CN113845384A - 一种由化丝含钼废酸制备含钼水溶肥料的方法 - Google Patents
一种由化丝含钼废酸制备含钼水溶肥料的方法 Download PDFInfo
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- CN113845384A CN113845384A CN202010521068.XA CN202010521068A CN113845384A CN 113845384 A CN113845384 A CN 113845384A CN 202010521068 A CN202010521068 A CN 202010521068A CN 113845384 A CN113845384 A CN 113845384A
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- Prior art keywords
- molybdenum
- soluble fertilizer
- waste acid
- water
- acid
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 97
- 239000011733 molybdenum Substances 0.000 title claims abstract description 97
- 239000003337 fertilizer Substances 0.000 title claims abstract description 93
- 239000002253 acid Substances 0.000 title claims abstract description 46
- 239000002699 waste material Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 150000001413 amino acids Chemical class 0.000 claims abstract description 16
- 238000007539 photo-oxidation reaction Methods 0.000 claims abstract description 15
- 239000000725 suspension Substances 0.000 claims abstract description 14
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004021 humic acid Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 15
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 239000000835 fiber Substances 0.000 claims description 11
- 238000004321 preservation Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002738 chelating agent Substances 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 229910021538 borax Inorganic materials 0.000 claims description 6
- 235000010333 potassium nitrate Nutrition 0.000 claims description 6
- 239000004323 potassium nitrate Substances 0.000 claims description 6
- 239000004328 sodium tetraborate Substances 0.000 claims description 6
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- PUKLDDOGISCFCP-JSQCKWNTSA-N 21-Deoxycortisone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2=O PUKLDDOGISCFCP-JSQCKWNTSA-N 0.000 claims description 4
- FCYKAQOGGFGCMD-UHFFFAOYSA-N Fulvic acid Natural products O1C2=CC(O)=C(O)C(C(O)=O)=C2C(=O)C2=C1CC(C)(O)OC2 FCYKAQOGGFGCMD-UHFFFAOYSA-N 0.000 claims description 4
- 229940095100 fulvic acid Drugs 0.000 claims description 4
- 239000002509 fulvic acid Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- NGLMYMJASOJOJY-UHFFFAOYSA-O azanium;calcium;nitrate Chemical compound [NH4+].[Ca].[O-][N+]([O-])=O NGLMYMJASOJOJY-UHFFFAOYSA-O 0.000 claims description 3
- 239000000084 colloidal system Substances 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
- 238000000227 grinding Methods 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 3
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 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 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- HPJCCRXHHUHXTM-UHFFFAOYSA-L dipotassium urea sulfate Chemical compound S(=O)(=O)([O-])[O-].[K+].NC(=O)N.[K+] HPJCCRXHHUHXTM-UHFFFAOYSA-L 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 2
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims 1
- 239000011573 trace mineral Substances 0.000 abstract description 36
- 235000013619 trace mineral Nutrition 0.000 abstract description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 18
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 229910052742 iron Inorganic materials 0.000 abstract description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052796 boron Inorganic materials 0.000 abstract description 8
- 229910052802 copper Inorganic materials 0.000 abstract description 8
- 239000010949 copper Substances 0.000 abstract description 8
- 229910052725 zinc Inorganic materials 0.000 abstract description 8
- 239000011701 zinc Substances 0.000 abstract description 8
- 238000001816 cooling Methods 0.000 abstract description 7
- 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 abstract description 7
- 235000015097 nutrients Nutrition 0.000 abstract description 6
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical group O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 abstract description 3
- 238000002844 melting Methods 0.000 abstract description 2
- -1 major elements Substances 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000012263 liquid product Substances 0.000 description 8
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 7
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 6
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 6
- XBDUTCVQJHJTQZ-UHFFFAOYSA-L iron(2+) sulfate monohydrate Chemical compound O.[Fe+2].[O-]S([O-])(=O)=O XBDUTCVQJHJTQZ-UHFFFAOYSA-L 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000011343 solid material Substances 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000000375 suspending agent Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 230000012010 growth Effects 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000010309 melting process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 235000021049 nutrient content Nutrition 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000010517 secondary reaction Methods 0.000 description 2
- 239000011684 sodium molybdate Substances 0.000 description 2
- 235000015393 sodium molybdate Nutrition 0.000 description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000219193 Brassicaceae Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 108090000913 Nitrate Reductases Proteins 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000004720 fertilization Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000010979 pH adjustment Methods 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
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 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
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001850 reproductive effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
Images
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- 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
-
- 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
- C05C—NITROGENOUS FERTILISERS
- C05C5/00—Fertilisers containing other nitrates
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F7/00—Fertilisers from waste water, sewage sludge, sea slime, ooze or similar masses
-
- 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
- C05G3/50—Surfactants; Emulsifiers
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/20—Liquid fertilisers
- C05G5/23—Solutions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Fertilizers (AREA)
Abstract
本发明公开了一种由化丝含钼废酸制备含钼水溶肥料的方法,包括含钼废酸经过光氧化转化将其中的低价态钼转化为钼酸形态的六价钼产生无色含钼废酸,大量元素、中量元素、氨基酸、腐植酸,依据作物对水溶肥料养分的不同需求,按比例将它们进行混合、搅拌、加热,适时加入锌、锰、铜、铁、硼等微量元素成分,然后,加入上述无色含钼废酸,并调节pH,冷却后获得各种含钼水溶肥料产品,本发明制备了大量元素水溶肥料(微量元素型)、中量元素水溶肥料(添加微量元素)、微量元素水溶肥料、含氨基酸水溶肥料(微量元素型)、含腐植酸水溶肥料(微量元素型)产品和悬浮型液体肥料(微量元素型),为化丝含钼废酸的后续利用提供了一种途径。
Description
【技术领域】
本发明涉及可再生领域和农用化学技术领域,特别涉及一种由化丝含钼废酸制备含钼水溶肥料的方法。
【背景技术】
电光源行业生产钨灯丝产生含钼废酸,这种废酸如果不经无害化和回收技术处理,不仅造成环境污染问题,同时也造成钼资源的浪费。目前含钼废酸的主要回收方法是制作成钼酸盐产品,用在钢铁、电子、化学、石油、医药等工业领域。回收钼制备钼酸盐的生产工艺路线较长,一般也比较复杂。含钼废酸直接用于钼水溶肥料生产是一个有发展前景的方向。
水溶肥料是经过水溶解或稀释,用于灌溉施肥、叶面施肥、无土栽培、浸种蘸根等用途的液体或固体肥料。根据中华人民共和国农业行业标准,水溶肥料有大量元素、中量元素、微量元素水溶肥料以及含氨基酸、含腐植酸水溶肥料等种类。水溶肥料养分含量高,含有作物所需要氮、磷、钾大量元素,钙、镁中量元素,铜、铁、锰、锌、硼、钼微量元素,还可以含有腐植酸、氨基酸等营养成分。水溶肥料具有肥料利用率高、施用方便、适于机械化和自动化生产的优点,是可持续发展的新型肥料。水溶肥料中含有微量元素,对植物的生长发育的作用起到不可或缺的作用,当某种微量元素缺乏时,作物生长发育受到影响。钼作为植物生长必需的微量元素之一,在豆科和十字花科等为代表的作物生长过程中起到重要的作用。钼作为固氮酶和硝酸还原酶的组成成分,直接影响着固氮菌发挥作用,此外钼对作物繁殖器官和光合作用也有重要影响。实践证明,钼对大豆、水稻、玉米、小麦、果蔬、烟草和牧草等作物有良好的增产效果,成为现代农业生产需求快速增加的微量元素。钼是钢铁电子、化学、石油、医药等工业领域不可或缺的稀有高熔点金属之一,工业上使用的钼主要来源于钼矿石中提炼,但钼矿资源为不可再生资源,其自然界的总储量相对于断增长的工业需求来说十分有限,导致钼的市场价格近年来不断攀升。通过对钼资源的合理二次资源化成为补充钼储量不足的重要途径。
水溶肥料的生产方法比较多,关键在于养分的比例、原料来源的控制,并且需防止长期存储过程析出结晶等问题。对于微量元素水溶肥料,还需要通过提供合适的有机配体与微量元素作用,使其不仅溶解于水溶肥料之中,还可以在施用过程中发挥最大的微量元素的养分作用。中国专利CN201811626094.8、CN201811455225.0和CN201710861902.8公开了几种大量元素水溶肥料及其制备方法。中国专利CN201911185650.7、CN201810186280.8和CN201710852354.2公开了几种中量元素水溶肥料及其制备方法。中国专利201711400891.X公开了一种螯合态微量元素水溶肥料的制备方法。中国专利CN201810599341.3公开了一种含氨基酸水溶肥料的制备方法。中国专利CN201910473110.2公开了一种含腐植酸肥料的制备方法。此外,中国专利CN201910773926.7公开了一种由光伏行业废酸溶液回收制备水溶肥料的方法。中国专利CN201910984068.0公开了一种锰渣生产微量元素水溶肥料的方法。这此方法拓展了水溶肥料的配方和制备方法,但它们也均有需要改进的方面。
悬浮型液体肥料是液体肥料的一个新种类,借助悬浮剂的作用将肥料固体微细颗粒物悬浮于水中成为悬浮液,它具有养分含量高,节省运输成本等方面的优势。悬浮型液体需解决的关键问题是储存过程时肥料的分层问题。通过选择合适的悬浮剂和生产工艺关键技术参数的控制,生产出悬浮效果优异的悬浮型液体肥料。中国专利CN201710850228.3公开了一种悬浮型液体肥料的稳定剂的配方及制备方法,可用于多种液体肥料,包括中量元素液体肥料。但其悬浮剂的成分极为复杂,且用到了价格较高的化学品。中国专利CN200910192150.6、CN201410208635.0、CN201510506105.9和CN201710364447.0分别公开了悬浮型液体肥料的不同制备方法。其养分种类和含量以及悬浮剂及制备方法各自也都存在不同程度的问题。
上述的制备水溶肥料方法中,微量元素钼的来源均来自于钼酸铵和钼酸钠等工业化学品,这些化学品的生产工艺复杂。将化丝含钼废酸不经过制备成钼酸铵和钼酸钠,而直接作为钼的来源,用于水溶肥料的制备,是一种高效利用含废钼酸中钼的方法。
我国现行农业行业标准NY1110-2010对水溶肥料中的汞、砷、镉、铅和铬重金属的限量有明确的规定,这使得利用回收原料进行水溶肥料的生产有了明确的限制。对于以重金属含量较多的回收原料生产水溶肥料,往往造成产品的重金属指标不能达到国家标准的要求。本发明使用的化丝含钼废酸,来自于高纯的金属钼丝经高纯的硝酸和硫酸混合物氧化而来,重金属含量极低,产品的重金属指标远远小于国家规定,不产生二次污染。
【发明内容】
本发明的目的在于提供一种由化丝含钼废酸制备含钼水溶肥料的方法,为化丝含钼废酸的后续利用提供了一种途径。
实现上述目的,本发明提供如下技术方案:
本申请公开了一种由化丝含钼废酸制备含钼水溶肥料的方法,包括如下步骤:
a)光氧化:将化丝含钼废酸加入到特制装置中,再加入氧化剂,通入压缩空气,并对化丝含钼废酸光照4~6小时,直至化丝含钼废酸的颜色由橙红变为无色;
b)混合:根据所需制备的含钼水溶肥料,在反应器中加入对应的区别原料和水,搅拌并加热;
c)再混合:在保温条件下,在反应器中依次加入硝酸锌、硫酸锰、硫酸铜、硫酸亚铁、螯合剂,继续加入表面活性剂、硼砂,搅拌至反应器中固体完全溶解;
d)制备肥料:将步骤a)中光氧化后的无色含钼废酸加入反应器中,调节pH,制备出所需的含钼水溶肥料。
作为优选,所述步骤b)中所述的区别原料为组分1、组分2、组分3、组分4或组分5中的其中一种,所述组分1包括硝酸铵、磷酸、硝酸钾、尿素和磷酸氢二钾;所述组分2包括硝酸钾、尿素、硝酸铵钙和氯化镁;所述组分3包括氨基酸原粉和黄腐酸;所述组分4包括腐殖酸和氨基酸;所述组分5包括尿素硫酸钾和磷酸二氢钾。
作为优选,所述步骤b)中采用组分5,并使用分散盘进行搅拌,所述步骤d)中调节pH后,得到分散液,将分散液加入胶体磨中研磨2~3次,制备出悬浮型含钼液体肥料。
作为优选,所述步骤c)中所述的螯合剂包括三聚磷酸钠、六偏磷酸钠、EDTA。
本发明的有益效果:
(1)将化丝含钼废酸经过光氧化转化后,作为制备水溶肥料的钼来源,光氧化可以将化丝含钼废酸中各种低价态的钼全部转化为六价态的钼,从而使化丝含钼废酸中钼的利用达到最大化。
(2)光氧化后的化丝含钼废酸中的硝酸和硫酸成分,作为制备水溶肥料过程中的pH调节以及提供部分硝酸根和硫酸根作为铵的平衡离子。
(3)依据作物对水溶肥料养分的不同需求,加入不同的组分的区别原料,从而可以制备出不同种类的含钼水溶肥料。
本发明的特征及优点将通过实施例结合附图进行详细说明。
【附图说明】
图1是本发明一种由化丝含钼废酸制备含钼水溶肥料的方法的工艺流程图;
图2是本发明制备悬浮型含钼液体肥料的工艺流程图。
【具体实施方式】
为使本发明的目的、技术方案和优点更加清楚明了,下面通过附图及实施例,对本发明进行进一步详细说明。但是应该理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限制本发明的范围。此外,在以下说明中,省略了对公知结构和技术的描述,以避免不必要地混淆本发明的概念。
为了实现钼的充分利用,我们先前的专利对化丝工艺的反应过程进行了监测,分析发现,化丝过程中存在主要化学反应和次要化学反应两种类型,其化学反应方程式如下:
主要反应:Mo+4HNO3→MoO2(NO3)2+2NO+2H2O
次要反应:W+2HNO3→WO2(NO3)2+2NO+2H2O
Mo+8HNO3→MoO2(NO3)2+6NO2+4H2O
Mo+6HNO3→Mo(NO3)3+3NO2+3H2O
次要反应中的某些产物如低价钼Mo3+和NOx等是呈现红色特征的物质,使得废钼酸呈橙红或棕红。为使红色的含钼废酸变为无色透明液体,我们将其加入适量的过氧化氢溶液,并在通入压缩空气和光照射下条件下,反应4~5小时,实现了低价钼向六价钼的转化。经过光氧化转化后,所得到的无色透明液体作为制备水溶肥料的钼和酸的来源,制备大量元素水溶肥料(微量元素型)液体产品、中量元素水溶肥料(添加微量元素)液体产品、微量元素水溶肥料液体产品、含氨基酸水溶肥料(微量元素型)液体产品、含腐植酸水溶肥料(微量元素型)产品和悬浮型液体肥料(微量元素型)产品。
实施例一:
参阅图1,在反应器中加入硝酸铵96g、磷酸101g、硝酸钾102g、尿素94g、磷酸氢二钾202g和水1000g,在剧烈搅拌下将反应器升温至60~65℃,继续搅拌保温反应2小时,在保温条件下,依次加入六水合硝酸锌5.5g、一水合硫酸锰2.9g、五水合硫酸铜3.5g、一水合硫酸亚铁2.9g、螯合剂10g,继续加入表面活性剂5g、硼砂6.1g到反应器中至固体物料完全溶解,反应2小时,将光氧化后的含钼废酸加入反应器中,调节pH至4,冷却后制备出大量元素液体肥料(微量元素型)液体产品。
大量元素液体肥料的总氮含量220~240g/L(其中硝态氮110~130g/L,铵态氮10~20g/L,尿态氮80~90g/L),总磷(P2O5)含量140~180g/L,总钾(K2O)含量140~180g/L,微量元素元素总含量为3~6g/L,各微量元素的含量分别锌0.9~1.2g/L、锰0.6~0.9g/L、铜0.6~0.9g/L、铁0.6~0.9g/L、硼0.6~0.9g/L、钼0.8~1.1g/L。
实施例二:
参阅图1:在反应器中加入硝酸钾30g、尿素60g、硝酸铵钙200g、氯化镁114g和水1000g,在剧烈搅拌下将反应器升温至60~65℃,继续搅拌保温反应2小时,在保温条件下,依次加入六水合硝酸锌6.1g、一水合硫酸锰3.0g、五水合硫酸铜3.4g、一水合硫酸亚铁2.8g、螯合剂10g,继续加入表面活性剂5g、硼砂6.2g到反应器中至固体物料完全溶解,反应2小时,将光氧化后的含钼废酸加入反应器中,调节pH至4,冷却后制备出中量元素液体肥料(微量元素型)液体产品。
中量元素液体肥料的总氮含量280~300g/L,总钙(CaO)含量50~70g/L,总镁(MgO)含量40~60g/L,总钾(K2O)含量10~30g/L,微量元素元素总含量为5~10g/L,各微量元素的含量分别锌1.2~1.5g/L、锰0.8~1.1g/L、铜0.7~1.0g/L、铁0.7~1.0g/L、硼0.6~0.9g/L、钼0.8~1.1g/L。
实施例三:
参阅图1,将六水合硝酸锌92g、一水合硫酸锰47g、五水合硫酸铜60g、一水合硫酸亚铁46g、螯合剂100g等原料,在剧烈搅拌下依次加入到装有水反的应器,升温至60~65℃,继续搅拌保温反应2~3小时,冷却,继续加入表面活性剂50g、硼砂140g到反应器中至固体物料完全溶解,将光氧化后的含钼废酸加入反应器中,调节pH至3~5,冷却后制备出微量元素水溶肥料液体产品。
微量元素水溶肥料中的微量元素总含量为100~110g/L,各微量元素占水溶肥料的质量百分比为锌20~30g/L、锰10~20g/L、铜10~20g/L、铁10~20g/L、硼10~20g/L、钼5~10g/L。
实施例四:
参阅图1,在反应器中加入氨基酸原粉、黄腐酸和水等原料,在剧烈搅拌下将反应器升温至60~65℃,继续搅拌保温反应2小时,在保温条件下,依次加入六水合硝酸锌19g、一水合硫酸锰7.1g、五水合硫酸铜9.2g、一水合硫酸亚铁7.3g、螯合剂30g,继续加入表面活性剂8g、硼砂21g到反应器中至固体物料完全溶解,反应2小时,将光氧化后的含钼废酸加入反应器中,调节pH至4,冷却后制备出含氨基酸水溶肥料(微量元素型)液体产品。
含氨基酸水溶肥料中游离氨基酸含量100~120g/L,黄腐酸含量20~30g/L,微量元素元素总含量为20~40g/L,各微量元素的含量分别铜2~6g/L、铁2~6g/L、锰2~6g/L、锌4~7g/L、硼2~6g/L、钼3~5g/L。
实施例五:
参阅图1,在反应器中加入腐植酸40g、氨基酸5g和水1000等原料,在剧烈搅拌下将反应器升温至60~65℃,继续搅拌保温反应2小时,在保温条件下,依次加入六水合硝酸锌9.1g、一水合硫酸锰2.5g、五水合硫酸铜3.0g、一水合硫酸亚铁2.6g、螯合剂15g,继续加入表面活性剂5g、硼砂6.8g到反应器中至固体物料完全溶解,反应2小时,将光氧化后的含钼废酸加入反应器中,调节pH至4,冷却后制备出含腐植酸水溶肥料(微量元素型)产品。
含腐植酸水溶肥料中腐植酸含量30~50g/L,游离氨基酸含量5~10g/L,微量元素元素总含量为6~10g/L,各微量元素的含量分别锌2~4g/L、锰1~2g/L、铜1~2g/L、铁1~2g/L、硼1~2g/L、钼0.2~0.5g/L。
实施例六:
参阅图2:在反应器中加入尿素340g、硫酸钾120g、磷酸二氢钾380g等原料和水,在分散盘的剧烈搅拌下将反应器升温至60~65℃,继续搅拌保温反应2小时,然后在保温条件下,依次加入六水合硝酸锌35g、一水合硫酸锰14g、五水合硫酸铜17g、一水合硫酸亚铁15g、螯合剂50g,继续加入表面活性剂10g、硼砂35g到反应器中至固体物料完全溶解,反应2小时,将光氧化后的含钼废酸加入反应器中,调节pH至4,将分散液送到胶体磨,研磨2~3次,制备出含微量元素的悬浮型液体肥料产品。
含微量元素的悬浮型液体肥料产品的总氮含量280~300g/,总磷(P2O5)含量150~170g/L,总钾(K2O)含量190~210g/L,微量元素元素总含量为20~30g/L,各微量元素的含量分别锌4~6g/L、锰3~5g/L、铜3~5g/L、铁3~5g/L、硼3~5g/L、钼2~4g/L。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换或改进等,均应包含在本发明的保护范围之内。
Claims (4)
1.一种由化丝含钼废酸制备含钼水溶肥料的方法,其特征在于:包括如下步骤:
a)光氧化:将化丝含钼废酸加入到特制装置中,再加入氧化剂,通入压缩空气,并对化丝含钼废酸光照4~6小时,直至化丝含钼废酸的颜色由橙红变为无色;
b)混合:根据所需制备的含钼水溶肥料,在反应器中加入对应的区别原料和水,搅拌并加热;
c)再混合:在保温条件下,在反应器中依次加入硝酸锌、硫酸锰、硫酸铜、硫酸亚铁、螯合剂,继续加入表面活性剂、硼砂,搅拌至反应器中固体完全溶解;
d)制备肥料:将步骤a)中光氧化后的无色含钼废酸加入反应器中,调节pH,制备出所需的含钼水溶肥料。
2.如权利要求1所述的一种由化丝含钼废酸制备含钼水溶肥料的方法,其特征在于:所述步骤b)中所述的区别原料为组分1、组分2、组分3、组分4或组分5中的其中一种,所述组分1包括硝酸铵、磷酸、硝酸钾、尿素和磷酸氢二钾;所述组分2包括硝酸钾、尿素、硝酸铵钙和氯化镁;所述组分3包括氨基酸原粉和黄腐酸;所述组分4包括腐殖酸和氨基酸;所述组分5包括尿素硫酸钾和磷酸二氢钾。
3.如权利要求2所述的一种由化丝含钼废酸制备含钼水溶肥料的方法,其特征在于:所述步骤b)中采用组分5,并使用分散盘进行搅拌,所述步骤d)中调节pH后,得到分散液,将分散液加入胶体磨中研磨2~3次,制备出悬浮型含钼液体肥料。
4.如权利要求1所述的一种由化丝含钼废酸制备含钼水溶肥料的方法,其特征在于:所述步骤c)中所述的螯合剂包括三聚磷酸钠、六偏磷酸钠、EDTA。
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