CN114560744B - Method for preparing multi-form phosphorus compound fertilizer - Google Patents
Method for preparing multi-form phosphorus compound fertilizer Download PDFInfo
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- CN114560744B CN114560744B CN202210248473.8A CN202210248473A CN114560744B CN 114560744 B CN114560744 B CN 114560744B CN 202210248473 A CN202210248473 A CN 202210248473A CN 114560744 B CN114560744 B CN 114560744B
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- phosphoric acid
- compound fertilizer
- mixing
- ammonium
- potassium
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- 239000003337 fertilizer Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000011574 phosphorus Substances 0.000 title claims abstract description 33
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 33
- -1 phosphorus compound Chemical class 0.000 title claims abstract description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 120
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 58
- 239000000463 material Substances 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 33
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004114 Ammonium polyphosphate Substances 0.000 claims abstract description 22
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims abstract description 22
- 229920001276 ammonium polyphosphate Polymers 0.000 claims abstract description 22
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 235000019828 potassium polyphosphate Nutrition 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 9
- OQZCJRJRGMMSGK-UHFFFAOYSA-M potassium metaphosphate Chemical compound [K+].[O-]P(=O)=O OQZCJRJRGMMSGK-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- 239000011268 mixed slurry Substances 0.000 claims description 16
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 14
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 239000011573 trace mineral Substances 0.000 claims description 11
- 235000013619 trace mineral Nutrition 0.000 claims description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 5
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 5
- 235000011151 potassium sulphates Nutrition 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- VGHYETQUYZQODY-UHFFFAOYSA-N aluminum magnesium iron(2+) oxygen(2-) Chemical compound [O-2].[Al+3].[Fe+2].[Mg+2] VGHYETQUYZQODY-UHFFFAOYSA-N 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- FQLQNUZHYYPPBT-UHFFFAOYSA-N potassium;azane Chemical compound N.[K+] FQLQNUZHYYPPBT-UHFFFAOYSA-N 0.000 claims description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 18
- 239000002994 raw material Substances 0.000 abstract description 14
- 239000004254 Ammonium phosphate Substances 0.000 abstract description 6
- 229910000148 ammonium phosphate Inorganic materials 0.000 abstract description 6
- 235000019289 ammonium phosphates Nutrition 0.000 abstract description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 239000005819 Potassium phosphonate Substances 0.000 abstract description 4
- PYCBFXMWPVRTCC-UHFFFAOYSA-N ammonium metaphosphate Chemical compound N.OP(=O)=O PYCBFXMWPVRTCC-UHFFFAOYSA-N 0.000 abstract description 4
- YXXXKCDYKKSZHL-UHFFFAOYSA-M dipotassium;dioxido(oxo)phosphanium Chemical compound [K+].[K+].[O-][P+]([O-])=O YXXXKCDYKKSZHL-UHFFFAOYSA-M 0.000 abstract description 4
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 abstract description 4
- 239000002002 slurry Substances 0.000 abstract description 4
- JDRJCBXXDRYVJC-UHFFFAOYSA-N OP(O)O.N.N.N Chemical compound OP(O)O.N.N.N JDRJCBXXDRYVJC-UHFFFAOYSA-N 0.000 abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 2
- 239000011230 binding agent Substances 0.000 abstract description 2
- 229920002842 oligophosphate Polymers 0.000 abstract description 2
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Polymers OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 abstract description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 46
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 7
- 125000005341 metaphosphate group Chemical group 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 229920000388 Polyphosphate Polymers 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000001205 polyphosphate Substances 0.000 description 5
- 235000011176 polyphosphates Nutrition 0.000 description 5
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 description 4
- 239000006012 monoammonium phosphate Substances 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 235000011180 diphosphates Nutrition 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000000618 nitrogen fertilizer Substances 0.000 description 3
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 3
- 229920000137 polyphosphoric acid Polymers 0.000 description 3
- 229940072033 potash Drugs 0.000 description 3
- 235000015320 potassium carbonate Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000004176 ammonification Methods 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 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 2
- 244000052769 pathogen Species 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 2
- 229910001950 potassium oxide Inorganic materials 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- FPWJLQXCGHQXLL-UHFFFAOYSA-N [P].OP(O)(O)=O Chemical compound [P].OP(O)(O)=O FPWJLQXCGHQXLL-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000021049 nutrient content Nutrition 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/40—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting fertiliser dosage or release rate; for affecting solubility
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
-
- 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
- C05G3/60—Biocides or preservatives, e.g. disinfectants, pesticides or herbicides; Pest repellants or attractants
-
- 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
Abstract
The application discloses a method for preparing a multi-form phosphorus compound fertilizer, and relates to the technical field of phosphorus compound fertilizer production. The method comprises the steps of taking low-grade phosphoric acid and wet-process phosphoric acid as raw materials, adopting a sectional manufacturing process, firstly utilizing the low-grade phosphoric acid or the wet-process phosphoric acid to combine a catalyst, ammonia gas and potassium salt in a mixing reactor to prepare an intermediate material with relatively high polymerization degree, and taking the intermediate material as a return material of a granulator; the mixed phosphoric acid is used as raw materials in a tubular reactor, sulfuric acid, ammonia gas, a catalyst and washing water are combined to prepare ammonium phosphate slurry with a certain polymerization degree, the ammonium phosphate slurry is used as a granulating binder to be sprayed on a returned material to prepare a compound fertilizer product containing ammonium polyphosphate, ammonium metaphosphate, ammonium phosphite, potassium phosphite and potassium polyphosphate, the problem that the polymerization degree of the product is influenced by the quality of the raw materials is effectively avoided, and compared with the existing two processes of directly adding a water-soluble ammonium polyphosphate finished product or preparing ammonium oligophosphate with high-quality phosphoric acid in the tubular reactor, the process has obvious advantages in cost.
Description
Technical Field
The application relates to the technical field of phosphorus compound fertilizer production, in particular to a method for preparing a multi-form phosphorus compound fertilizer.
Background
The major elements in the fertilizer demand of most crops are mainly nitrogen, phosphorus and potassium, wherein the phosphorus is most varied in form, such as metaphosphate, polyphosphate and orthophosphateAnd phosphite radicals. Wherein the polyphosphate is most commonly used as ammonium polyphosphate and contains a large amount of nitrogen and phosphorus, and has a chemical molecular formula of (NH) 4 ) n+2 P n O 3n+1 The method can be divided into 3 types of oligomerization, medium polymerization and high polymerization, and when n is less than 20, the method is water-soluble ammonium polyphosphate. The oligomeric ammonium phosphate has the characteristics of high solubility, nearly neutral pH value, lower crystallization temperature, chelating effect on metal ions, slow release, long acting and the like. The potassium phosphite in the phosphite can not only meet the requirement of crops on potassium, but also directly attack pathogens and induce the crops to produce plant protection elements which are substances toxic to the pathogens, thus being a high-potassium phosphate fertilizer and a systemic bactericide. Ammonium metaphosphate among metaphosphates is used less and less at present, but the high nitrogen and phosphorus content and the slow release property of the metaphosphate are also important in the compound fertilizer. In the preparation of the existing phosphorus compound fertilizer, the phosphorus form in the finished product is one or two of the above, and phosphoric acid with higher quality or concentration is generally adopted in the raw material selection, so that the problems of high production cost, high energy consumption and easy equipment corrosion are caused.
CN112979386a discloses a low polymerization degree ammonium polyphosphate particle multielement compound fertilizer and a preparation method thereof, wherein the compound fertilizer is prepared from the following raw materials in percentage by mass: solid raw materials: acidic ammonium polyphosphate viscous solution: the mass ratio of the ammoniating agent is 4.0-8.0:1.0:0.05-1.0. The preparation method of the low-polymerization-degree ammonium polyphosphate particle multielement compound fertilizer comprises a drum gas ammonia ammonification granulation method under the working condition of an ammonia station and a drum ammonium bicarbonate ammonification granulation method under the working condition of an ammonia-free station. The method has the problems of high raw material consumption, high energy consumption, equipment corrosion, easy agglomeration in the granulating process, uneven dispersion and the like of the synthesized acidic ammonium polyphosphate.
CN102718588A describes the reaction of phosphoric acid (P 2 O 5 The content is 47% -54%), sulfuric acid, ammonia and washing water are introduced into a pipeline reactor according to a certain mass ratio, the reaction temperature of phosphoric acid, sulfuric acid and ammonia is 200-300 ℃ to generate mixed slurry containing ammonium sulfate and ammonium polyphosphate with polymerization degree not more than 10, and water in the raw materials is evaporated into steam by reaction heat; the mixed slurry is fed into a rotary drum granulator, and the potash fertilizer, the nitrogenous fertilizer and the trace elements are respectively fed into a potash fertilizer feeder,The nitrogenous fertilizer feeder and the trace element feeder enter a lifting machine, and then are introduced into a rotary drum granulator to be mixed with the mixed slurry for granulation, so that a compound fertilizer is obtained; and (3) introducing the compound fertilizer particles into a cooling cylinder for cooling, sieving by a sieve, and finally performing powder extinguishing and oil spraying wrapping on the qualified compound fertilizer particles to obtain the compound fertilizer. The method has the problems of high quality requirement of raw material phosphoric acid, high energy consumption, easy corrosion of equipment and the like.
CN105272477a describes a water-soluble ammonium polyphosphate NPK compound fertilizer and a preparation method thereof, the water-soluble ammonium polyphosphate NPK compound fertilizer comprises monoammonium phosphate, potassium sulfate or potassium chloride and a low-melting mixture, wherein the low-melting mixture comprises urea and an additive, and the mass ratio of the urea to the monoammonium phosphate to the potassium sulfate or the potassium chloride is (1.0-7.0): 1.0: (1.0-2.0). The preparation method of the water-soluble ammonium polyphosphate NPK compound fertilizer comprises the following steps: providing urea and an additive to form a low-melting mixture, and carrying out melting treatment on the low-melting mixture to obtain a first melt; adding a blend formed by monoammonium phosphate, potassium sulfate or potassium chloride into the first melt for heating reaction; granulating. The application solves the problems of serious ammonia damage, environmental pollution, poor bubble control effect and rapid attenuation of the polymerization rate of the product caused by low pH value in the existing method for synthesizing ammonium polyphosphate. The method has the problems of high raw material quality requirement, high equipment corrosion resistance requirement and the like.
Disclosure of Invention
The application aims to provide a method for preparing a multi-form phosphorus compound fertilizer, which solves the problems of single phosphorus form, high requirement on the quality of raw material phosphoric acid, easy corrosion of equipment and high cost in the preparation process of the existing phosphorus compound fertilizer.
In order to solve the technical problems, the application adopts the following technical scheme: the method for preparing the multi-form phosphorus compound fertilizer is characterized by comprising the following steps:
s1, mixing wet phosphoric acid or low-grade phosphoric acid and a catalyst according to a proportion of 1: mixing 1-2 proportion, adding into a mixing reactor, mixing with at least one of ammonia gas, potassium salt and microelements, controlling the reaction temperature to be 150-200 ℃, and generating a mixture a of ammonium sulfate, ammonium polyphosphate containing microelements with the polymerization degree not more than 5 and potassium polyphosphate;
s2, introducing mixed phosphoric acid, sulfuric acid, ammonia gas, a catalyst and washing water into a tubular reactor, generating mixed slurry b containing one or more materials of metaphosphate, pyrophosphates, phosphites and polyphosphates, sulfate and orthophosphate at the reaction temperature of 120-250 ℃, and introducing into a granulator;
s3, adding the mixture a in the step S1 into a granulator as return materials, controlling the temperature to be 70-150 ℃, spraying the mixed slurry b in the step S2 into the return materials of the granulator, wherein the ratio of the mixture a to the mixed slurry b is 4-10: 1, preparing the granular compound fertilizer containing one or more forms of phosphorus, nitrogen, potassium and trace elements in metaphosphate, pyrophosphates, phosphites, polyphosphates and orthophosphates.
The further technical proposal is that the mass concentration of the wet phosphoric acid in the step S1 is 38 to 46 percent based on phosphorus pentoxide, wherein the content of iron, magnesium and aluminum oxides is 1 to 5 percent; the mass concentration of the low-grade phosphoric acid is 35-45% based on phosphorus pentoxide, wherein the content of iron, magnesium and aluminum oxides is 5-15%.
The further technical proposal is that the low-grade phosphoric acid is one or two of slag acid which is a byproduct of wet-process phosphoric acid and raffinate acid which is a byproduct of wet-process purified phosphoric acid.
The further technical scheme is that the mixed phosphoric acid in the step S2 is a mixture obtained by one or more compositions of 70-90% of wet-process phosphoric acid, 1-5% of metaphosphoric acid, 1-10% of phosphorous acid, 1-20% of polyphosphoric acid and 1-5% of phosphorus pentoxide.
A further technical scheme is that the potassium salt in the step S1 is one or a mixture of more of potassium sulfate, potassium carbonate, potassium chloride, potassium nitrate and potassium oxide.
The catalyst is one or a mixture of urea, hydrogen peroxide, melamine and monoammonium phosphate, and preferably urea and hydrogen peroxide are used for preparing the catalyst in a ratio of 3: 1.
The further technical proposal is that the microelements in the step S1 are one or more of copper, manganese, zinc, boron and molybdenum, and the content is 0.005-0.5 percent.
The further technical proposal is that the mixed phosphoric acid in the step S2 is preheated to 50-150 ℃ before entering the tubular reactor.
The further technical proposal is that the grain size of the granular compound fertilizer is 0.5-4.75 mm.
Compared with the prior art, the application has the beneficial effects that: the method for preparing the multi-form phosphorus compound fertilizer is characterized in that low-grade phosphoric acid and wet-process phosphoric acid are used as raw materials, a sectional manufacturing process is adopted, and the low-grade phosphoric acid or the wet-process phosphoric acid is combined with a catalyst, ammonia gas and potassium salt in a mixing reactor to prepare a mixture of ammonium phosphate, ammonium potassium polyphosphate and polyphosphoric acid trace element salt with relative polymerization degree within 5, and the mixture is used as a return material of a granulator; the method is characterized in that mixed phosphoric acid is used as a raw material in a tubular reactor, phosphoric acid, ammonia gas, a catalyst and washing water are combined to prepare ammonium phosphate slurry with various phosphorus forms, and the ammonium phosphate slurry is simultaneously used as a granulating binder to be sprayed on a returned material to prepare the granular compound fertilizer containing one or more forms of phosphorus in metaphosphate, pyrophosphates, phosphites, polyphosphates and orthophosphates, nitrogen, potassium and trace elements, so that the problem that the polymerization degree of the product is influenced by the quality of the raw material is effectively avoided, and compared with the existing two processes of directly adding a water-soluble ammonium polyphosphate finished product or preparing ammonium oligophosphate with high-quality phosphoric acid in the tubular reactor, the method has obvious advantages in terms of process and cost.
The compound fertilizer prepared by the application can simultaneously contain one or more of orthophosphoric acid heel, ammonium polyphosphate, ammonium metaphosphate, ammonium phosphite, potassium phosphite and potassium polyphosphate and trace elements, the orthophosphoric acid root provides water-soluble quick-acting phosphorus nutrient, the ammonium polyphosphate can chelate trace elements such as copper, manganese, zinc, molybdenum and the like to generate completely water-soluble substances, the ammonium metaphosphate improves higher nutrient content and slow release property, the ammonium phosphite, the potassium phosphite and the like provide antibacterial function, and the compound fertilizer can simultaneously supplement high-nutrient nitrogen fertilizer, phosphate fertilizer, potash fertilizer and trace elements for plants. In addition, the low-grade phosphoric acid has high iron and magnesium content, and can supplement trace elements in the product compound fertilizer.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application will be described in further detail with reference to the following examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
Example 1
The method for preparing the multi-form phosphorus compound fertilizer comprises the following steps of: 2:1:1:0.1, adding the mixture into a mixing reactor, wherein the low-grade phosphoric acid is raffinate acid with the concentration of phosphorus pentoxide of 35% and the iron-magnesium-aluminum oxide of 5% of the total mass fraction of the phosphoric acid; the catalyst is urea, hydrogen peroxide and melamine in a proportion of 3:1:1, mixing; the molar ratio of the microelements is 1:1, and the addition amount of the zinc and the copper is 0.5 percent of the total weight. Controlling the reaction temperature to be 150 ℃ and reacting for 70 minutes to generate microelement-containing ammonium polyphosphate, ammonium potassium polyphosphate and potassium polyphosphate materials with the polymerization degree of 3-4, and drying and crushing the materials to obtain the pelleting and returning materials for producing the multi-form phosphorus compound fertilizer. Mixing phosphoric acid, a catalyst, washing water and sulfuric acid according to a mole ratio of 9:1:0.5:0.1, and preheating to 50 ℃ and adding into a mixer, wherein the mixed phosphoric acid is wet-process phosphoric acid with 46% of phosphorus pentoxide concentration (iron, magnesium and aluminum oxides are 1% of the total mass fraction of the phosphoric acid) and phosphorous acid according to the mass ratio of 9:1, and mixing. After the reaction materials in the mixer are uniformly mixed, the mixture is conveyed into a tubular reactor, proper ammonia gas is introduced to ensure that the neutralization degree is 1.70-1.85, and the reaction temperature of the tubular reactor is controlled to be 250 ℃ to generate mixed slurry with the polymerization degree of 1-2.
Granulating and returning materials and mixed slurry in a granulator according to the weight ratio of 4:1, mixing and granulating, controlling the temperature to 70-150 ℃ and preparing the polymorphic phosphorus compound fertilizer with the particle size of 0.5-2 mm. The analysis result of the product is as follows: n% = 12.21%, P 2 O 5 ％＝40.12％，K 2 O% = 10%, mgo=0.61%, fe% = 0.52%, S% = 0.32%, te (zn+cu) = 0.5%, wherein P is contained 3 O 6 Percent=1.27%, containP 4 O 6 ％＝0.54，H 3 PO 3 ％＝0.46％。
Example 2
A method for preparing a multi-form phosphorus compound fertilizer comprises the following steps of: 4:1:1:0.1, adding the mixture into a mixing reactor, wherein the concentration of phosphorus pentoxide in the wet-process phosphoric acid is 46%, and the iron, magnesium and aluminum oxides are 1% of the total mass fraction of the phosphoric acid; the catalyst is urea; the molar ratio of the microelements is 1:1:1, and the addition amount of the zinc, the boron and the molybdenum is 0.5 percent of the total weight. Controlling the reaction temperature to be 200 ℃, reacting for 70 minutes to generate microelement-containing ammonium polyphosphate and potassium polyphosphate materials with the polymerization degree of 3-4, and drying and crushing the materials to obtain the pelleting and returning materials for producing the multi-form phosphorus compound fertilizer. Mixing phosphoric acid, a catalyst, washing water and sulfuric acid according to a mole ratio of 9:1:0.5:0.1, wherein the mixed phosphoric acid is wet phosphoric acid with a phosphorus pentoxide concentration of 38% (the iron, magnesium and aluminum oxides are 5% of the total mass fraction of the phosphoric acid) and polyphosphoric acid and metaphosphoric acid in a mass ratio of 70:10:1, and mixing. After the reaction materials in the mixer are uniformly mixed, the mixture is conveyed into a tubular reactor, proper ammonia gas is introduced to ensure that the neutralization degree is 1.70-1.85, and the reaction temperature of the tubular reactor is controlled to be 150 ℃ to generate mixed slurry with the polymerization degree of 1-2.
Granulating and returning materials and mixed slurry in a granulator according to the weight ratio of 6:1, mixing and granulating, controlling the temperature to be 70-150 ℃ and preparing the polymorphic phosphorus compound fertilizer with the particle size of 2-4.75 mm. The analysis result of the product is as follows: n% = 12.23%, P 2 O 5 ％＝41.33％，K 2 O% = 11.12%, mgo=0.42%, fe% = 0.49%, S% = 0.28%, te (zn+b+mu) = 0.56%, wherein P is contained 3 O 6 Percent=4.27% containing P 4 O 6 ％＝2.34，PO 3 ％＝0.32％。
Example 3
The method for preparing the multi-form phosphorus compound fertilizer comprises the following steps of: 3:1:1:0.1, adding the mixture into a high-strength mixing reactor, wherein the low product is slag acid with the phosphorus pentoxide concentration of 45% and the total mass fraction of the iron-magnesium-aluminum oxide of 8%; the catalyst is urea and hydrogen peroxide in a proportion of 3:1, mixing; the microelements are boron and manganese 1:1, and the addition amount is 0.5 percent of the total weight. Controlling the reaction temperature to be 200 ℃, reacting for 70 minutes to generate microelement-containing ammonium polyphosphate and potassium polyphosphate materials with the polymerization degree of 3-4, and drying and crushing the materials to obtain the pelleting and returning materials for producing the multi-form phosphorus compound fertilizer. Mixing phosphoric acid, a catalyst, washing water and sulfuric acid according to a mole ratio of 9:1:0.5:0.1, wherein the mixed phosphoric acid is wet phosphoric acid with 46% phosphorus pentoxide concentration (iron, magnesium, aluminum oxide is 2% of the total mass fraction of phosphoric acid) and metaphosphoric acid in a mass ratio of 95:5, mixing. After the reaction materials in the mixer are uniformly mixed, the mixture is conveyed into a tubular reactor, proper ammonia gas is introduced to ensure that the neutralization degree is 1.70-1.85, and the reaction temperature of the tubular reactor is controlled to be 250 ℃ to generate mixed slurry with the polymerization degree of 1-2.
Granulating and returning materials and mixed slurry in a granulator according to the weight ratio of 10:1, mixing and granulating, controlling the temperature to be 70-150 ℃ and preparing the polymorphic phosphorus compound fertilizer with the particle size of 2-4.75 mm. The analysis result of the product is as follows: n% = 13.21%, P 2 O 5 ％＝40.44％，K 2 O% =10.53%, mgo=0.51%, fe% =0.32%, S% =0.33%, te (b+mn) =0.54%, wherein P is contained 3 O 6 Percent=5.12% containing P 4 O 6 ％＝3.22，PO 3 ％＝0.41％。
Example 4
The method for preparing the multi-form phosphorus compound fertilizer comprises the following steps of: 3:1:1:0.1, adding the mixture into a high-strength mixing reactor, wherein the concentration of low-grade phosphoric acid phosphorus pentoxide is 40%, and the total mass fraction of iron, magnesium and aluminum oxides is 15%; the catalyst is urea and hydrogen peroxide in a proportion of 3:1, mixing; potassium salts are potassium carbonate and potassium oxide 1: 1; the trace element is zinc, and the addition amount is 0.5 percent of the total weight. Controlling the reaction temperature to be 200 ℃, reacting for 70 minutes to generate microelement-containing ammonium polyphosphate and potassium polyphosphate materials with the polymerization degree of 3-4, and drying and crushing the materials to obtain the pelleting and returning materials for producing the multi-form phosphorus compound fertilizer. Mixing phosphoric acid, a catalyst, washing water and sulfuric acid according to a mole ratio of 9:1:0.5:0.1, wherein the mixed phosphoric acid is wet phosphoric acid with 46 percent of phosphorus pentoxide concentration (iron, magnesium and aluminum oxides are 2 percent of the total mass fraction of phosphoric acid), metaphosphoric acid and phosphorus pentoxide in a mass ratio of 90:5:5, mixing. After the reaction materials in the mixer are uniformly mixed, the mixture is conveyed into a tubular reactor, proper ammonia gas is introduced to ensure that the neutralization degree is 1.70-1.85, and the reaction temperature of the tubular reactor is controlled to be 250 ℃ to generate mixed slurry with the polymerization degree of 1-2.
Granulating and returning materials and mixed slurry in a granulator according to the weight ratio of 8:1, mixing and granulating, controlling the temperature to be 70-150 ℃ and preparing the polymorphic phosphorus compound fertilizer with the particle size of 2-4.75 mm. The analysis result of the product is as follows: n% = 14.21%, P 2 O 5 ％＝44.44％，K 2 O% = 10.33%, mgO = 0.42%, fe% = 0.28%, S% = 0.35%, zn = 0.61%, where P is contained 3 O 6 Percent=6.12% containing P 4 O 6 ％＝7.22。
While the application has been described herein with reference to a number of illustrative embodiments thereof, it should be understood that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the scope of the disclosure. More specifically, various modifications and improvements may be made to the component parts or arrangements within the scope of the disclosure and claims. In addition to variations and modifications in the component parts or arrangements, other uses will be apparent to those skilled in the art.
Claims (1)
1. The method for preparing the multi-form phosphorus compound fertilizer is characterized by comprising the following steps:
s1, low-grade phosphoric acid, a catalyst, potassium sulfate, ammonia gas and trace elements according to the molar ratio of 2:2:1:1:0.1, adding the mixture into a mixing reactor, wherein the low-grade phosphoric acid is raffinate acid with the concentration of phosphorus pentoxide of 35% and the iron-magnesium-aluminum oxide of 5% of the total mass fraction of the phosphoric acid; the catalyst is urea, hydrogen peroxide and melamine in a proportion of 3:1: 1. mixing; the molar ratio of the microelements is 1: 1. mixing zinc and copper, controlling the addition amount to be 0.5 percent of the total weight, controlling the reaction temperature to be 150 ℃, reacting for 70 minutes to generate microelement-containing ammonium polyphosphate, ammonium potassium polyphosphate and potassium polyphosphate materials with the polymerization degree of 3-4, and drying and crushing the materials to be used as granulating and returning materials for producing the multi-form phosphorus compound fertilizer;
s2, mixing phosphoric acid, a catalyst, washing water and sulfuric acid according to the molar ratio of 9:1:0.5:0.1, preheating to 50 ℃ and adding into a mixer, wherein the mixed phosphoric acid is wet-process phosphoric acid with the phosphorus pentoxide concentration of 46% and phosphorous acid according to the mass ratio of 9:1, mixing to obtain the 46% wet-process phosphoric acid, wherein the iron, magnesium and aluminum oxides account for 1% of the total mass fraction of the phosphoric acid, uniformly mixing the reaction materials in a mixer, conveying the mixture into a tubular reactor, introducing ammonia gas to ensure that the neutralization degree is 1.70-1.85, controlling the reaction temperature of the tubular reactor to be 250 ℃, and generating mixed slurry with the polymerization degree of 1-2;
s3, in a granulator, mixing the granulating and returning charge with the mixed slurry according to a weight ratio of 4: 1. mixing and granulating, controlling the temperature to be 70-150 ℃ and preparing the polymorphic phosphorus compound fertilizer with the particle size of 0.5-2 mm.
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| GB1083916A (en) * | 1964-03-30 | 1967-09-20 | Armour & Co | Improvements in or relating to ammonium phosphate and the production thereof |
| GB1226256A (en) * | 1968-05-15 | 1971-03-24 | ||
| CN102718588A (en) * | 2012-05-31 | 2012-10-10 | 深圳市芭田生态工程股份有限公司 | Compound fertilizer produced by tubular reaction and method for preparing compound fertilizer |
| CN104355734A (en) * | 2014-10-24 | 2015-02-18 | 瓮福（集团）有限责任公司 | Production method of ammonium sulfate-ammonium phosphate composite fertilizer |
| CN106865517A (en) * | 2017-03-31 | 2017-06-20 | 三峡大学 | A kind of method and device that water-soluble poly ammonium phosphate is prepared by phosphoric acid by wet process |
| CN109704818A (en) * | 2017-10-25 | 2019-05-03 | 四川大学 | DAP compound fertilizer and preparation method thereof |
| CN112341251A (en) * | 2020-11-10 | 2021-02-09 | 云南云天化股份有限公司 | Method for preparing ammonium phosphate containing polymeric phosphorus by using wet-process phosphoric acid |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| GB1083916A (en) * | 1964-03-30 | 1967-09-20 | Armour & Co | Improvements in or relating to ammonium phosphate and the production thereof |
| GB1226256A (en) * | 1968-05-15 | 1971-03-24 | ||
| CN102718588A (en) * | 2012-05-31 | 2012-10-10 | 深圳市芭田生态工程股份有限公司 | Compound fertilizer produced by tubular reaction and method for preparing compound fertilizer |
| CN104355734A (en) * | 2014-10-24 | 2015-02-18 | 瓮福（集团）有限责任公司 | Production method of ammonium sulfate-ammonium phosphate composite fertilizer |
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