CN113845394A - Preparation method of non-full water-soluble secondary element solid fertilizer - Google Patents
Preparation method of non-full water-soluble secondary element solid fertilizer Download PDFInfo
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- 239000003337 fertilizer Substances 0.000 title claims abstract description 63
- 239000007787 solid Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 52
- 239000011575 calcium Substances 0.000 claims abstract description 35
- 239000002367 phosphate rock Substances 0.000 claims abstract description 34
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 33
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000011777 magnesium Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 28
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 26
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000013078 crystal Substances 0.000 claims abstract description 21
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 21
- 238000001914 filtration Methods 0.000 claims abstract description 20
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000002844 melting Methods 0.000 claims abstract description 10
- 230000008018 melting Effects 0.000 claims abstract description 10
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 59
- 239000000843 powder Substances 0.000 claims description 35
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 14
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 13
- 239000001099 ammonium carbonate Substances 0.000 claims description 13
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 13
- 239000002826 coolant Substances 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 238000003763 carbonization Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- ICSSIKVYVJQJND-UHFFFAOYSA-N calcium nitrate tetrahydrate Chemical compound O.O.O.O.[Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ICSSIKVYVJQJND-UHFFFAOYSA-N 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- LFMYQKSTJULFQX-UHFFFAOYSA-N diazanium nitric acid sulfate Chemical compound [NH4+].[NH4+].O[N+]([O-])=O.[O-]S([O-])(=O)=O LFMYQKSTJULFQX-UHFFFAOYSA-N 0.000 claims 1
- 239000002689 soil Substances 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 5
- 235000015097 nutrients Nutrition 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 13
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 6
- 235000011130 ammonium sulphate Nutrition 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 238000012271 agricultural production Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000012010 growth Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000011573 trace mineral Substances 0.000 description 3
- 235000013619 trace mineral Nutrition 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- 238000011112 process operation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QHKMFBOMGWRWHN-UHFFFAOYSA-N [N+](=O)(O)[O-].P(O)(O)O Chemical compound [N+](=O)(O)[O-].P(O)(O)O QHKMFBOMGWRWHN-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- AWADHHRPTLLUKK-UHFFFAOYSA-N diazanium sulfuric acid sulfate Chemical compound [NH4+].[NH4+].OS(O)(=O)=O.[O-]S([O-])(=O)=O AWADHHRPTLLUKK-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000004720 fertilization Effects 0.000 description 1
- 244000037666 field crops Species 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
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
- C05G5/10—Solid or semi-solid fertilisers, e.g. powders
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D3/00—Calcareous fertilisers
- C05D3/02—Calcareous fertilisers from limestone, calcium carbonate, calcium hydrate, slaked lime, calcium oxide, waste calcium products
-
- 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
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/80—Soil conditioners
-
- 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
- C05G5/10—Solid or semi-solid fertilisers, e.g. powders
- C05G5/12—Granules or flakes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Soil Sciences (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses a preparation method of a non-full water-soluble secondary element solid fertilizer, belonging to the technical field of chemical fertilizers. The method comprises the steps of carrying out acidolysis reaction on dry powdered rock phosphate and nitric acid to generate multi-component acidolysis solution, removing acid insoluble substances in the acidolysis solution, cooling and crystallizing, filtering and separating out crystal calcium nitrate tetrahydrate, heating and melting the calcium nitrate tetrahydrate to obtain molten calcium nitrate tetrahydrate, reacting with ammonium bisulfate solution to generate spherical polycrystalline calcium carbonate, and filtering again to obtain the non-full-water-soluble medium-element solid fertilizer with calcium and magnesium as main components. The fertilizer has comprehensive nutrients and good soil improvement and restoration effects. The medium element fertilizer can effectively reduce the pressure of stacking by-product crystal calcium to the environment in the process of producing the nitrophosphate fertilizer by decomposing phosphorite with nitric acid, and can create hundred million yuan of benefit for society every year.
Description
Technical Field
The invention belongs to the technical field of chemical fertilizers, and particularly relates to a preparation method of a non-full water-soluble secondary element solid fertilizer.
Background
The non-full water-soluble secondary element fertilizer which is prepared by converting calcium nitrate tetrahydrate generated by decomposing phosphorite by nitric acid and takes calcium and magnesium elements as main components is a non-full water-soluble secondary element fertilizer rich in various nutrient elements. The fertilizer has the characteristics of crop supplement, acid and alkali regulation, soil restoration and improvement and the like in agricultural production, can be widely applied to base fertilizer and additional fertilizer of various field crops and economic crops, and has good economic benefit and social benefit.
The medium element (not all water soluble) fertilizer which is formed by converting tetrahydrate calcium nitrate generated by decomposing phosphorite with nitric acid contains medium elements such as calcium, magnesium, sulfur, silicon and the like, and also contains trace elements such as iron, boron, manganese, zinc, molybdenum and the like. After the rapid development of agriculture in China for about forty years, the large-element fertilizer is widely applied to agricultural production, so that the content of trace elements in soil is sharply reduced, and the development of modern agriculture is restricted. Various nutrient elements required by the growth of crops can be well provided by additionally applying the secondary element fertilizer, so that the growth of the crops is promoted.
Disclosure of Invention
Aiming at the problem that the growth of crops is limited due to the lack of trace elements in soil in the current agricultural production, the invention provides a preparation method of a non-full water-soluble medium element fertilizer, which is used for producing and popularizing the medium element fertilizer and promoting the agricultural production.
In order to achieve the purpose, the invention adopts the following technical scheme:
a process for preparing the non-full-water-soluble solid fertilizer containing secondary elements includes acidolysis reaction between dry powdered rock phosphate and nitric acid to obtain multi-component acidolysis liquid, acidolysisRemoving acid insoluble substances in the liquid, cooling and crystallizing, filtering to separate out crystal substance calcium nitrate tetrahydrate, heating and melting the calcium nitrate tetrahydrate to obtain molten calcium nitrate tetrahydrate, reacting with ammonium sulfate solution to generate spherical polycrystalline calcium carbonate, and filtering again to obtain the non-full water-soluble medium element solid fertilizer with calcium and magnesium as main components. The multicomponent acidolysis solution is prepared by decomposing phosphate rock powder with nitric acid, and the acidolysis solution is frozen to produce crystal Ca (NO)3)2·4H2And O, thereby filtering and separating the calcium nitrate tetrahydrate.
Further, the weight ratio of the nitric acid to the powdered rock phosphate is 1.5-3.5; the mass percentage of the nitric acid is 50-60%. If the concentration of the nitric acid is too low, a large amount of water is brought into the multi-component acidolysis solution, the subsequent crystallization process is directly influenced, the crystallization of calcium nitrate in the acidolysis solution is difficult, the crystallization end point temperature is lower, and the difficulty in crystallization can cause the incomplete calcium removal of the acidolysis solution; the low crystallization end point temperature leads to a significant increase in energy consumption for production. If the concentration of the nitric acid is too high, the acidolysis reaction speed is more violent, so that the temperature of the multi-component acidolysis solution is too high and exceeds 80 ℃, a large amount of nitrogen oxides can escape, and even the raw material nitric acid is directly decomposed. The concentration of the nitric acid is moderate, so that the multicomponent acidolysis solution can be controlled to have good crystallization performance, and meanwhile, the temperature of the multicomponent acidolysis solution is maintained in a reasonable range.
Further, the reaction time of the acidolysis reaction is 0.5h to 1.5h, and the acidolysis temperature is 45 ℃ to 70 ℃. In the continuous production process, a large amount of ground phosphate rock and nitric acid continuously enter an acidolysis tank and are subjected to accelerated reaction in a stirring state, if the reaction residence time is short, the thoroughness of the acidolysis reaction is difficult to ensure (the process requirement cannot be met), and if the reaction residence time is too long, a large acidolysis reaction tank is required, so that the aspects of production operation, process control, equipment cost and the like are unreasonable. The acidolysis reaction is controlled to be 0.5 h-1.5 h, which is the summary of production experience of many years, not only can ensure the thoroughness of the acidolysis reaction, but also is convenient for production operation and process control.
Further, the end point temperature of the cooling crystallization is-5 ℃ to-20 ℃; the coolant is ammonia water with mass concentration of 20%. The ammonia water solidifying point is related to the ammonia water concentration, the solidifying point of the ammonia water with the mass concentration of 20 percent is-35 ℃, and the process requirements are completely met. If the concentration of the ammonia water is reduced, the solidification point is increased, and the ammonia water is likely to be solidified under the extreme operation condition so as not to meet the process requirement and even cause production accidents; if the ammonia water concentration increases, the freezing point can be reduced, the requirement of low temperature is met obviously without problems, but the temperature (about 25 ℃) of the ammonia water as a coolant after heat exchange is higher, the vapor pressure of the ammonia water at the temperature can be very high, the difficulty of process operation is increased, and the cooling system becomes more complex.
Further, the ammonium sulfate-ammonium sulfate solution is a mixed solution of an ammonium carbonate solution and an ammonium nitrate solution, wherein the mass concentration of ammonium carbonate in the mixed solution is 25% -40%, and the mass concentration of ammonium nitrate is 25% -40%. The ammonium bromide solution (mixed solution of ammonium carbonate and ammonium nitrate) is prepared in an absorption tower. After the gaseous carbon dioxide and the gaseous ammonia enter the absorption tower, the gaseous carbon dioxide and the gaseous ammonia are absorbed by the absorbent ammonium nitrate solution, so that the ammonium nitrate solution is formed. The reaction of the ammonium nitrate solution with the calcium nitrate melt produces a mixture of calcium carbonate crystals and ammonium nitrate solution, which can be separated by filtration. The ammonium sulfate solution is specially prepared for removing calcium element in the product calcium nitrate in the previous working procedure, and the low concentration of the ammonium sulfate solution is not beneficial to forming calcium carbonate crystals to be separated out, so that the process requirement cannot be met; if the concentration of the ammonium bisulfate solution is too high, the ammonium bisulfate solution is easy to crystallize, and the process operation is difficult.
Further, in the conversion reaction of the tetrahydrate calcium nitrate molten liquid and the ammonium bisulfate solution, the pH value of the reaction liquid is controlled to be 7.2-8.0.
Further, the temperature of the tetrahydrate calcium nitrate molten liquid and the ammonium bisulfate solution for reaction is 50-70 ℃. Calcium nitrate tetrahydrate (Ca (NO)3)2·4H2O) the molten liquid and the ammonium bisulfate solution are subjected to conversion reaction to generate spherical polycrystalline calcium carbonate, and the generated spherical polycrystalline calcium carbonate is a multi-component substance and is derived from a multi-nutrient element component formed by decomposing natural phosphate rock powder by nitric acid.
Further, the carbonization degree of the spherical polycrystalline calcium carbonate is 90-99%.
Further, the particle size of the ground phosphate rock is 0.02 mm-2 mm. The powdered rock phosphate contains a part of acid insoluble substances, if the particle size of the powdered rock phosphate is too large, only a part of mineral powder particles are reacted with nitric acid, and the inside of the particles does not participate in the reaction.
The non-full water-soluble medium element fertilizer is a solid powder finished product or a granular finished product; the total content of calcium, magnesium and silicon elements (Ca + Mg + Si) in the solid powder finished product is not less than 25 percent (mass percentage); the total content of calcium, magnesium and silicon elements (Ca + Mg + Si) in the solid particle finished product is not less than 20%. The solid powder has stable contents of calcium, magnesium and silicon, wherein the content of calcium is more than 25%, the content of magnesium is more than 0.5%, and the content of silicon is more than 3.5%.
Compared with the prior art, the invention has the following advantages:
(1) the non-full water-soluble medium element fertilizer adopts a nitric acid phosphorite decomposition production process, has comprehensive nutrients in the fertilizer, is beneficial to absorption of crops, and has good soil improvement and restoration effects.
(2) The non-full water-soluble secondary element fertilizer can effectively reduce the pressure of stacking by-product crystal calcium to the environment in the process of producing the nitrophosphate fertilizer by decomposing phosphorite with nitric acid, and can create hundred million yuan of benefit for society every year.
(3) The granular fertilizer prepared by adding functional substances into the non-full water-soluble medium element fertilizer is a product which is well-sold in the market at present and is beneficial supplement for scientific fertilization in agricultural production.
Drawings
FIG. 1 is a flow chart of a process for producing a non-full water-soluble secondary element fertilizer by decomposing phosphorite with nitric acid.
Detailed Description
Example 1
The production process of non-full water-soluble medium element fertilizer by the nitric acid decomposition phosphate rock production process shown in figure 1 comprises the main equipment of phosphate rock powder drying equipment, a phosphate rock powder storage hopper, a metering scale, an acidolysis tank, a settling tank, acid insoluble substance separation equipment, a crystallizer feeding tank, a crystallizer, a refrigeration system, a filter feeding tank, a calcium nitrate filtration system, a calcium nitrate melting tank, a conversion tank, an adjusting tank, a calcium carbonate filter, a tail gas absorption tower, a belt conveyor, an absorption tower, a heat exchanger and the like.
Because the phosphorite contains a plurality of elements, the calcium carbonate crystal obtained by further processing after decomposing the phosphorite by nitric acid contains a plurality of elements required by plant growth, and the test and analysis results are as follows (mass percentage): nitrogen (N) 5.4%, phosphorus (P) 0.7%, calcium (Ca) 30.5%, magnesium (Mg) 0.6%, sulfur (S) 0.005%, iron (Fe) 0.08%, manganese (Mn) 0.005%, zinc (Zn) 0.006%, copper (Cu) 0.0007%, molybdenum (Mo) 0.006%, boron (B) 0.003%.
The production method of the non-full water-soluble medium element fertilizer comprises the following steps:
1) the dried phosphate rock powder reaches a phosphate rock storage hopper through a conveying system, and the phosphate rock powder is sampled, tested and analyzed, wherein the phosphate rock powder contains (by mass percent) 50% of CaO, 1% of MgO and Fe2O31% of Al2O3Is 1%. Taking 1t of phosphate rock powder as reference, the CaO content is 0.5t, MgO content is 0.01t, and Fe content is calculated2O30.01t, Al2O3And 0.01t, the dosage of the pure nitric acid for decomposing the phosphorite is as follows:
substituting the analysis calculation data into a calculation formula to obtain the pure nitric acid with the use amount of 1.22t, wherein if the mass concentration of the nitric acid is 50% and the excess of the nitric acid is 10%, the actual use amount of the nitric acid is as follows: 1.22 ÷ 50% × (1+ 10%) -2.68 t. Adding 50% nitric acid and powdered rock phosphate into an acidolysis tank according to the weight ratio of 2.68:1, and reacting for 1 hour under a stirring state to obtain multi-component acidolysis solution.
2) Settling and separating the multi-component acidolysis solution, separating acid insoluble substance, cooling and crystallizing in crystallizerExchanging heat with coolant until the acidolysis solution is cooled to the end temperature of-5 to-20 ℃, and using calcium nitrate tetrahydrate (Ca (NO) in the acidolysis solution3)2·4H2O) crystal form is completely separated out, and then the crystal is filtered to obtain the crystal of calcium nitrate tetrahydrate.
The cooling crystallization process requires a cooling agent: 20% ammonia water, the temperature of the fresh coolant is not higher than-20 ℃, and the temperature of the coolant returned after heat exchange is not higher than 25 ℃.
Heating and melting the obtained calcium nitrate tetrahydrate crystal at 50-70 ℃, then sending the crystal into a transfer tank to perform conversion reaction with an ammonium sulfate solution at 50-70 ℃, controlling the pH of the reaction solution to be 7.2-8.0, generating an ammonium nitrate solution containing spherical polycrystalline calcium carbonate with the carbonization degree of 90-99%, and filtering to obtain a solid crystal, namely the non-full water-soluble medium element fertilizer meeting the requirements. Or further processing the obtained powdery crystal, and adding additives to prepare a granular finished product of the medium element fertilizer.
The ammonium nitrate and ammonium carbonate solution is a mixed solution of ammonium nitrate and ammonium carbonate, and the mass concentration ranges of the ammonium nitrate and the ammonium carbonate are both 25-40%; the preparation method of the ammonium sulfate solution comprises the following steps: after the gaseous carbon dioxide and the gaseous ammonia enter the absorption tower, the gaseous carbon dioxide and the gaseous ammonia are absorbed by the absorbent ammonium nitrate solution to form ammonium sulfate solution.
Example 2
A preparation method of a non-full water-soluble medium element solid fertilizer comprises the steps of carrying out acidolysis reaction on dry phosphate rock powder with the particle size of 0.05mm and nitric acid with the mass percentage of 60% at 70 ℃ for 0.5h to generate multi-component acidolysis solution, removing acid insoluble substances in the acidolysis solution, cooling and crystallizing at-5 ℃, using ammonia water with the mass percentage of 20% as a cooling agent, filtering and separating out crystal calcium nitrate tetrahydrate, heating and melting the calcium nitrate tetrahydrate to obtain molten calcium nitrate tetrahydrate, reacting with ammonium carbonate with the concentration of 35% and ammonium nitrate solution mixed with the concentration of 35% at 70 ℃ to generate spherical polycrystalline calcium carbonate with the carbonization degree of about 99%, and filtering again to obtain the non-full water-soluble medium element solid fertilizer with calcium and magnesium as main components. And the total content of calcium, magnesium and silicon elements (Ca + Mg + Si) in the solid particle finished product is not less than 32 percent.
Example 3
A preparation method of a non-full water-soluble medium element solid fertilizer comprises the steps of carrying out acidolysis reaction on dry phosphate rock powder with the particle size of 0.1mm and 58% by mass of nitric acid at 65 ℃ for 1.0h to generate multi-component acidolysis solution, removing acid insoluble substances in the acidolysis solution, cooling and crystallizing at-10 ℃, using 20% by mass of ammonia water as a coolant, filtering and separating out crystal calcium nitrate tetrahydrate, heating and melting the calcium nitrate tetrahydrate to obtain molten calcium nitrate tetrahydrate, reacting with a diammonium solution formed by mixing 30% ammonium carbonate and 30% ammonium nitrate at 65 ℃ to generate spherical polycrystalline calcium carbonate with the carbonization degree of about 96%, and filtering again to obtain the non-full water-soluble medium element solid powder fertilizer with calcium and magnesium as main components. The total content of calcium, magnesium and silicon elements (Ca + Mg + Si) in the solid powder finished product is not lower than 30 percent;
example 4
A preparation method of a non-full water-soluble medium element solid fertilizer comprises the steps of carrying out acidolysis reaction on dried phosphate rock powder with the particle size of 0.2mm and 55% by mass of nitric acid at 60 ℃ for 1.0h to generate multi-component acidolysis solution, removing acid insoluble substances in the acidolysis solution, cooling and crystallizing at-10 ℃, using 20% by mass of ammonia water as a coolant, filtering and separating out crystal calcium nitrate tetrahydrate, heating and melting the calcium nitrate tetrahydrate to obtain molten calcium nitrate tetrahydrate, reacting with a diammonium solution formed by mixing 30% ammonium carbonate and 30% ammonium nitrate at 60 ℃ to generate spherical polycrystalline calcium carbonate with the carbonization degree of about 96%, and filtering again to obtain the non-full water-soluble medium element solid granular fertilizer with calcium and magnesium as main components. The total content of Ca, Mg and Si elements (Ca + Mg + Si) in the solid particle finished product is not less than 28%.
Example 5
A preparation method of a non-full water-soluble medium element solid fertilizer comprises the steps of carrying out acidolysis reaction on dry phosphate rock powder with the particle size of 0.5mm and 50% by mass of nitric acid at 55 ℃ for 1.5 hours to generate multi-component acidolysis solution, removing acid insoluble substances in the acidolysis solution, cooling and crystallizing at-15 ℃, using 20% by mass of ammonia water as a coolant, filtering and separating out crystal calcium nitrate tetrahydrate, heating and melting the calcium nitrate tetrahydrate to obtain molten calcium nitrate tetrahydrate, reacting with a diammonium solution formed by mixing 25% ammonium carbonate and 25% ammonium nitrate at 50 ℃ to generate spherical polycrystalline calcium carbonate with the carbonization degree of about 90%, and filtering again to obtain the non-full water-soluble medium element solid powder fertilizer with calcium and magnesium as main components. The total content of calcium, magnesium and silicon elements (Ca + Mg + Si) in the solid powder finished product is not lower than 25 percent;
example 6
A preparation method of a non-full water-soluble medium element solid fertilizer comprises the steps of carrying out acidolysis reaction on dry phosphate rock powder with the particle size of 0.02mm and 50% by mass of nitric acid at 45 ℃ for 0.5h to generate multi-component acidolysis solution, removing acid insoluble substances in the acidolysis solution, cooling and crystallizing at-20 ℃, using 20% by mass of ammonia water as a coolant, filtering and separating out crystal calcium nitrate tetrahydrate, heating and melting the calcium nitrate tetrahydrate to obtain molten calcium nitrate tetrahydrate, reacting with ammonium carbonate with the concentration of 40% and ammonium nitrate solution mixed with the concentration of 40% at 70 ℃ to generate spherical polycrystalline calcium carbonate with the carbonization degree of about 95%, and filtering again to obtain the non-full water-soluble medium element solid powder fertilizer with calcium and magnesium as main components. The total content of Ca, Mg and Si elements (Ca + Mg + Si) in the solid powder finished product is not less than 22%.
Experience proves that the moderate element fertilizer can obviously improve soil hardening when being applied to soil with hardening, and the soil hardening can be eliminated after continuous application. The main component of the secondary element fertilizer is calcium carbonate (pH value is neutral or slightly alkaline), and the pH value of normal rainwater is 5.6, after the fertilizer is applied, the calcium carbonate and the rainwater can slowly react to release CO2Not only can loosen the soil and release CO2Is also the main raw material for crop photosynthesis.
At present, medium element fertilizers (by-product calcium carbonate powder for producing nitrophosphate fertilizers) stacked in a certain company site exceed 100 ten thousand tons, occupy 500 mu of land, and partially dissolve and diffuse with rainwater in rainy days to cause certain environmental pollution. If the calcium carbonate powder is directly changed into the medium element fertilizer, the calcium carbonate powder can be directly changed into a product for sale, the calcium carbonate powder in the device design productivity is 800 t/day, the calcium carbonate powder is calculated according to 300 days per year, the calcium carbonate powder is 240 ten thousand t per year, the profit can break through one hundred million yuan after the medium element fertilizer is prepared, and meanwhile, the pollution to the environment caused by the accumulation of a large amount of calcium carbonate powder is avoided.
Those skilled in the art will appreciate that the invention may be practiced without these specific details. Although illustrative embodiments of the present invention have been described above to facilitate the understanding of the present invention by those skilled in the art, it should be understood that the present invention is not limited to the scope of the embodiments, and various changes may be made apparent to those skilled in the art as long as they are within the spirit and scope of the present invention as defined and defined by the appended claims, and all matters of the invention which utilize the inventive concepts are protected.
Claims (10)
1. A preparation method of a non-full water-soluble secondary element solid fertilizer is characterized by comprising the following steps: carrying out acidolysis reaction on dried phosphate rock powder and nitric acid to generate multi-component acidolysis solution, removing acid insoluble substances in the acidolysis solution, cooling and crystallizing, filtering to separate out crystal calcium nitrate tetrahydrate, heating and melting the calcium nitrate tetrahydrate to obtain molten calcium nitrate tetrahydrate, reacting with ammonium bisulfate solution to generate spherical polycrystalline calcium carbonate, and filtering again to obtain the non-full-water-soluble medium element solid fertilizer.
2. The method for preparing a non-fully water-soluble medium element solid fertilizer according to claim 1, wherein the method comprises the following steps: the weight ratio of the nitric acid to the phosphorite powder is 1.5-3.5; the mass percentage of the nitric acid is 50-60%.
3. The method for preparing a non-fully water-soluble medium element solid fertilizer according to claim 1, wherein the method comprises the following steps: the reaction time of the acidolysis reaction is 0.5h to 1.5h, and the acidolysis temperature is 45 ℃ to 70 ℃.
4. The method of claim 1 for preparing a non-fully water-soluble medium element fertilizer, wherein the method comprises the steps of: the final temperature of the cooling crystallization is-5 ℃ to-20 ℃; the coolant is 20% ammonia water solution by mass percent.
5. The method for preparing a non-fully water-soluble medium element solid fertilizer according to claim 1, wherein the method comprises the following steps: the ammonium nitrate-ammonium sulfate solution is a mixed solution of an ammonium carbonate solution and an ammonium nitrate solution, wherein the mass concentration of ammonium carbonate in the mixed solution is 25% -40%, and the mass concentration of ammonium nitrate is 25% -40%.
6. The method for preparing a non-fully water-soluble medium element solid fertilizer according to claim 1, wherein the method comprises the following steps: in the conversion reaction of the calcium nitrate tetrahydrate molten liquid and the ammonium bisulfate solution, the pH value of the reaction liquid is controlled to be 7.2-8.0.
7. The method for preparing a non-fully water-soluble medium element solid fertilizer according to claim 1, wherein the method comprises the following steps: the reaction temperature of the tetrahydrate calcium nitrate molten liquid and the ammonium bisulfate solution is 50-70 ℃.
8. The method for preparing a non-fully water-soluble medium element solid fertilizer according to claim 1, wherein the method comprises the following steps: the carbonization degree of the spherical polycrystalline calcium carbonate is 90-99%.
9. The method for preparing a non-fully water-soluble medium element solid fertilizer according to claim 1, wherein the method comprises the following steps: the particle size of the phosphate rock powder is 0.02 mm-2 mm.
10. A non-fully water-soluble medium element solid fertilizer prepared by the preparation method of claim 1, wherein: the non-full water-soluble medium element fertilizer is a solid powder finished product or a granular finished product; the total content of calcium, magnesium and silicon elements in the solid powder finished product is not lower than 25%; the total content of calcium, magnesium and silicon elements in the solid particle finished product is not less than 20%.
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CN101486595A (en) * | 2009-02-25 | 2009-07-22 | 天脊煤化工集团股份有限公司 | Technological process for producing high concentration nitric-phosphate fertilizer |
CN104119194A (en) * | 2014-08-12 | 2014-10-29 | 许盛英 | Production method of calcium carbonate residue compressed nutritional soil |
CN108834828A (en) * | 2018-08-13 | 2018-11-20 | *** | The preparation method of multifunctional calcium carbonate slag desert storage water suction nutrient bag |
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