~80 DEG C, completely cuts off air, puts into green vitriol, is warming up to 88~92 DEG C instead
It should obtain divalent iron supply liquid.
Wherein, in step 1), 8~12 batches is divided to be slowly added to sodium carbonate with stirring, every batch of stirs 4~8 points after adding
Clock, wherein the ratio of powdered sodium carbonate, Citric Acid Mono powder and water is 2.5~3.5mol:2.5mol:10L.
In step 2), the molar ratio of the green vitriol and the sodium carbonate is 1mol:2.5~3.5mol, excellent
Select 1mol:3mol.After being warming up to 75 DEG C, completely cut off air, puts into green vitriol, be warming up to 90 DEG C of reactions and obtain ferrous iron
Supply liquid.
It is warming up to 88~92 DEG C of reactions and is cooled to room temperature to obtain divalent iron supply liquid in completely cutting off under air conditions in 2~5 hours
Body.
Further object of the present invention is that providing the divalent iron supply liquid is promoting the application in plant growth.Institute
The divalent iron supply liquid stated concentration of ferrous ion when using is 0.1 × 10-3Mol/L~1 × 10-3mol/L。
The main purpose of the present invention is to provide the divalent iron supply liquid that one kind can keep stability for a long time.
Applicant have noted that citric acid has strong chelating ability to iron, then ferrous citrate is done and has been investigated.Knot
Fruit discovery, after citric acid is in conjunction with two iron ions, mainly generates ferrous citrate, but under strongly acidic conditions, as pH value is lower than 2
Under conditions of, citric acid is not easy to generate ferrous citrate chelated iron in conjunction with ferrous ion.Ferrous citrate is water-soluble simultaneously
Property and it is bad, and be easy slowly to be oxidized to ironic citrate, white ironic citrate precipitating be precipitated, to reduce solvable in iron preparation
Property iron ratio, without being absorbed by plant, so more stable using a kind of soluble easily in water and chemical property is prepared in the present invention
Chemical substance, that is, tetrasodium biscitrate ferrate mode manufacture water-soluble liquid divalent iron preparation.The applicant has selected to close
Suitable ferrous sulfate, citric acid, sodium carbonate have prepared stable divalent iron supply liquid by series of chemical finally
Body.The concentration of its ferrous ions is the mixed liquor of 0.095mol/L.
Divalent iron supply liquid of the invention is highly stable, can keep stable for a long time in air, without by air oxygen
It is melted into ferric iron.In order to verify the stability of divalent iron supply liquid of the invention.With the distilled water of pH=7 by of the invention two
Valence iron supply liquid is diluted, respectively prepare ferrous iron concentration be 0.001mol/L, 0.0002mol/L, 0.0001mol/L,
The solution of 0.00002mol/L and the sulfuric acid of 0.001mol/L, 0.0002mol/L, 0.0001mol/L, 0.00002mol/L are sub-
Ferrous solution, prepared each 300mL of ferrous iron liquid are put into the beaker of 500mm, are opened wide and are placed in 20 DEG C of room temperature.By
6hr, 12hr, for 24 hours after r, 48hr, 72hr, the concentration of ferrous ion in each divalent iron supply liquid is measured respectively.Each ferrous iron
It is as shown in table 1 to supply the variation of liquid ferrous ions concentration.
Ferrous variation in the divalent iron supply liquid of the invention of table 1
It can be found that the stability that divalent iron supply liquid of the present invention can be maintained for a long time in air from table 1,
Offer ferrous ion that can be stable.In the feelings that ferrous ion concentration is 0.001mol/L, 0.0002mol/L, 0.0001mol/L
Under condition, even if being exposed in air 72 hours, ferrous ion therein is also 60% or more, and ferrous sulfate as a control group
After placing 6 hours, ferrous ion is largely aoxidized solution, substantially all after placing 12 hours to be oxidized, and has been risen not
To the effect of supply ferrous ion.Illustrate that divalent iron supply liquid of the invention can be protected for a long time under conventional environment
It is fixed to keep steady, and can be used as relatively stable divalent iron supply reagent.
The positive effect of the present invention is that: divalent iron supply liquid of the invention can provide stable divalent to plant
Iron can promote the germination of seedling, take root, and promote plant growth.
Specific embodiment
The preparation of 1 divalent iron supply liquid of embodiment
It is that >=99% Citric Acid Mono powder (2.5mol) is put into the reaction kettle of 10L water by purity, is warming up to 60
DEG C, dividing 10 batches to be slowly added to the purity that total amount is 3mol with stirring is >=97% sodium carbonate, and every batch of stirs 6 minutes after adding
80 DEG C are warming up to, completely cuts off air with nitrogen, the disposable purity for putting into 1mol is >=95% green vitriol, is finally heated up
To 92 DEG C, and kept for 92 DEG C react 2 hours while stirring.It is warmed to room temperature in isolation air drop.Divalent iron supply is finally made
Liquid.
By examining, in the divalent iron supply liquid of the present embodiment, the total concentration of mixed liquor ferrous ions (ferrous iron)
For 0.095mol/L, tetrasodium biscitrate ferrate, ferrous sulfate, ferrous citrate molal weight ratio be 1:0.28:0.23.
The preparation of 2 divalent iron supply liquid of embodiment
It is that >=99% Citric Acid Mono powder (2.5mol) is put into the reaction kettle of 10L water by purity, is warming up to 50
DEG C, dividing 8 batches to be slowly added to the purity that total amount is 3mol with stirring is >=97% sodium carbonate, and every batch of stirs 8 minutes after adding
70 DEG C are warming up to, completely cuts off air with nitrogen, the disposable purity for putting into 1mol is >=95% green vitriol, is finally heated up
To 88, and kept for 88 DEG C react 5 hours while stirring.It is warmed to room temperature in isolation air drop.Divalent iron supply liquid is finally made
Body.
By examining, in the divalent iron supply liquid of the present embodiment, the total concentration of mixed liquor ferrous ions (ferrous iron)
For 0.095mol/L, tetrasodium biscitrate ferrate, ferrous sulfate, ferrous citrate molal weight ratio be 1:0.38:0.17.
The preparation of 3 divalent iron supply liquid of embodiment
It is that >=99% Citric Acid Mono powder (2.5mol) is put into the reaction kettle of 10L water by purity, heats up 55 DEG C,
Dividing 12 batches to be slowly added to the purity that total amount is 3mol with stirring is >=97% sodium carbonate, and every batch of is stirred 4 minutes after adding and risen
Temperature completely cuts off air to 75 DEG C, with nitrogen, and the disposable purity for putting into 1mol is >=95% green vitriol, is finally warming up to
90 DEG C, and kept for 90 DEG C react 2 hours while stirring.It is warmed to room temperature in isolation air drop.Divalent iron supply liquid is finally made
Body.
By examining, in the divalent iron supply liquid of the present embodiment, the total concentration of mixed liquor ferrous ions (ferrous iron)
For 0.095mol/L, tetrasodium biscitrate ferrate, ferrous sulfate, ferrous citrate molal weight ratio are as follows: 1:0.35:0.2.
The preparation of 4 divalent iron supply liquid of embodiment
It is that >=99% Citric Acid Mono powder (2.5mol) is put into the reaction kettle of 10L water by purity, is warming up to 60
DEG C, dividing 10 batches to be slowly added to the purity that total amount is 2.5mol with stirring is >=97% sodium carbonate, and every batch of stirs 6 points after adding
Clock is warming up to 80 DEG C, completely cuts off air with nitrogen, the disposable purity for putting into 1mol is >=95% green vitriol, is finally risen
Temperature is kept for 90 DEG C react 4 hours while stirring to 90 DEG C.It is warmed to room temperature in isolation air drop.Ferrous iron is finally made to supply
To liquid.
By examining, in the divalent iron supply liquid of the present embodiment, the total concentration of mixed liquor ferrous ions (ferrous iron)
For 0.095mol/L, tetrasodium biscitrate ferrate, ferrous sulfate, ferrous citrate molal weight ratio are as follows: 1:0.30:0.19.
The preparation of 5 divalent iron supply liquid of embodiment
It is that >=99% Citric Acid Mono powder (2.5mol) is put into the reaction kettle of 10L water by purity, is warming up to 50
DEG C, dividing 10 batches to be slowly added to the purity that total amount is 3.5mol with stirring is >=97% sodium carbonate, and every batch of stirs 6 points after adding
Clock is warming up to 80 DEG C, completely cuts off air with nitrogen, the disposable purity for putting into 1mol is >=95% green vitriol, is finally risen
Temperature is kept for 90 DEG C react 4 hours while stirring to 90 DEG C.It is warmed to room temperature in isolation air drop.Ferrous iron is finally made to supply
To liquid.
By examining, in the divalent iron supply liquid of the present embodiment, the total concentration of mixed liquor ferrous ions (ferrous iron)
For 0.095mol/L, tetrasodium biscitrate ferrate, ferrous sulfate, ferrous citrate molal weight ratio be 1:0.36:0.22.
Effect example 1
Divalent iron supply liquid of the invention can provide stable ferrous iron to plant, promote plant growth, promote seedling
Germination, take root.The embodiment of the present invention is on June 15,12 days to 2018 March in 2018 in Zhoushan Dinghai District Lincheng street
It is carried out in the farmland of section.It is loam, pH value 6.4 for examination soil.Soil organic matter content 1.25%；Ammonium nitrogen, nitrate nitrogen are
15.43 and 68.64mg/L；Available phosphorus, potassium content are 9.41 and 34.21mg/L.Planting plants are spinach.
This experiment takes randomized block experiment to design, by 3 100 times of divalent iron supply liquid diluting of embodiment, 500 times,
1000 times, 5000 times of 4 groups of difference gradients, clear water control totally 5 processing, are repeated 3 times, 15 minizones totally.Each plot area
It is 8m2, the field management such as weeding, the prevention and control of plant diseases, pest control, fertilising of 15 cells are unified to synchronize progress, and common fertilizer usage amount has
Machine fertilizer, urea, calcium superphosphate, potassium sulfate are as follows: 800g/m2、8g/m2、30g/m2、15g/m2.The ferrous iron of 4 groups of difference gradients supplies
It was applied once to liquid, clear water every 14 days, amount of application is each 300mL/m2, method of application be with atomizers spray uniformly extremely
Designated area block.Spinach is harvested on the 15th June.Every block of cells randomly selects 30 plants of spinach, measures its plant height, maximum leaf
Length, the number of blade, overground part fresh weight, underground part fresh weight, calculates maximum leaf area (maximum leaf length × maximum width of blade) at maximum width of blade.
The biological character of Different treatments spinach is as shown in table 2.
The biological character of 2 different disposal spinach of table
The results show that promoting when by 100 times, 500 times, 1000 times of this divalent iron supply reagent dilutions the growth of spinach
Effect is obvious, it can be found that after applied divalent iron supply liquid of the invention, it is reachable to the overground part fresh weight value added of spinach
To 20% or more, and to the root promotion rate of underground part also 8% or so.Two various concentration gradients at 100 times, 500 times of dilution
Under the conditions of the growth of spinach is promoted most obvious, when diluting 1000 times under gradient, facilitation is slightly weaker than the gradient of front two,
But also relatively dilute 5000 times when, facilitation effect is significantly much.Consider by the way that cost, effect etc. are many-sided, is promoting spinach growth
During, effect at 1000 times of this ferrous iron reagent dilutions is most obvious and most economical.
Effect example 2
Can to verify the divalent iron supply liquid of the invention of different mol ratio obtained under the conditions of differential responses
Effect of increasing production is played to the plantation of vegetables, the embodiment of the present invention is fixed in Zhoushan on June 25,10 days to 2018 April in 2018
Sea area Lincheng street carries out.Cultivating container is that (specification is 0.450m × 0.270m × 0.195m to Box of foamed plastics, and cultivated area is
0.1215m2).It tests soil and uses Zhoushan Dinghai District common agricultural farms soil, fertility level is not high, pH value 6.2.Soil is organic
Matter content 1.02%；Ammonium nitrogen, nitrate nitrogen are 13.22 and 59.18mg/L；Available phosphorus, potassium content are 6.02 and 33.4mg/L.Kind
Plant plant is leek.1000 times of diluent As of divalent iron supply liquid containing different mol ratio of this experiment, tri- kinds of B, C, D, E and clear water
6 processing are compareed, are repeated 3 times, totally 18 bubble chambers.Wherein tetrasodium biscitrate ferrate, ferrous sulfate, citric acid are sub- in A dilution
The molal weight ratio of iron are as follows: 1:0.28:0.23；Mole of tetrasodium biscitrate ferrate, ferrous sulfate, ferrous citrate in B dilution
Mass ratio are as follows: 1:0.38:0.17；The molal weight ratio of tetrasodium biscitrate ferrate, ferrous sulfate, ferrous citrate in C dilution are as follows:
1:0.35:0.2；The molal weight ratio of tetrasodium biscitrate ferrate, ferrous sulfate, ferrous citrate in D dilution are as follows: 1:0.30:
0.19；The molal weight ratio of tetrasodium biscitrate ferrate, ferrous sulfate, ferrous citrate in E dilution are as follows: 1:0.36:0.22.
Field planting on April 10th, 2018,8 clumps of leek of every case, 6 plants every clump, spacing 9cm × 9cm.The weeding of 6 bubble chambers, disease
The unified synchronous progress of the field management such as pest control, fertilising, common fertilizer usage amount organic fertilizer, urea, calcium superphosphate, potassium sulfate
Are as follows: 600g/m2、10g/m2、35g/m2、20g/m2.A, B, C group and clear water group applied once every 14 days, and amount of application is each
300mL/m2, method of application is with atomizers spray uniformly to designated area block.Leek is harvested on the 25th June.From each heavy
Three clumps of leek are randomly selected in multiple, measure its plant height, stem thickness, leaf width and yield.The biological character of Different treatments leek
As shown in table 3.
The biological character of 3 different disposal leek of table
The results show that 1000 times of dilutions of the divalent iron supply liquid of the invention of different mol ratio ingredient are to leek
Growth be obviously promoted effect, to the effect of increasing production of leek 16.8~24.6%.
Claims (10)
1. a kind of divalent iron supply liquid, it is characterised in that the divalent iron supply liquid is a kind of mixed containing ferrous ion
Liquid is closed, the mixed liquor includes tetrasodium biscitrate ferrate, ferrous sulfate, ferrous citrate, tetrasodium biscitrate ferrate, sulfuric acid in mixed liquor
Ferrous, ferrous citrate molal weight ratio is 1:0.28~0.38:0.17~0.23, and the pH of the divalent iron supply liquid is
4.5~5.5.
2. divalent iron supply liquid as described in claim 1, which is characterized in that the mixed liquor also includes impurity: citric acid,
Sodium citrate and sodium sulphate.
3. divalent iron supply liquid as described in claim 1, which is characterized in that the total concentration of the mixed liquor ferrous ions
For 0.09mol/L~0.1mol/L, the pH of the divalent iron supply liquid is 5.0.
4. a kind of method for preparing divalent iron supply liquid described in claim 1, which is characterized in that the described method includes:
Step 1) after Citric Acid Mono powder is dissolved in water, is warming up to 50~60 DEG C, is slowly added to sodium carbonate in batches with stirring
Powder is reacted；
Step 2) after being warming up to 70~80 DEG C, completely cuts off air, puts into green vitriol, be warming up to 88~92 DEG C and react
To divalent iron supply liquid.
5. method as claimed in claim 4, which is characterized in that in step 1), 8~12 batches is divided to be slowly added to carbon with stirring
Sour sodium, every batch of stir 4~8 minutes after adding, wherein the ratio of powdered sodium carbonate, Citric Acid Mono powder and water be 2.5~
3.5mol:2.5mol:10L。
6. method as claimed in claim 5, which is characterized in that in step 2), the green vitriol and the carbonic acid
The molar ratio of sodium is 1mol:2.5~3.5mol, preferably 1mol:3mol.
7. method as claimed in claim 5, which is characterized in that in step 2), after being warming up to 75 DEG C, completely cut off air, investment seven
Ferrous sulfate hydrate is warming up to 90 DEG C of reactions and obtains divalent iron supply liquid.
8. method as claimed in claim 5, which is characterized in that in step 2), be warming up to 88~92 DEG C reaction 2~5 hours in
It is cooled to room temperature to obtain divalent iron supply liquid under isolation air conditions.
9. divalent iron supply liquid as described in claim 1 is promoting the application in plant growth.
10. the use as claimed in claim 7, which is characterized in that the divalent iron supply liquid in use when ferrous iron from
The concentration of son is 0.1 × 10-3Mol/L~1 × 10-3mol/L。
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110079326A (en) * | 2019-06-04 | 2019-08-02 | 金正大生态工程集团股份有限公司 | A kind of preparation method of iron content soil conditioner |
| CN110105142A (en) * | 2019-06-04 | 2019-08-09 | 金正大生态工程集团股份有限公司 | A kind of chelating ferrous salt fertilizer of acidity and the preparation method and application thereof |
| CN110352875A (en) * | 2019-07-03 | 2019-10-22 | 天津现代晨辉科技集团有限公司 | The compensation process of iron, calcium and potassium element in a kind of fish and vegetable symbiotic system |
| CN114436811A (en) * | 2021-12-27 | 2022-05-06 | 郑州瑞普生物工程有限公司 | Preparation method of sodium ferrous citrate |
| JP7348610B1 (en) * | 2023-04-10 | 2023-09-21 | ソブエクレー株式会社 | Iron supply agent for plant growth |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101128116A (en) * | 2005-02-22 | 2008-02-20 | 丸尾钙株式会社 | Plant quality improver and manufacturing method thereof |
| CN101328087A (en) * | 2008-06-16 | 2008-12-24 | 山东农业大学 | Foliar fertilizer effervescent tablet and preparation method thereof |
| WO2013024589A1 (en) * | 2011-08-12 | 2013-02-21 | Ｓｂｉファーマ株式会社 | Prophylactic agent and/or therapeutic agent for sepsis |
| CN109809846A (en) * | 2019-02-02 | 2019-05-28 | 浙江科罗尼生物科技有限公司 | The application of divalent iron supply liquid and processing organic waste composition |
| CN109848183A (en) * | 2019-02-21 | 2019-06-07 | 浙江科罗尼生物科技有限公司 | Application of the divalent iron supply liquid in terms of promoting petroleum residue processing microflora fermentation |
-
2019
- 2019-02-02 CN CN201910106700.1A patent/CN109608249A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101128116A (en) * | 2005-02-22 | 2008-02-20 | 丸尾钙株式会社 | Plant quality improver and manufacturing method thereof |
| CN101328087A (en) * | 2008-06-16 | 2008-12-24 | 山东农业大学 | Foliar fertilizer effervescent tablet and preparation method thereof |
| WO2013024589A1 (en) * | 2011-08-12 | 2013-02-21 | Ｓｂｉファーマ株式会社 | Prophylactic agent and/or therapeutic agent for sepsis |
| CN103747784A (en) * | 2011-08-12 | 2014-04-23 | 思佰益药业股份有限公司 | Prophylactic agent and/or therapeutic agent for sepsis |
| CN109809846A (en) * | 2019-02-02 | 2019-05-28 | 浙江科罗尼生物科技有限公司 | The application of divalent iron supply liquid and processing organic waste composition |
| CN109848183A (en) * | 2019-02-21 | 2019-06-07 | 浙江科罗尼生物科技有限公司 | Application of the divalent iron supply liquid in terms of promoting petroleum residue processing microflora fermentation |
Non-Patent Citations (5)
| Title |
|---|
| TAN, CQ (TAN, CHAOQUN): "《Degradation of diuron by persulfate activated with ferrous ion》", 《SEPARATION AND PURIFICATION TECHNOLOGY》 * |
| 孙儒品: "《枸橼酸亚铁钠的制备》", 《中国医药工业杂质》 * |
| 张国平: "《100种常见农业化合物质使用指南》", 31 December 1994 * |
| 谷村显雄: "《食品添加剂公定书 注释 解说 第6版》", 30 September 1997 * |
| 陈骿声: "《有机酸发酵生产技术》", 31 January 1991 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110079326A (en) * | 2019-06-04 | 2019-08-02 | 金正大生态工程集团股份有限公司 | A kind of preparation method of iron content soil conditioner |
| CN110105142A (en) * | 2019-06-04 | 2019-08-09 | 金正大生态工程集团股份有限公司 | A kind of chelating ferrous salt fertilizer of acidity and the preparation method and application thereof |
| CN110352875A (en) * | 2019-07-03 | 2019-10-22 | 天津现代晨辉科技集团有限公司 | The compensation process of iron, calcium and potassium element in a kind of fish and vegetable symbiotic system |
| CN114436811A (en) * | 2021-12-27 | 2022-05-06 | 郑州瑞普生物工程有限公司 | Preparation method of sodium ferrous citrate |
| CN114436811B (en) * | 2021-12-27 | 2023-10-31 | 郑州瑞普生物工程有限公司 | Preparation method of sodium ferrous citrate |
| JP7348610B1 (en) * | 2023-04-10 | 2023-09-21 | ソブエクレー株式会社 | Iron supply agent for plant growth |
| WO2024214128A1 (en) * | 2023-04-10 | 2024-10-17 | ソブエクレー株式会社 | Iron supply agent for plant growth |
| EP4470997A4 (en) * | 2023-04-10 | 2025-02-26 | Sobue Clay Co., Ltd. | IRON SUPPLEMENT FOR PLANT GROWTH |
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