CN111689805A - 一种复合肥的生产方法 - Google Patents
一种复合肥的生产方法 Download PDFInfo
- Publication number
- CN111689805A CN111689805A CN202010580423.0A CN202010580423A CN111689805A CN 111689805 A CN111689805 A CN 111689805A CN 202010580423 A CN202010580423 A CN 202010580423A CN 111689805 A CN111689805 A CN 111689805A
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- China
- Prior art keywords
- compound fertilizer
- fertilizer
- acid
- potassium
- wet
- Prior art date
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- 239000003337 fertilizer Substances 0.000 title claims abstract description 114
- 150000001875 compounds Chemical class 0.000 title claims abstract description 74
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 98
- 238000000034 method Methods 0.000 claims abstract description 69
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 48
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 43
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000011591 potassium Substances 0.000 claims abstract description 42
- 239000011573 trace mineral Substances 0.000 claims abstract description 29
- 235000013619 trace mineral Nutrition 0.000 claims abstract description 29
- 238000005469 granulation Methods 0.000 claims abstract description 19
- 230000003179 granulation Effects 0.000 claims abstract description 19
- 230000008636 plant growth process Effects 0.000 claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011575 calcium Substances 0.000 claims abstract description 5
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 239000011777 magnesium Substances 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims 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 description 37
- 239000002738 chelating agent Substances 0.000 claims description 19
- 239000004254 Ammonium phosphate Substances 0.000 claims description 18
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 18
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 18
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 12
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 238000006386 neutralization reaction Methods 0.000 claims description 11
- 230000009920 chelation Effects 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- 239000000618 nitrogen fertilizer Substances 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000001103 potassium chloride Substances 0.000 claims description 6
- 235000011164 potassium chloride Nutrition 0.000 claims description 6
- 239000004323 potassium nitrate Substances 0.000 claims description 6
- 235000010333 potassium nitrate Nutrition 0.000 claims description 6
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 4
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 4
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 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 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 3
- 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 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 3
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 3
- 229940072033 potash Drugs 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 235000015320 potassium carbonate Nutrition 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 22
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 21
- 239000011574 phosphorus Substances 0.000 abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 11
- 239000012535 impurity Substances 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 6
- 239000002609 medium Substances 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 235000011007 phosphoric acid Nutrition 0.000 abstract 2
- 150000003016 phosphoric acids Chemical class 0.000 abstract 1
- 229960003975 potassium Drugs 0.000 description 40
- 235000007686 potassium Nutrition 0.000 description 40
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 26
- 239000011734 sodium Substances 0.000 description 26
- 229910052708 sodium Inorganic materials 0.000 description 26
- 235000015424 sodium Nutrition 0.000 description 26
- 239000000047 product Substances 0.000 description 25
- 150000003863 ammonium salts Chemical class 0.000 description 24
- 239000002002 slurry Substances 0.000 description 22
- 239000000203 mixture Substances 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 235000015165 citric acid Nutrition 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- -1 dimethylene triaminepentaacetic acid Chemical compound 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 6
- 229960001484 edetic acid Drugs 0.000 description 6
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 3
- 229940005740 hexametaphosphate Drugs 0.000 description 3
- 229960003330 pentetic acid Drugs 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- ZMJBYMUCKBYSCP-UHFFFAOYSA-N (+)-Erythro-hydroxycitric acid Natural products OC(=O)C(O)C(O)(C(O)=O)CC(O)=O ZMJBYMUCKBYSCP-UHFFFAOYSA-N 0.000 description 2
- XNCSCQSQSGDGES-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)C(C)CN(CC(O)=O)CC(O)=O XNCSCQSQSGDGES-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
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- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- SVFOMDDAWOLOME-UHFFFAOYSA-N [N].[Mg] Chemical compound [N].[Mg] SVFOMDDAWOLOME-UHFFFAOYSA-N 0.000 description 2
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- 238000005576 amination reaction Methods 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
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- 239000004615 ingredient Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 239000006012 monoammonium phosphate Substances 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002686 phosphate fertilizer Substances 0.000 description 2
- 230000008635 plant growth Effects 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
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- 235000002906 tartaric acid Nutrition 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
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- CIOXZGOUEYHNBF-UHFFFAOYSA-N (carboxymethoxy)succinic acid Chemical compound OC(=O)COC(C(O)=O)CC(O)=O CIOXZGOUEYHNBF-UHFFFAOYSA-N 0.000 description 1
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- LMHAGAHDHRQIMB-UHFFFAOYSA-N 1,2-dichloro-1,2,3,3,4,4-hexafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(Cl)C1(F)Cl LMHAGAHDHRQIMB-UHFFFAOYSA-N 0.000 description 1
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- 239000000176 sodium gluconate Substances 0.000 description 1
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- RVYQXTPUVCOSPF-UHFFFAOYSA-M sodium;2-(2,2-dihydroxyethylamino)acetate Chemical compound [Na+].OC(O)CNCC([O-])=O RVYQXTPUVCOSPF-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 235000010356 sorbitol Nutrition 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229920006029 tetra-polymer Polymers 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 229940080258 tetrasodium iminodisuccinate Drugs 0.000 description 1
- GYBINGQBXROMRS-UHFFFAOYSA-J tetrasodium;2-(1,2-dicarboxylatoethylamino)butanedioate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CC(C([O-])=O)NC(C([O-])=O)CC([O-])=O GYBINGQBXROMRS-UHFFFAOYSA-J 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- XFLNVMPCPRLYBE-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;tetrahydrate Chemical compound O.O.O.O.[Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O XFLNVMPCPRLYBE-UHFFFAOYSA-J 0.000 description 1
- 229910021654 trace metal Inorganic materials 0.000 description 1
- YIYBQIKDCADOSF-ONEGZZNKSA-N trans-pent-2-enoic acid Chemical compound CC\C=C\C(O)=O YIYBQIKDCADOSF-ONEGZZNKSA-N 0.000 description 1
- XKWFRVVFRZYIFP-UHFFFAOYSA-N triazanium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxymethyl)amino]acetate Chemical compound N.N.N.OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O XKWFRVVFRZYIFP-UHFFFAOYSA-N 0.000 description 1
- 229940048081 trisodium ethylenediamine disuccinate Drugs 0.000 description 1
- QEHXDDFROMGLSP-VDBFCSKJSA-K trisodium;(2s)-2-[2-[[(1s)-1-carboxy-2-carboxylatoethyl]amino]ethylamino]butanedioate Chemical compound [Na+].[Na+].[Na+].OC(=O)C[C@@H](C([O-])=O)NCCN[C@H](C([O-])=O)CC([O-])=O QEHXDDFROMGLSP-VDBFCSKJSA-K 0.000 description 1
- HERBOKBJKVUALN-UHFFFAOYSA-K trisodium;2-[bis(carboxylatomethyl)amino]acetate;hydrate Chemical compound O.[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O HERBOKBJKVUALN-UHFFFAOYSA-K 0.000 description 1
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 1
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Classifications
-
- 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
- C05G5/00—Fertilisers characterised by their form
- C05G5/10—Solid or semi-solid fertilisers, e.g. powders
- C05G5/12—Granules or flakes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Fertilizers (AREA)
Abstract
本发明涉及一种复合肥的生产方法,属于肥料技术领域。本发明解决的技术问题是提供一种复合肥的生产方法,其工艺简单成本低。该方法通过螯合‑氨化‑混合造粒工艺,得到复合肥。本发明方法,制备工艺简单,操作安全,生产成本低,可适用于各种浓度的湿法磷酸及配制各种不同氮、磷、钾及植物生长过程中所必需的中微量元素比例的复合肥料。本发明可有效提高复合肥中水溶磷含量及活化植物生长过程中所必需的中微量元素。本发明可充分利用湿法磷酸中的杂质离子,如铁、镁、钙等,防止在复合肥配置过程中磷素沉淀。本发明制备的复合肥水溶磷含量高,含植物生长过程中所必需的中微量元素,产品无毒无害,对环境友好,可广泛应用于农业。
Description
技术领域
本发明涉及一种复合肥的生产方法,属于肥料技术领域。
背景技术
当前我国复合肥生产主要以物理混配为主,即将不同的氮、磷、钾源及其他中微量元素按照一定比例掺混在一起或制成颗粒。此法生产复合肥的方式较为粗放,且对不同肥料原料的品质较高。同时,在添加中微量元素后,复合肥在施用过程中常会出现磷素沉淀等问题,造成磷及中微量元素失活。专利CN201910525981.4公开了一种节能环保高塔造粒缓释长效复合肥的制备工艺,即将尿素、磷酸铵和氯化钾熔化状态的混合体通过高塔造粒设备制备紧密状复合肥颗粒。该法生产过程中需对原料进行熔融处理,能耗高,生产成本高。专利CN201911420417.2公开了一种氮镁复合肥及其制备方法,即将尿素及硫酸镁按照一定比例混合形成复盐,从而制得氮镁复合肥。该法复合肥不含磷及钾元素,功能单一,不能广泛满足农业需求。专利CN201410713163.4公开了一种反应热可调的硫酸钾型复合肥氨化生产工艺,用氯化钾与浓硫酸直接反应,制取硫酸氢钾,溶解后经过一系列的反应制得含氮、磷、钾三元素的复合肥料浆,并通过转鼓造粒、烘干制得复合肥成品。该法工艺流程长,需将原料溶解后再烘干,能耗高。我国关于复合肥的研发主要集中在生产装置上及研发作物专用肥上。生产一般性复合肥的方法主要为通过不同方式进行混合原料,工艺冗长,能耗高,生产成本高,逐渐不能满足我国农业的需求。
申请号为201210154344.9的中国专利申请公开了一种大量元素全水溶肥生产方法,将特定的螯合剂加入粗磷酸中螯合,然后再通入氨气调节pH值为5-6,得到水溶性磷肥;水溶性磷肥与水溶性氮肥、水溶性钾肥混合造粒,经烘干、冷却,得到大量元素全水溶肥。该方法虽然能够以粗磷酸为原料制备得到大量元素水溶肥,但由于其需要特定的螯合剂,螯合剂的成分较为复杂,成本较高。
申请号为201910339366.4的中国专利申请公开了含中微量元素的全水溶磷酸一铵的制备方法,以湿法磷酸为原料,采用二次氨化技术,得到了全水溶磷酸一铵,该方法虽然能得到全水溶肥,但其需要两次氨化反应,工艺较为复杂,成本较高。
发明内容
针对以上缺陷,本发明解决的技术问题是提供一种复合肥的生产方法,其工艺简单成本低。
本发明复合肥的生产方法,其步骤如下:
a、螯合反应:将湿法磷酸与螯合剂混合,保持温度30~120℃,恒温反应10~120min,得到螯合液;
b、氨化反应:向螯合液中通入氨气中和至中和度为0.5~2.0后,反应30~60min,得到含磷酸铵物料;
c、混合造粒:含磷酸铵物料与附加肥料混合,造粒,得到复合肥;所述附加肥料为氮肥、钾肥和植物生长过程中所必需的中微量元素肥料中的至少一种。
作为其中一种实施方式,所用湿法磷酸的pH值在0.5以下。
作为一种实施方式,a步骤中,所述螯合剂为柠檬酸、EDTA、聚磷酸铵中的至少一种。
作为一种实施方式,a步骤中,螯合剂用量为湿法磷酸中的中微量元素发生螯合反应所需理论用量的1.0~1.5倍。
在一个具体实施方式中,螯合时,保持温度90℃,恒温反应30min。
在一个具体实施例中,b步骤反应30min。
作为一个实施方式,c步骤中,所述钾肥为硫酸钾、氯化钾、硝酸钾、磷酸二氢钾及磷酸氢二钾中的至少一种。
作为一个实施方式,c步骤中,所述氮肥为尿素、硝酸铵、硝酸钾中的至少一种。
作为一个实施方式,c步骤中,所述植物生长过程中所必需的中微量元素肥料为含钙、镁、硫、铁、锌、锰、铜、硼、钼、氯元素中的至少一种的肥料。
作为一种实施方式,c步骤中,所述造粒为喷浆造粒。
与现有技术相比,本发明具有如下优点:
1、本发明的复合肥以湿法磷酸为原料,制备工艺简单,无需特殊的螯合剂,只需经过一步氨化反应即可制得复合肥产品。
2、本发明的制备方法可适应各种浓度的湿法磷酸原料,复合肥产品中的水溶磷含量高,且可通过调节工艺条件从而调节复合肥中水溶磷含量。
3、本发明的复合肥含植物生长过程中所必须的中微量元素。
4、本发明充分利用了湿法磷酸中的杂质离子,提高了P2O5及杂质离子利用率,降低了生产成本。
5、本发明的复合肥含植物生长过程中所必需的中微量元素,产品无毒无害,对环境友好,可广泛应用于农业。
具体实施方式
本发明复合肥的生产方法,其步骤如下:
a、螯合反应:将湿法磷酸与螯合剂混合,保持温度30~120℃,恒温反应10~120min,得到螯合液;
b、氨化反应:向螯合液中通入氨气中和至中和度为0.5~2.0后,反应30~60min,得到含磷酸铵物料;
c、混合造粒:含磷酸铵物料与附加肥料混合,造粒,得到复合肥;所述附加肥料为氮肥、钾肥和植物生长过程中所必需的中微量元素肥料中的至少一种。
本发明方法,直接采用含湿法磷酸为原料,将湿法磷酸中的中微量金属元素采用螯合剂进行螯合,经氨化反应得到含中微量元素的磷酸铵料浆,通过混合反应添加钾源、氮源及其他中微量元素肥料,再经造粒制备得到营养元素丰富的复合肥。本发明的复合肥除了为植物提供N、P、K营养元素外,还可为提供植物提供生长过程中所必须的中微量元素。其方法简单成本较低。本发明采用螯合技术螯合湿法磷酸中部分金属离子以提高金属离子在磷酸氨化过程不被磷沉淀,因而能在提高磷和金属离子的利用率同时,大幅提高复合肥中水溶磷的含量。
作为其中一种实施方式,所用湿法磷酸为工业湿法磷酸,pH值在0.5以下。湿法磷酸的浓度可为目前国内任何厂家生产的湿法磷酸。
a步骤为螯合反应过程,即加入螯合剂后对湿法磷酸中的中微量元素进行螯合。本发明的目的是提高湿法磷酸中金属离子、P2O5的利用率及复合肥产品中水溶磷的含量,因此,本领域常用的螯合剂均适用于本发明,比如,乙二胺四乙酸(EDTA),乙二胺四乙酸二钠(EDTA-2Na),乙二胺四乙酸四钠(EDTA-4Na),乙二胺四乙酸二铵,乙二胺四乙酸三铵,二亚甲基三胺五乙酸,乙二胺四乙酸氢钾,乙二胺四乙酸二氢二钠二水合物,二乙烯三胺五乙酸(DTPA),二乙烯三胺五乙酸五钠(DTPA-5Na),三乙烯二胺(TEDA),丙二胺四乙酸(PDTA),羟乙基乙二胺三乙酸(HEDTA),羟乙基乙二胺三乙酸三钠(HEDTA-3Na),羟乙基乙二胺(AEEA),羟乙基乙二胺四乙酸三钠,二羟乙基甘氨酸钠,次氮基三乙酸钠,次氮基三乙酸,次氮基三乙酸三钠,次氮基三乙酸三钠一水合物,羟乙基二磷酸,乙二胺二邻苯基乙酸(EDDHA),乙二胺二邻苯基乙酸钠(EDDHA-Na),羟基乙叉二膦酸及其钾、钠、铵盐,氨基三甲叉膦酸及其钾、钠、铵盐,乙二胺四甲叉膦酸及其钾、钠、铵盐,二乙烯三胺五甲叉膦酸及其钾、钠、铵盐,2-膦酸丁烷-1,2,4-三羧酸及其钾、钠、铵盐,多元醇磷酸酯,2-羟基膦酸基乙酸及其钾、钠、铵盐,己二胺四甲叉膦酸及其钾、钠、铵盐,多氨基多醚基甲叉膦酸及其钾、钠、铵盐,双1,6-亚己基三胺五甲叉膦酸及其钾、钠、铵盐,三亚乙基四胺六乙酸及其钾、钠、铵盐,二羟乙基甘氨酸及其钾、钠、铵盐,2-氧乙酸基丙二酸及其钾、钠、铵盐,2-氧乙酸基丁导酸及其钾、钠、铵盐,1,2,3,4-环戊烷四羧酸及其钾、钠、铵盐,醋酸及其钾、钠、铵盐,柠檬酸,柠檬酸钾,柠檬酸一钠,植酸,葡萄糖酸,葡萄糖酸钠,葡萄糖酸钾,葡萄糖-δ-内脂,焦磷酸钠,三聚磷酸钠,焦磷酸钾,(多)聚磷酸,(多)聚磷酸钠,(多)聚磷酸铵,六偏磷酸,六偏磷酸钠,六偏磷酸钾,六偏磷酸铵,葡庚糖酸及其钾、钠、铵盐,山梨糖醇,山梨糖醇糖浆,羧甲基氧代琥珀酸,羧甲基酒石酸,酒石酸及其钠盐,酒石酸及其钾盐,萘三磺酸,马来酸,氨基酸及其钾、钠、铵盐,木素磺酸及其可溶性盐,戊酸,戊烯酸,戊烯酸五钠,腐殖酸及其钾、钠、铵盐,草酸及其钾、钠、铵盐,海藻酸及其钾、钠、铵盐,糖醇,甘露醇,木糖醇,苹果酸及其钾、钠、铵盐,黄腐酸及其钾、钠、铵盐,木质素磺酸及其钾、钠、铵盐,HBED,EDDMA,聚丙烯酸及其钾、钠、铵盐,聚乙二醇,甲酸,乙酸,丙酸,丁酸,乳酸,丙二酸,富马酸,枸椽酸,抗坏血酸,丁二酸,羟基乙酸,聚甲基丙烯酸,水解聚马来酸酐,马来酸-丙烯酸共聚物,丙烯酸-2-丙烯酰胺-2-甲基丙磺酸多元共聚物,丙烯酸丙烯酸羟丙酯共聚物,丙烯酸-丙烯酸酯-膦酸-磺酸盐四元共聚物,丙烯酸-丙烯酸酯-磺酸盐三元共聚物,羧酸盐-磺酸盐-非离子三元共聚物,聚环氧琥珀酸(钠),聚天冬氨酸(钠),乙二胺,2,2'-联吡啶,1,10-邻二氮杂菲,氨基三乙酸钠,亚氨基二乙酸,亚氨基二乙琥珀酸四钠,乙二胺二琥珀酸三钠(IDS),制糖工业的废酸或滤泥、糠醛及其废渣、酒精及味精生产排放的高浓度有机废液、发酵废液、禽畜粪便及其沼液、氨基酸废液、木醋液、寡糖、盐藻多糖、黄原胶、酵母废液等。
在一些具体实施例中,所述螯合剂为柠檬酸、EDTA、聚磷酸铵中的至少一种。
螯合剂的加入量与复合肥中水溶磷含量相关,螯合剂的加入量越多,则螯合中微量元素越多,复合肥产品中水溶磷含量越高,反之亦然。优选的,螯合剂用量为湿法磷酸中中微量元素发生螯合反应所需理论用量的1.0~1.5倍,则此时步骤b中,湿法磷酸经氨化反应后得到澄清溶液。
在一个具体实施方式中,螯合时,保持温度90℃,恒温反应30min。
b步骤为氨化反应过程,加入氨气至一定中和度(0.5~2.0)后,反应一定时间后即可。所得液体为含磷酸铵的料浆或者澄清溶液,即复合肥中的磷源。该溶液中含有湿法磷酸中的杂质离子,例如Fe、Mg、Ca、Mn、Cu、Zn等。
在一个具体的实施例中,b步骤的氨化反应的反应时间为30min。
c步骤为混合反应以及造粒过程,即向b步骤所得含磷酸铵的料浆或者澄清溶液添加钾源、氮源或中微量元素等肥料制得含复合肥的料浆。常用的钾源、氮源及中微量元素肥料均适用此步骤用于生产复合肥。
作为一个实施方式,所述钾肥为硫酸钾、氯化钾、硝酸钾、磷酸二氢钾及磷酸氢二钾中的至少一种。作为具体实施方式,所述钾肥为氯化钾。
作为一个实施方式,所述氮肥为尿素、硝酸铵、硝酸钾中的至少一种。作为具体实施方式,所述氮肥为尿素。
作为一个实施方式,所述植物生长过程中所必需的中微量元素肥料为含钙、镁、硫、铁、锌、锰、铜、硼、钼、氯元素中的至少一种的肥料。
c步骤中,常用的从溶液中制备得到固体的方法均适用于本发明复合肥的固体产品。作为一种实施方式,采用喷浆造粒的方式,制备复合肥的固体产品。
本发明对氨化反应的温度没有限定,湿法磷酸沸点以下的温度均适用于本发明,比如,可以选择室温,也可以选择加热来加快反应。当温度升高时,反应速率将会加快,为了加快反应速度,提高生产效率,同时综合考虑能耗问题,优选的反应温度为30~120℃。
所述复合肥产品的水溶磷含量与总磷含量的比值可根据螯合剂的添加量进行调节。
下面结合实施例对本发明的具体实施方式做进一步的描述,并不因此将本发明限制在所述的实施例范围之中。
实施例1
采用如下方法制备得到复合肥:
a,螯合反应:向湿法磷酸中加入湿法磷酸质量的5.0%的柠檬酸,并升温至60℃,反应30min,得到螯合之后的湿法磷酸;所述湿法磷酸的成分为如表1所示。
表1湿法磷酸的成分表
成分 | P<sub>2</sub>O<sub>5</sub> | Fe<sub>2</sub>O<sub>3</sub> | Al<sub>2</sub>O<sub>3</sub> | MgO | CaO | MnO |
含量/% | 41.68 | 0.31 | 0.31 | 1.14 | 0.24 | 0.15 |
b,氨化反应:向步骤a所得溶液中通入氨气至中和度为1.0后,反应30min,制得含磷酸铵的料浆。
c,混合反应:向步骤b所得的含磷酸铵的料浆或者澄清溶液中添加钾源、氮源肥料及植物生长过程中所必需的中微量元素,得到复合肥料的料浆。
d,造粒:将c中所得的复合肥料的料浆通过喷浆造粒的方式粒制得复合肥成品。
通过相同步骤,不添加柠檬酸制得空白复合肥产品。产品对比如表2所示。
表2添加柠檬酸后产品中水溶P2O5含量对比
产品 | N/% | 总P<sub>2</sub>O<sub>5</sub>/% | K<sub>2</sub>O/% | 水溶P<sub>2</sub>O<sub>5</sub>/% | P<sub>2</sub>O<sub>5</sub>利用率/% |
空白 | 16.06 | 16.32 | 16.15 | 15.46 | 94.72 |
添加柠檬酸 | 16.12 | 16.24 | 16.29 | 16.12 | 99.27 |
实施例2
采用如下方法制备得到复合肥:
a,螯合反应:向湿法磷酸中加入湿法磷酸质量的2.5%的乙二胺四乙酸二钠(EDTA-2Na),并升温至60℃,反应30min,得到螯合之后的湿法磷酸;所述湿法磷酸的成分为如表3所示。
表3湿法磷酸的成分表
成分 | P<sub>2</sub>O<sub>5</sub> | Fe<sub>2</sub>O<sub>3</sub> | Al<sub>2</sub>O<sub>3</sub> | MgO | CaO | MnO |
含量/% | 41.68 | 0.31 | 0.31 | 1.14 | 0.24 | 0.15 |
b,氨化反应:向步骤a所得溶液中通入氨气至中和度为1.1后,反应30min,制得含磷酸铵的料浆或者澄清溶液。
c,混合反应:向步骤b所得的含磷酸铵的料浆或者澄清溶液中添加钾源、氮源肥料及植物生长过程中所必需的中微量元素,得到复合肥料的料浆。
d,造粒:将c中所得的复合肥料的料浆通过喷浆造粒的方式制得复合肥成品。
通过相同步骤,不添加乙二胺四乙酸二钠制得空白复合肥产品。产品对比如表4所示。
表4添加乙二胺四乙酸二钠后产品中水溶P2O5含量对比
产品 | N/% | 总P<sub>2</sub>O<sub>5</sub>/% | K<sub>2</sub>O/% | 水溶P<sub>2</sub>O<sub>5</sub>/% | P<sub>2</sub>O<sub>5</sub>利用率/% |
空白 | 17.18 | 17.22 | 17.09 | 16.07 | 93.35 |
添加EDTA-2Na | 17.27 | 17.32 | 17.15 | 16.95 | 97.88 |
实施例3
采用如下方法制备得到复合肥:
a,螯合反应:向湿法磷酸中加入湿法磷酸质量的5.0%的柠檬酸,并升温至120℃,反应10min,得到螯合之后的湿法磷酸;所述湿法磷酸的成分为如表5所示。
表5湿法磷酸的成分表
成分 | P<sub>2</sub>O<sub>5</sub> | Fe<sub>2</sub>O<sub>3</sub> | Al<sub>2</sub>O<sub>3</sub> | MgO | CaO | MnO |
含量/% | 24.21 | 0.96 | 0.87 | 1.09 | 0.15 | 0.13 |
b,氨化反应:向步骤a所得溶液中通入氨气至中和度为1.0后,反应30min,制得含磷酸铵的料浆或者澄清溶液。
c,混合反应:向步骤b所得的含磷酸铵的料浆或者澄清溶液中添加钾源、氮源肥料及植物生长过程中所必需的中微量元素,得到复合肥料的料浆。
d,造粒:将c中所得的复合肥料的料浆通过喷浆造粒的方式制得复合肥成品。
通过相同步骤,不添加柠檬酸制得空白复合肥产品。产品对比如表6所示。
表6添加柠檬酸后产品中水溶P2O5含量对比
产品 | N/% | 总P<sub>2</sub>O<sub>5</sub>/% | K<sub>2</sub>O/% | 水溶P<sub>2</sub>O<sub>5</sub>/% | P<sub>2</sub>O<sub>5</sub>利用率/% |
空白 | 16.31 | 16.09 | 16.07 | 13.56 | 84.33 |
添加柠檬酸 | 16.15 | 16.18 | 16.13 | 15.14 | 93.56 |
实施例4
采用如下方法制备得到复合肥:
a,螯合反应:向湿法磷酸中加入湿法磷酸质量的2.5%的乙二胺四乙酸二钠,并升温至30℃,反应120min,得到螯合之后的湿法磷酸;所述湿法磷酸的成分为如表7所示。
表7湿法磷酸的成分表
成分 | P<sub>2</sub>O<sub>5</sub> | Fe<sub>2</sub>O<sub>3</sub> | Al<sub>2</sub>O<sub>3</sub> | MgO | CaO | MnO |
含量/% | 24.21 | 0.96 | 0.87 | 1.09 | 0.15 | 0.13 |
b,氨化反应:向步骤a所得溶液中通入氨气至中和度为1.1后,反应30min,制得含磷酸铵的料浆或者澄清溶液。
c,混合反应:向步骤b所得的含磷酸铵的料浆或者澄清溶液中添加钾源、氮源肥料及植物生长过程中所必需的中微量元素,得到复合肥料的料浆。
d,造粒:将c中所得的复合肥料的料浆通过喷浆造粒的方式制得复合肥成品。
通过相同步骤,不添加乙二胺四乙酸二钠制得空白复合肥产品。产品对比如表8所示。
表8添加乙二胺四乙酸二钠后产品中水溶P2O5含量对比
产品 | N/% | 总P<sub>2</sub>O<sub>5</sub>/% | K<sub>2</sub>O/% | 水溶P<sub>2</sub>O<sub>5</sub>/% | P<sub>2</sub>O<sub>5</sub>利用率/% |
空白 | 17.02 | 17.18 | 17.06 | 14.30 | 83.26 |
添加EDTA-2Na | 16.98 | 17.23 | 17.14 | 16.83 | 97.72 |
可见,通过本发明方法,可以充分利用湿法磷酸中的杂质离子,提高P2O5及杂质离子利用率,得到水溶磷含量高的复合肥。
Claims (10)
1.复合肥的生产方法,其特征在于,其步骤如下:
a、螯合反应:将湿法磷酸与螯合剂混合,保持温度30~120℃,恒温反应10~120min,得到螯合液;
b、氨化反应:向螯合液中通入氨气中和至中和度为0.5~2.0后,反应30~60min,得含磷酸铵物料;
c、混合造粒:含磷酸铵物料与附加肥料混合,造粒,得到复合肥;所述附加肥料为氮肥、钾肥和植物生长过程中所必需的中微量元素肥料中的至少一种。
2.根据权利要求1所述的复合肥的生产方法,其特征在于:湿法磷酸的pH值≤0.5。
3.根据权利要求1所述的复合肥的生产方法,其特征在于:a步骤中,所述螯合剂为柠檬酸、EDTA、聚磷酸铵中的至少一种。
4.根据权利要求1所述的复合肥的生产方法,其特征在于:a步骤中,螯合剂用量为湿法磷酸中的中微量元素发生螯合反应所需理论用量的1.0~1.5倍。
5.根据权利要求1所述的复合肥的生产方法,其特征在于:a步骤中,保持温度90℃,恒温反应30min。
6.根据权利要求1所述的复合肥的生产方法,其特征在于:b步骤中,反应30min。
7.根据权利要求1所述的复合肥的生产方法,其特征在于:c步骤中,所述钾肥为硫酸钾、氯化钾、硝酸钾、磷酸二氢钾及磷酸氢二钾中的至少一种。
8.根据权利要求1所述的复合肥的生产方法,其特征在于:c步骤中,所述氮肥为尿素、硝酸铵、硝酸钾中的至少一种。
9.根据权利要求1所述的复合肥的生产方法,其特征在于:c步骤中,所述植物生长过程中所必需的中微量元素肥料为含钙、镁、硫、铁、锌、锰、铜、硼、钼、氯元素中的至少一种的肥料。
10.根据权利要求1所述的复合肥的生产方法,其特征在于:c步骤中,所述造粒为喷浆造粒。
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