CN110079326B - Preparation method of iron-containing soil conditioner - Google Patents
Preparation method of iron-containing soil conditioner Download PDFInfo
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- CN110079326B CN110079326B CN201910481978.7A CN201910481978A CN110079326B CN 110079326 B CN110079326 B CN 110079326B CN 201910481978 A CN201910481978 A CN 201910481978A CN 110079326 B CN110079326 B CN 110079326B
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000003516 soil conditioner Substances 0.000 title claims abstract description 50
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims abstract description 27
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 25
- 239000011640 ferrous citrate Substances 0.000 claims abstract description 24
- 235000019850 ferrous citrate Nutrition 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 5
- 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 5
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims description 50
- 239000004021 humic acid Substances 0.000 claims description 48
- 239000003245 coal Substances 0.000 claims description 28
- 229960004106 citric acid Drugs 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000003415 peat Substances 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 239000003077 lignite Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229960002303 citric acid monohydrate Drugs 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- UMEAURNTRYCPNR-UHFFFAOYSA-N azane;iron(2+) Chemical compound N.[Fe+2] UMEAURNTRYCPNR-UHFFFAOYSA-N 0.000 claims 1
- GLMQHZPGHAPYIO-UHFFFAOYSA-L azanium;2-hydroxypropane-1,2,3-tricarboxylate;iron(2+) Chemical compound [NH4+].[Fe+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O GLMQHZPGHAPYIO-UHFFFAOYSA-L 0.000 claims 1
- 239000004313 iron ammonium citrate Substances 0.000 claims 1
- 235000000011 iron ammonium citrate Nutrition 0.000 claims 1
- 239000002689 soil Substances 0.000 description 28
- 239000003337 fertilizer Substances 0.000 description 26
- 239000000047 product Substances 0.000 description 25
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 19
- 238000011282 treatment Methods 0.000 description 18
- 239000011573 trace mineral Substances 0.000 description 10
- 235000013619 trace mineral Nutrition 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 239000002609 medium Substances 0.000 description 9
- 238000001994 activation Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 230000004913 activation Effects 0.000 description 7
- 239000011790 ferrous sulphate Substances 0.000 description 7
- 235000003891 ferrous sulphate Nutrition 0.000 description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 108090000790 Enzymes Proteins 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000006174 pH buffer Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 206010022971 Iron Deficiencies Diseases 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- -1 iron ions Chemical class 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000016709 nutrition Nutrition 0.000 description 2
- 230000035764 nutrition Effects 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 1
- 229910001309 Ferromolybdenum Inorganic materials 0.000 description 1
- 102000005298 Iron-Sulfur Proteins Human genes 0.000 description 1
- 108010081409 Iron-Sulfur Proteins Proteins 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229940090496 Urease inhibitor Drugs 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 229910001586 aluminite Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000021112 essential micronutrients Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 235000018343 nutrient deficiency Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000029219 regulation of pH Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- 239000002601 urease inhibitor Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/14—Soil-conditioning materials or soil-stabilising materials containing organic compounds only
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2101/00—Agricultural use
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2109/00—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE pH regulation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Materials Engineering (AREA)
- Fertilizers (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Abstract
The invention relates to a preparation method of a soil conditioner containing iron, which comprises the steps of preparing ferrous ammonium citrate; preparing a soil conditioner containing iron; the preparation method of the ferrous ammonium citrate comprises the following steps: citric acid and water are mixed and heated, iron powder is added for stirring reaction, the temperature is reduced after the reaction, ammonia gas is introduced for neutralization until the pH value is 5.5-6.5, and water is removed, so that ammonium ferrous citrate is obtained.
Description
Technical Field
The invention relates to a preparation method of a soil conditioner containing iron, belonging to the technical field of soil conditioners.
Background
At present, the problems of soil pollution, acidification, salinization, degeneration, nutrient deficiency and the like are increasingly highlighted in China due to unreasonable application of chemical fertilizers, and the problems become the biggest obstacle influencing the sustainable development of agriculture in China. At present, more than 40% of cultivated land of soil in China is degraded, and 1.5 hundred million acres of cultivated land are polluted. Meanwhile, from the 80 th century, the soil conditioner products in China begin to be developed, and through the common efforts of scientific research personnel and the whole industry, the types of the products are more and more, the technical level is continuously improved, and the soil conditioner is rapidly developed in recent years. However, most of the current domestic soil conditioner products are common universal soil conditioners, lack pertinence, cannot be used for symptomatic medicine administration, and cause resource waste.
Humic acid soil conditioners are generally known to have certain improving and enhancing effects on the structure of soil and the fertility of the soil. At present, the varieties of humic acid fertilizers and humic acid soil conditioners are numerous, three types of humic acid soil conditioners are mainly used, one type is the humic acid soil conditioner prepared by directly using low-rank coal, the cost of the method is low, but the humic acid in the low-rank coal is water-insoluble humic acid, the effect is difficult to generate in the season, and the soil improvement effect is poor. One is that macromolecule humic acid is changed into micromolecule water-soluble humic acid by oxidation mode, the humic acid prepared by the method has better water-solubility and anti-flocculation property, but the preparation process is relatively complex and the cost is higher. The third category is that humic acid is prepared into salt by a simple method, insoluble humic acid is converted into water-soluble humic acid salt, the method has simple process and low cost, but the obtained water-soluble humic acid has poor flocculation resistance.
Iron is an essential micronutrient for plant growth and participates in many key physiological and biochemical processes of organisms. Iron is a catalyst for many enzymes during chlorophyll synthesis; iron is also involved in redox reactions and electron transport processes in plant cells, for example, nitrogen fixation enzymes of leguminous plants, whose active center is a complex of ferromolybdenum and iron-sulfur proteins, act as nitrogen fixation; iron is also an active ingredient of the relevant enzymes in the respiration of plant cells. Fe2+Is the main form of plant absorption, except that gramineous plants can directly absorb part of Fe3+Besides, most plants can only directly utilize Fe in soil2+。Fe3+Reduced to Fe only on the surface of the root system2+Can be absorbed later. Ferrous sulfate is a common ferrite fertilizer, but insoluble ferric iron precipitate is easily formed in the fertilizer and soil, so the ferrous sulfate is only suitable for single foliage spraying and is not suitable for being added into the fertilizer, and the application of ferrous form iron elements is greatly limited.
Chinese patent document CN106831239A discloses a saline-alkali soil conditioner, which comprises the following raw materials: the biological fertilizer comprises calcium sulfate, ferrous sulfate, humic acid, a microbial agent, a urease inhibitor, a nitrification inhibitor, lignin, bentonite, zeolite powder, carboxymethyl chitosan, polyacrylamide, starch and an auxiliary material, wherein the auxiliary material is any one or a mixture of at least two of attapulgite powder, medical stone powder and aluminite trihydrate powder. The saline-alkali soil conditioner fully exerts the synergistic effect of the raw materials, can effectively reduce the pH value and the salt content of saline-alkali soil, lightens soil hardening, and increases the contents of calcium, iron and organic matters in the soil. Iron in the conditioner is provided by ferrous sulfate, and indissolvable ferric iron precipitate is easily formed in fertilizers and soil, so that the conditioner is only suitable for single foliage spraying, and the application of ferrous iron element is limited.
The organic molecule is utilized to prepare the chelated iron to protect iron ions from being fixed, thereby improving the utilization efficiency of Fe and exerting better effectGood nutrition effect, which is a common method for preparing iron element nutrition in the fertilizer. EDTA is generally used as a chelating agent to protect iron ions, but EDTA is not easy to degrade and is easy to cause environmental pollution when applied to soil; and EDTA chelating agent can not effectively avoid Fe2+So that the iron in the existing EDTA chelate product is mostly Fe3+。
In order to solve the problems of soil improvement and low iron absorption efficiency of crops, a need exists for developing an iron-containing soil conditioner product which is simple to prepare, low in cost and good in humic acid water solubility and flocculation resistance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a soil conditioner containing iron, which comprises the steps of adding ammonium ferrous citrate into low-rank coal, activating insoluble humic acid in the low-rank coal into water-soluble humic acid to obtain the soil conditioner containing iron, wherein the conditioner contains the water-soluble humic acid and ferrous citrate, can effectively improve the granular structure of soil, activates and chelates medium and trace elements in the soil, and simultaneously provides iron elements, so that the problem of iron-deficiency yellowing of crops is solved, and the yield of the crops in the season is improved. The preparation process is simple and the cost is low.
The invention solves the technical problems by adopting the following technical scheme:
a preparation method of a soil conditioner containing iron comprises the following steps:
preparing ferrous ammonium citrate;
preparing a soil conditioner containing iron;
the preparation method of the ferrous ammonium citrate comprises the following steps: mixing citric acid with water, heating, adding iron powder, stirring for reaction, cooling after reaction, introducing ammonia gas for neutralization until the pH value is 5.5-6.5, and removing water to obtain the ammonium ferrous citrate.
According to the invention, in the step of preparing the ferrous ammonium citrate, the citric acid is citric acid monohydrate or citric acid anhydrous.
According to the invention, in the preferable preparation step of the ferrous ammonium citrate, the addition amount of water is 1-2 times of the mass of citric acid.
According to the preferable preparation method, in the preparation step of the ferrous ammonium citrate, the molar ratio of citric acid to iron powder is 12-15: 1, the particle size of the iron powder is 0.075-0.15 mm.
According to the invention, in the preferable preparation step of the ferrous ammonium citrate, citric acid and water are mixed and heated to 55-85 ℃, and then the iron powder is slowly added.
According to the optimization of the invention, in the preparation step of the ferrous ammonium citrate, the ferrous powder is added and then stirred for reaction for 2-4h, and the temperature is reduced to 40 +/-5 ℃ after the reaction.
According to the invention, in the preferable preparation step of the ferrous ammonium citrate, the solution is subjected to reduced pressure distillation to remove water, wherein the reduced pressure distillation pressure is 10-25kp, and the temperature is 70-90 ℃.
According to the invention, the preferable preparation steps of the iron-containing soil conditioner are as follows: grinding low-rank coal into low-rank coal powder, adding ammonium ferrous citrate and water, continuously stirring, reacting at 60-80 ℃, and drying reactants in vacuum to obtain the iron-containing soil conditioner.
According to the invention, the preferable mass ratio of the low-rank coal to the ammonium ferrous citrate is 1: 0.4-0.5; the mass ratio of the low-rank coal to the water is 1: 1-2.
According to the invention, the low-rank coal is preferably weathered coal, lignite or peat, and the total humic acid content in the low-rank coal is 45-62%.
According to the preferable preparation method, in the step of preparing the iron-containing soil conditioner, the reaction time is 2-6h, the particle size of the low-order coal powder is 0.15-0.38 mm, the vacuum drying temperature is 30-100 ℃, and the vacuum degree is 0-0.09 Mpa.
According to the optimization of the invention, the prepared iron-containing soil conditioner contains citric acid, ammonium citrate, citric acid chelated medium trace elements, humic acid chelated medium trace elements and ammonium ferrous citrate, and is weakly acidic after being dissolved in water, the pH value is 3.5-6.5, and the humic acid in the iron-containing soil conditioner is water-soluble humic acid.
In the preparation of the ferrous ammonium citrate, excessive citric acid reacts with iron powder and then ammonia is introduced for neutralization, so that the ferrous ammonium citrateThe mixture of ammonium ferrous citrate and ammonium citrate, and the ammonium citrate can form chelation stabilization effect on the ammonium ferrous citrate. Then adding a mixture containing ammonium ferrous citrate and ammonium citrate into weathered coal, wherein part of the ammonium citrate chelates the trace elements in calcium, magnesium, iron, silicon and the like in the low-rank coal to enable humic acid to be more easily dissociated, and in addition, NH4 in the ammonium citrate+Part of the humic acid is combined with humic acid to form ammonium humate and citric acid, the final product contains citric acid, ammonium citrate, medium and trace elements chelated with citric acid, humic acid, medium and trace elements chelated with humic acid and ammonium ferrous citrate, and the product can form a pH buffer system after being dissolved in water and is weakly acidic.
The invention has the following beneficial effects:
1. the iron element in the iron-containing soil conditioner prepared by the invention is ferrous iron and is easier to be absorbed by crops, in addition, ammonium citrate, ammonium humate and the whole pH buffer system are beneficial to the stability of ammonium ferrous citrate, and the ammonium ferrous citrate as a water-soluble salt is easier to be absorbed by the crops and can be used for quickly relieving the phenomenon of iron deficiency and avoiding the phenomenon of yellowing of the crops.
2. According to the preparation method, ammonium ferrous citrate is added into the low-rank coal, so that the water-insoluble humic acid in the low-rank coal is activated into the water-soluble humic acid, the activation process is simple, the activation rate of the humic acid can reach more than 50%, the performance of the soil improved by the unactivated humic acid is poor, and the improvement effect of the activated water-soluble humic acid on the soil is obvious.
3. The iron-containing soil conditioner prepared by the invention contains citric acid, ammonium citrate, medium and trace elements chelated with citric acid, humic acid, medium and trace elements chelated with humic acid and ammonium ferrous citrate, and the product can form a pH buffer system after being dissolved in water, is weakly acidic, has an obvious soil improvement effect, can play a good pH regulation role particularly in acid and alkaline soil, can activate phosphorus and medium and trace elements in soil, improve the soil structure, chelate the active medium and trace elements in soil, and achieves the purpose of increasing the yield of crops.
Detailed Description
The present invention is further illustrated by the following specific examples.
The weathered coal is purchased from Shengda biological development Limited company of Lvjiao city, wherein the total amount of humic acid is 46.59%; the lignite is purchased from Heilongjiang Jiahe humic acid Limited company, wherein the total content of humic acid in the lignite is 48.36 percent; the peat is purchased from black soil agriculture science and technology limited company in Xiamen city, wherein the total amount of humic acid is 61.85 percent.
Example 1
A preparation method of an iron-containing soil conditioner comprises the following specific steps:
preparation of ferrous ammonium citrate: mixing 210g of citric acid monohydrate and 192g of water, stirring, heating to 55 ℃, slowly adding 4.6g of 250-mesh iron powder, continuously stirring for reaction for 4 hours, cooling to 40 ℃, introducing ammonia gas for neutralization until the pH value is 6.5, and distilling the obtained solution at 10kp and 70 ℃ under reduced pressure to remove water to obtain 244.7g of a product containing ammonium ferrous citrate.
Grinding 100g of weathered coal into 40 meshes, adding 40g of the prepared ammonium ferrous citrate product and 200g of water, continuously stirring at 60 ℃ for reacting for 2 hours, and drying reactants at 25kp and 70 ℃ after the reaction is finished to obtain the soil conditioner product A.
Example 2
A preparation method of an iron-containing soil conditioner comprises the following specific steps:
preparation of ferrous ammonium citrate: 192g of citric acid and 288g of water are stirred and heated to 70 ℃, 4.1g of 150-mesh iron powder is slowly added, the mixture is continuously stirred and reacted for 3 hours, the temperature is reduced to 45 ℃, ammonia gas is introduced to neutralize the mixture to pH 6, the obtained solution is decompressed and distilled at the temperature of 85 ℃ and 20kp to remove water, and 244.6g of product containing ammonium ferrous citrate is obtained.
Grinding 100g of lignite into 60 meshes, adding 45g of the prepared ferrous ammonium citrate-containing product and 150g of water, continuously stirring at 70 ℃ for reacting for 4 hours, and drying reactants at 50kp and 80 ℃ after the reaction is finished to obtain a soil conditioner product B.
Example 3
A preparation method of an iron-containing soil conditioner comprises the following specific steps:
preparation of ferrous ammonium citrate: 192g of citric acid and 384g of water are stirred and heated to 85 ℃, 3.8g of 100-mesh iron powder is slowly added, the mixture is continuously stirred and reacts for 2 hours, the temperature is reduced to 35 ℃, ammonia gas is introduced to neutralize the mixture until the pH value is 5.5, the obtained solution is decompressed and distilled at the temperature of 90 ℃ and at the temperature of 25kp to remove water, and 244.4g of product containing ammonium ferrous citrate is obtained.
Grinding 100g of peat into powder of 100 meshes, adding 50g of the prepared ferrous ammonium citrate-containing product and 100g of water, continuously stirring at 80 ℃ for reaction for 6 hours, and drying reactants at 25kp and 90 ℃ after the reaction is finished to obtain a soil conditioner product C.
Comparative example 1
A preparation method of a soil conditioner containing iron comprises the following steps:
grinding 100g of peat into powder of 100 meshes, adding 50g of ferrous sulfate and 100g of water, continuously stirring at 80 ℃ for reacting for 6 hours, and drying reactants at 25kp and 90 ℃ after the reaction is finished to obtain a soil conditioner product D.
Experimental example:
the water-soluble humic acid content in the products of examples 1 to 3 and comparative example 1 was respectively tested, and the humic acid activation rate was calculated, and the results are shown in table 1.
TABLE 1 content of water-soluble humic acid in soil conditioner product, activation Rate index
| Soil conditioner product | A | B | C | D |
| Content of water-soluble humic acid | 18.80％ | 19.32％ | 21.97％ | 0.8％ |
| Activation rate of humic acid | 56.45％ | 57.85％ | 53.21％ | 1.94％ |
As can be seen from table 1 above, according to the invention, ammonium ferrous citrate is added to the low-rank coal, so that the water-insoluble humic acid in the low-rank coal is activated into the water-soluble humic acid, the activation rate of the humic acid in examples 1-3 can reach more than 50%, whereas the iron-containing soil conditioner prepared by using ferrous sulfate in comparative example 1 has a very low activation rate of the humic acid, which is only 1.94%, and the ferrous sulfate has no activation capability to the humic acid.
In order to further illustrate the effect of the soil conditioner prepared by the invention, the prepared product is subjected to field experiments, and the experimental arrangement is as follows:
1. the experimental site: the test is carried out in riverway villages in Wugong county of Shaanxi province, Xiyangyang city, the pH value of soil is 8.44 and is slightly alkaline, the content of organic matters is 0.92 percent, the alkaline hydrolysis nitrogen is 108ppm, the available phosphorus is 11ppm and the available potassium is 88 ppm. The compound fertilizer used in the test is 15-15-15 compound fertilizer. The experimental crop is summer corn.
2. The experimental treatments were as follows:
2.1 treatment 1: applying fertilizer according to the habit, using 40kg of compound fertilizer as base fertilizer in 15-15-15 per mu, and applying 10kg of urea in the small-horn period and the large-horn period respectively.
2.2 treatment 2: 45kg of compound fertilizer 15-15-15 per mu is used as base fertilizer, and 10kg of urea is applied additionally at the small-horn period and the large-horn period respectively.
2.3, treatment 3: 40kg and 10kg of compound fertilizer and soil conditioner product A are used as base fertilizer per mu, and 10kg of urea is applied additionally at the small-horn period and the large-horn period respectively.
2.4, treatment 4: 40kg and 10kg of compound fertilizer and soil conditioner product B are used as base fertilizer per mu of 15-15-15, and 10kg of urea is applied additionally at the small-horn period and the large-horn period respectively.
2.5, treatment 5: 40kg of compound fertilizer and 10kg of soil conditioner product C per mu of 15-15-15 are used as base fertilizer, and 10kg of urea is applied additionally at the small-horn period and the large-horn period respectively.
2.6 treatment 6: 40kg and 10kg of compound fertilizer and soil conditioner product D of 15-15-15 per mu are used as base fertilizer, and 10kg of urea is applied additionally at the small-horn period and the large-horn period respectively.
TABLE 2
| Treatment of | Yield (kg/mu) | Increase yield in comparison with treatment 1 |
| Process 1 | 576kg | ---- |
| Treatment 2 | 580kg | 0.69％ |
| Treatment 3 | 656kg | 13.89％ |
| Treatment 4 | 651kg | 13.02％ |
| Treatment 5 | 660kg | 14.58％ |
| Treatment 6 | 589kg | 2.26％ |
As can be seen from the comparison of the experimental results in the table 2, the difference between the acre yield of the treatment 1 and the acre yield of the treatment 2 is small, which indicates that the crop yield can not be effectively improved by increasing the fertilizer again under the condition of applying enough compound fertilizer, and the yield of the treatments 3, 4 and 5 is respectively increased by 13.89 percent, 13.02 percent and 14.58 percent compared with the yield of the treatment 1. Compared with the traditional fertilizer application, the ferrous-containing soil conditioner prepared by the invention can obviously increase the yield, the yield is increased by 12.32% when the green-iron-containing soil conditioner is applied for 6 times, and the yield is increased by 5 times, which shows that the effect of the green-iron citrate on processing peat is far better than that of the green-iron sulfate.
Claims (6)
1. A preparation method of a soil conditioner containing iron comprises the following steps:
the preparation method comprises the following steps: mixing citric acid and water, heating, adding iron powder, stirring for reaction, cooling after reaction, introducing ammonia gas for neutralization until the pH value is 5.5-6.5, and removing water to obtain ferrous ammonium citrate; the molar ratio of the citric acid to the iron powder is 12-15: 1, the particle size of the iron powder is 0.075-0.15 mm;
the preparation method of the iron-containing soil conditioner comprises the following steps: grinding low-rank coal into low-rank coal powder, adding ammonium ferrous citrate and water, continuously stirring, reacting at 60-80 ℃, and drying reactants in vacuum to obtain the iron-containing soil conditioner; the mass ratio of the low-rank coal to the ferrous ammonium citrate is 1: 0.4-0.5; the mass ratio of the low-rank coal to the water is 1: 1-2; the low-rank coal is weathered coal, lignite or peat, and the total humic acid content in the low-rank coal is 45-62%.
2. The method for preparing the iron-containing soil conditioner according to claim 1, wherein in the step of preparing the ammonium ferrous citrate, the citric acid is citric acid monohydrate or citric acid anhydrous.
3. The preparation method of the iron-containing soil conditioner according to claim 1, wherein in the step of preparing the iron-containing ammonium ferrous citrate, the addition amount of water is 1-2 times of the mass of citric acid.
4. The preparation method of the iron-containing soil conditioner according to claim 1, wherein in the preparation step of the iron ammonium ferrous citrate, citric acid and water are mixed and heated to 55-85 ℃, and then iron powder is slowly added; adding iron powder, stirring for reaction for 2-4h, and cooling to 40 +/-5 ℃ after reaction.
5. The preparation method of the iron-containing soil conditioner according to claim 1, wherein in the preparation step of the iron ammonium citrate, the solution is subjected to reduced pressure distillation to remove water, wherein the reduced pressure distillation pressure is 10-25kp, and the temperature is 70-90 ℃.
6. The preparation method of the iron-containing soil conditioner according to claim 1, wherein in the preparation step of the iron-containing soil conditioner, the reaction time is 2-6h, the particle size of the low-rank coal powder is 0.15-0.38 mm, the vacuum drying temperature is 30-100 ℃, and the vacuum degree is 0-0.09 MPa.
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