CN107500856A - A kind of method, selenium-enriched organic fertilizer and its application that Enteromorpha fast liquefying is produced to selenium-enriched organic fertilizer - Google Patents
A kind of method, selenium-enriched organic fertilizer and its application that Enteromorpha fast liquefying is produced to selenium-enriched organic fertilizer Download PDFInfo
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- CN107500856A CN107500856A CN201710700918.0A CN201710700918A CN107500856A CN 107500856 A CN107500856 A CN 107500856A CN 201710700918 A CN201710700918 A CN 201710700918A CN 107500856 A CN107500856 A CN 107500856A
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- enteromorpha
- selenium
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- organic fertilizer
- acid
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- 241000196252 Ulva Species 0.000 title claims abstract description 193
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000011669 selenium Substances 0.000 title claims abstract description 79
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 70
- 239000003895 organic fertilizer Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000002002 slurry Substances 0.000 claims abstract description 94
- 238000006366 phosphorylation reaction Methods 0.000 claims abstract description 44
- 239000003337 fertilizer Substances 0.000 claims abstract description 40
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 40
- 230000007062 hydrolysis Effects 0.000 claims abstract description 39
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 37
- JRPHGDYSKGJTKZ-UHFFFAOYSA-K selenophosphate Chemical compound [O-]P([O-])([O-])=[Se] JRPHGDYSKGJTKZ-UHFFFAOYSA-K 0.000 claims abstract description 29
- 230000026731 phosphorylation Effects 0.000 claims abstract description 23
- 239000012141 concentrate Substances 0.000 claims abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 44
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 42
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 35
- 239000002253 acid Substances 0.000 claims description 31
- 239000003513 alkali Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 22
- 102000004190 Enzymes Human genes 0.000 claims description 21
- 108090000790 Enzymes Proteins 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 18
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 17
- 229920002472 Starch Polymers 0.000 claims description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 13
- 239000004202 carbamide Substances 0.000 claims description 13
- 235000019698 starch Nutrition 0.000 claims description 13
- 108091005804 Peptidases Proteins 0.000 claims description 12
- 239000004365 Protease Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 claims description 11
- 229910019213 POCl3 Inorganic materials 0.000 claims description 8
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 8
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 238000010612 desalination reaction Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 4
- 239000004576 sand Substances 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 3
- 150000003863 ammonium salts Chemical group 0.000 claims description 3
- 239000011344 liquid material Substances 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- 229940082569 selenite Drugs 0.000 abstract description 16
- MCAHWIHFGHIESP-UHFFFAOYSA-L selenite(2-) Chemical compound [O-][Se]([O-])=O MCAHWIHFGHIESP-UHFFFAOYSA-L 0.000 abstract description 12
- 230000001590 oxidative effect Effects 0.000 abstract description 10
- 235000015097 nutrients Nutrition 0.000 abstract description 9
- 230000000295 complement effect Effects 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000005416 organic matter Substances 0.000 abstract description 2
- 229940091258 selenium supplement Drugs 0.000 description 51
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- 235000001014 amino acid Nutrition 0.000 description 14
- 239000001913 cellulose Substances 0.000 description 14
- 229920002678 cellulose Polymers 0.000 description 14
- 235000016709 nutrition Nutrition 0.000 description 14
- 150000001413 amino acids Chemical class 0.000 description 13
- 239000004615 ingredient Substances 0.000 description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 12
- 239000011574 phosphorus Substances 0.000 description 12
- 229910052698 phosphorus Inorganic materials 0.000 description 12
- 239000002131 composite material Substances 0.000 description 10
- 235000019419 proteases Nutrition 0.000 description 10
- 235000018102 proteins Nutrition 0.000 description 10
- 102000004169 proteins and genes Human genes 0.000 description 10
- 108090000623 proteins and genes Proteins 0.000 description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 9
- 239000011591 potassium Substances 0.000 description 9
- 229910052700 potassium Inorganic materials 0.000 description 9
- 102000004196 processed proteins & peptides Human genes 0.000 description 9
- 108090000765 processed proteins & peptides Proteins 0.000 description 9
- 229920001184 polypeptide Polymers 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 7
- 239000012047 saturated solution Substances 0.000 description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000011573 trace mineral Substances 0.000 description 6
- 235000013619 trace mineral Nutrition 0.000 description 6
- 239000013505 freshwater Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- -1 selenite amino acid Chemical class 0.000 description 5
- 235000013616 tea Nutrition 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 4
- 229920002488 Hemicellulose Polymers 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 4
- 230000004720 fertilization Effects 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- 230000002262 irrigation Effects 0.000 description 4
- 238000003973 irrigation Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 230000001954 sterilising effect Effects 0.000 description 4
- 238000004659 sterilization and disinfection Methods 0.000 description 4
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 3
- 229930003268 Vitamin C Natural products 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 230000007071 enzymatic hydrolysis Effects 0.000 description 3
- 235000019197 fats Nutrition 0.000 description 3
- 150000004676 glycans Chemical class 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 230000012010 growth Effects 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 229920001282 polysaccharide Polymers 0.000 description 3
- 239000005017 polysaccharide Substances 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000001360 synchronised effect Effects 0.000 description 3
- 235000019154 vitamin C Nutrition 0.000 description 3
- 239000011718 vitamin C Substances 0.000 description 3
- 108091005508 Acid proteases Proteins 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 108010082495 Dietary Plant Proteins Proteins 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 101000693530 Staphylococcus aureus Staphylokinase Proteins 0.000 description 2
- 244000269722 Thea sinensis Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 210000002421 cell wall Anatomy 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000001066 destructive effect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000000413 hydrolysate Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 230000008635 plant growth Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009822 protein phosphorylation Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229930003231 vitamin Natural products 0.000 description 2
- 235000013343 vitamin Nutrition 0.000 description 2
- 239000011782 vitamin Substances 0.000 description 2
- 229940088594 vitamin Drugs 0.000 description 2
- 150000003722 vitamin derivatives Chemical class 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- QCVGEOXPDFCNHA-UHFFFAOYSA-N 5,5-dimethyl-2,4-dioxo-1,3-oxazolidine-3-carboxamide Chemical compound CC1(C)OC(=O)N(C(N)=O)C1=O QCVGEOXPDFCNHA-UHFFFAOYSA-N 0.000 description 1
- 244000291564 Allium cepa Species 0.000 description 1
- 235000002732 Allium cepa var. cepa Nutrition 0.000 description 1
- 240000002234 Allium sativum Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 241000040710 Chela Species 0.000 description 1
- 235000002722 Dioscorea batatas Nutrition 0.000 description 1
- 235000006536 Dioscorea esculenta Nutrition 0.000 description 1
- 240000001811 Dioscorea oppositifolia Species 0.000 description 1
- 235000003416 Dioscorea oppositifolia Nutrition 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 102000004157 Hydrolases Human genes 0.000 description 1
- 108090000604 Hydrolases Proteins 0.000 description 1
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 240000000249 Morus alba Species 0.000 description 1
- 235000008708 Morus alba Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 102000035195 Peptidases Human genes 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 241000196246 Ulvaceae Species 0.000 description 1
- 244000273928 Zingiber officinale Species 0.000 description 1
- 235000006886 Zingiber officinale Nutrition 0.000 description 1
- FZQSLXQPHPOTHG-UHFFFAOYSA-N [K+].[K+].O1B([O-])OB2OB([O-])OB1O2 Chemical compound [K+].[K+].O1B([O-])OB2OB([O-])OB1O2 FZQSLXQPHPOTHG-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000010828 animal waste Substances 0.000 description 1
- 239000005557 antagonist Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 238000009933 burial Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229940038879 chelated zinc Drugs 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 235000014103 egg white Nutrition 0.000 description 1
- 210000000969 egg white Anatomy 0.000 description 1
- 238000001976 enzyme digestion Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 229960001781 ferrous sulfate Drugs 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000004611 garlic Nutrition 0.000 description 1
- 235000008397 ginger Nutrition 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 235000008935 nutritious Nutrition 0.000 description 1
- 235000020567 organic tea Nutrition 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- JVUYWILPYBCNNG-UHFFFAOYSA-N potassium;oxido(oxo)borane Chemical compound [K+].[O-]B=O JVUYWILPYBCNNG-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000007065 protein hydrolysis Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000020995 raw meat Nutrition 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 230000001932 seasonal effect Effects 0.000 description 1
- DVKSWHJSYVACNT-UHFFFAOYSA-N selanylidenephosphane Chemical compound [Se]=P DVKSWHJSYVACNT-UHFFFAOYSA-N 0.000 description 1
- QYHFIVBSNOWOCQ-UHFFFAOYSA-N selenic acid Chemical compound O[Se](O)(=O)=O QYHFIVBSNOWOCQ-UHFFFAOYSA-N 0.000 description 1
- 239000011781 sodium selenite Substances 0.000 description 1
- 229960001471 sodium selenite Drugs 0.000 description 1
- 235000015921 sodium selenite Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000003516 soil conditioner Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000009955 starching Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 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
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B15/00—Organic phosphatic fertilisers
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F11/00—Other organic fertilisers
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Fertilizers (AREA)
Abstract
The present invention relates to organic fertilizer manufacture technology field, there is provided a kind of method, selenium-enriched organic fertilizer and its application that Enteromorpha fast liquefying is produced to selenium-enriched organic fertilizer.It will concentrate, hydrolyze after fresh Enteromorpha physics defibrination, starched using concentration Enteromorpha slurry obtained by phosphoroselenoate agent phosphorylation or hydrolysis Enteromorpha, prepare selenium-enriched organic fertilizer.The method provided by the invention that Enteromorpha fast liquefying is produced to selenium-enriched organic fertilizer, can rapidly and efficiently handle Enteromorpha, and selenium-enriched organic fertilizer is made.Gained selenium-enriched organic fertilizer does not contain the selenate with strong oxidizing property, selenite, strong oxidizing property selenate, selenite be effectively prevent to the Oxidative demage of organic matter, avoid selenate, selenite be reduced to insoluble elemental selenium in itself and caused by se complementary effect forfeiture, Organic nutrient has been sufficiently reserved, has improved selenium-rich fertilizer efficiency.The selenium-enriched organic fertilizer that the present invention is prepared can use as the outer fertilizer of the base fertilizer of various crop, top dressing and root, improve the utilization rate of selenium.
Description
Technical field
It is more particularly to a kind of that Enteromorpha fast liquefying is produced into selenium-enriched organic fertilizer the present invention relates to organic fertilizer manufacture technology field
Method, selenium-enriched organic fertilizer and its application.
Background technology
The existing selenium hardening agent produced used in the technology of selenium-enriched organic fertilizer is mainly selenate and Asia with strong oxidizing property
Selenate.Selenate and selenite, all with strong oxidizing property, can be broken either in alkalescence, neutrality or under acid state
Many nutriments such as the amino acid in bad organic fertilizer, itself are reduced to insoluble elemental selenium and reduce se complementary effect.No matter
It is that Glycine Oxidation, selenite radical can be reduced to mulberry in itself by selenite under acid, alkalescence or neutral state
Elemental selenium.The oxidation reaction speed of the selenite amino acid stronger to reproducibility such as cysteine, vitamin C, sulfhydryl compound
Degree is exceedingly fast, and selenite radical is reduced to grey black elemental selenium.The presence of these redox reactions, was both destroyed in organic fertilizer
Many nutriments such as amino acid, selenic acid and selenite are reduced to insoluble elemental selenium and lose se complementary effect again in itself.
Se-enriched bio-organic fertilizer and preparation method thereof as disclosed in patent CN101717294B, it is extracted with dregs of beans enzyme hydrolysis
Amino acid, the amino acid extracted is prepared into chelating selenium, chelated zinc, chela with sodium selenite, zinc sulfate, ferrous sulfate chelating respectively
Iron is closed, gained chelating liquid compounding boric acid, calcium ions and magnesium ions antagonist prepare organic trace element composite fertilizer.Its selenite radical used
Easily obtained amino acid, vitamin C, phenolic compound can be aoxidized, itself is reduced to elemental selenium.This was both destroyed
Many nutriments such as amino acid, vitamin C in organic fertilizer, selenite are reduced to insoluble elemental selenium and lost again in itself
Lose se complementary effect.
The content of the invention
The purpose of the present invention is the oxidisability selenizing agent (selenate, selenite) used in existing selenium-enriched organic fertilizer
To the Oxidative demage of the organic matters such as amino acid, vitamin, aldehydes matter, itself it is reduced to insoluble elemental selenium and is difficult to be planted
The problem that thing absorbs, there is provided a kind of method for producing non-oxidizable selenium-enriched organic fertilizer using fresh Enteromorpha fast liquefying, be prepared
Selenium-enriched organic fertilizer be sufficiently reserved Organic nutrient, improve selenium-rich fertilizer efficiency.
In order to solve the above-mentioned technical problem, technical scheme is as follows：
The invention provides a kind of method that Enteromorpha fast liquefying is produced to selenium-enriched organic fertilizer, comprise the following steps：
(1) fresh Enteromorpha desalination is removed into defibrination after sand, Enteromorpha slurry is obtained after concentrating and separating；
(2) Enteromorpha is starched and mixed with the phosphoroselenoate agent of Enteromorpha slurry solid masses 2~500%, in temperature
It is that 0~100 DEG C and pH value carry out phosphorylation reaction under conditions of 7~12, the reaction time is 2~6h, is distilled in course of reaction
Concentration, obtain phosphorylation Enteromorpha slurry；
(3) pH value for adjusting the phosphorylation Enteromorpha slurry is 7~9, centrifugal filtration, removes residue and obtains selenium-enriched organic fertilizer.
Preferably, the phosphoroselenoate agent is phosphoroselenoate and its salt, seleno polyphosphoric acid and its salt, the oxidation of seleno ten four
The one or more of phosphorus and seleno POCl3；The seleno polyphosphoric acid is that seleno tripolyphosphate, the polyphosphoric acid of seleno four, seleno are more
Polyphosphoric acid or seleno cyclic polyphosphoric acid；The salt is ammonium salt, sylvite or sodium salt.
Preferably, the phosphoroselenoate agent replaces with the mixture of phosphoroselenoate agent and phosphoric acid agent, wherein, it is described
Phosphoric acid agent is the one or more of polyphosphoric acid and its salt, ten tetraphosphine oxides and POCl3；The polyphosphoric acid be tripolyphosphate,
Four polyphosphoric acids, polyphosphoric acids or cyclic polyphosphoric acid.
Preferably, citric acid, the addition of the citric acid have been additionally added in the Enteromorpha slurry and/or phosphorylation Enteromorpha slurry
The 0.05%~5% of quality is starched for Enteromorpha slurry or phosphorylation Enteromorpha.
Preferably, urea, the matter of the urea are additionally added in the solution before phosphorylation reaction and/or after phosphorylation reaction
Amount independently is the 0~300% of the Enteromorpha slurry or phosphorylation Enteromorpha slurry solid masses.
Preferably, also include after the centrifugal filtration：The liquid material drying-granulating that the centrifugal filtration is obtained.
Preferably, the Enteromorpha slurry replaces with the hydrolysis Enteromorpha slurry that the Enteromorpha slurry obtains after hydrolysis concentrates.
It is furthermore preferred that the hydrolysis includes acid, alkali or enzyme hydrolysis.
It is furthermore preferred that the acid or basic hydrolysis Enteromorpha include the step of slurry：By Enteromorpha slurry and Enteromorpha slurry quality
0.05%~5% acid or alkali mixing, 2~48h of hydrolysis concentration at 50~105 DEG C, obtain acid or basic hydrolysis Enteromorpha slurry.
It is furthermore preferred that the step of enzyme hydrolysis Enteromorpha slurry, includes：By Enteromorpha slurry and Enteromorpha slurry solid masses
0.05%~5% protease mixing, it is 1.5~12.0 in pH value, temperature is at 20~80 DEG C, hydrolysis 2~72h of concentration, is obtained
Starched to enzyme hydrolysis Enteromorpha.
Present invention additionally comprises the selenium-enriched organic fertilizer that the above method is prepared.
Present invention also offers the application of above-mentioned selenium-enriched organic fertilizer, it is characterised in that：The selenium-enriched organic fertilizer is diluted with water
100~10000 times use, fertilizer outside base fertilizer, top dressing and root as crop.
Compared with prior art, the present invention has advantages below：
(i), selenium-rich organic is produced with phosphoroselenoate agent phosphorylation using the protein in Enteromorpha, polypeptide and amino acid to answer
Hefei, the oxidation and the reduction of itself of the selenate, selenite of strong oxidizing property to Organic nutrient are avoided, has been avoided
The destruction of machine nutritional ingredient and selenate, selenite be reduced to insoluble elemental selenium and caused by se complementary effect forfeiture.
Protein, polypeptide and amino acid can be modified with phosphorylation, dissolubility, foaming capacity after protein phosphorylation, breast
Change ability, moisture holding capacity and solution viscosity are all greatly improved.The present invention using seleno polyphosphoric acid, the tetraphosphine oxide of seleno ten,
The phosphoroselenoate such as seleno phosphorous oxychloride agent carry out protein phosphorylation, phosphoroselenoate agent in neutral and alkali environment with albumen
Matter, polypeptide, amino acid carry out phosphorylation reaction, generate corresponding phosphoroselenoate compound.The phosphoroselenoate compound of generation is in, alkali
It is stable in property solution.Contain substantial amounts of nitrogen, phosphorus, potassium and trace elements of selenium in product, there is good fertilizer efficiency.Selenium atom can
Easily it is absorbed by crops with phosphorylation reaction liquid, there is good selenium-supply function, may be used as selenium-supply organic fertilizer.Seleno phosphorus
The use of acidulant, the selenate of strong oxidizing property, selenite are effectively prevent to the Oxidative demage of organic matter, is sufficiently reserved
Organic nutrient, improve fertilizer efficiency.Meanwhile eliminate selenate again, selenite is reduced to insoluble elemental selenium and drawn
The decline of the se complementary effect risen.Meanwhile the selenium in the selenophosphates in product readily can be absorbed by crops with phosphate, be carried
The high utilization rate of selenium.
(ii), the present invention extracts the nutritional ingredient in Enteromorpha to the direct defibrination of fresh Enteromorpha, and speed is fast, efficiency high, and recovery rate is high,
Energy consumption is low, low to nutritional ingredient destructive rate.
The skeleton structure and cellulose, hemicellulose therebetween that the macroscopic form structure of Enteromorpha is supported by cellulose, hemicellulose
Plain molecule is wrapped in nutriment and the physical aspect structure of a large amount of water collectively constitutes.Main organic nutrient substance in Enteromorpha is
The organic matters such as protein, polypeptide, polysaccharide.By physics defibrination, this macroscopic form of Enteromorpha can be abolished rapidly, breaks fiber
Element, hemicellulose molecule connect to the parcel and key of nutriment and water, and these nutritional ingredients that rapid extraction goes out in Enteromorpha are easy
Realize Enteromorpha liquefy.The method technique of physics defibrination is simple, and efficiency high, treating capacity is big, and does not have to chemical agent, is normal again
Carried out in aqueous medium under temperature, the nutritional ingredient of Enteromorpha is not destroyed substantially, nutritional ingredient retention rate is high.
Because fresh Enteromorpha contains substantial amounts of water, water content is even up to more than 90%.In order to improve the concentration of reaction solution, improve
Compoiste fertilizer solid content, go water to concentrate in Enteromorpha slurry, can both improve treatment effeciency, can obtain concentrating organic composite again
Fertilizer.
Embodiment
It is the invention provides a kind of method that Enteromorpha fast liquefying is produced to selenium-enriched organic fertilizer, fresh Enteromorpha physics defibrination is fast
The nutritional ingredients such as speed extraction protein, realize the separation of nutriment and cellulose, and Enteromorpha slurry is made.The slurry distillation of gained Enteromorpha is dense
Direct Phosphorylation after contracting, selenium-enriched organic fertilizer is prepared, also Enteromorpha can be starched by fast degradation, phosphorylation system after concentration using technology for hydrolyzing
Take selenium-rich organic composite fertilizer.Specifically include following steps：
(1) fresh Enteromorpha desalination is removed into defibrination after sand, Enteromorpha slurry is obtained after concentrating and separating；
(2) Enteromorpha is starched and mixed with the phosphoroselenoate agent of Enteromorpha slurry solid masses 2~500%, in temperature
It is that 0~100 DEG C and pH value carry out phosphorylation reaction under conditions of 7~12, the reaction time is 2~6h, is distilled in course of reaction
Concentration, obtain phosphorylation Enteromorpha slurry；
(3) pH value for adjusting the phosphorylation Enteromorpha slurry is 7~9, centrifugal filtration, removes residue and obtains selenium-enriched organic fertilizer.
The present invention is that raw material prepares selenium-enriched organic fertilizer using fresh Enteromorpha.Enteromorpha is one kind of Chlorophyta Ulvaceae, rich in egg
White matter, vitamin, fat, cellulose, carbohydrate and mineral matter, enriched with nutriment and bioactive substance it is famous,
Also contain iodine, calcium, phosphorus, iron, potassium and other trace elements, amino acid classes are complete, can prepare the nutriment and height of high-quality
Imitate organic fertilizer.Due to Enteromorpha in the characteristics of seasonal, disastrous outburst, it is necessary to concentrate salvaging, the Enteromorpha number salvaged in a short time
Amount is especially huge.Enteromorpha salvage process and salvage disembarkation after, easily rotted under normal temperature, can not normality preserve, can not also shine
Dry, drying process can rot, it is necessary to which flash baking preserves.But stoving process is extremely complex, energy consumption is high, and investment is huge.
The present invention is directly by fresh Enteromorpha physics defibrination, and by Enteromorpha fast liquefying slurrying, phosphorylation prepares selenium-enriched organic fertilizer.
Because fresh Enteromorpha seawater content is very high, up to more than 90%, its salt content is also very high.In order to avoid high in fresh Enteromorpha
Influence of the salt content to enteromorpha products, the present invention carry out immersion desalination to fresh Enteromorpha and removed sand first.In the present invention, preferably by fresh waterside
Tongue is soaked in water the salinity removed in fresh Enteromorpha.It is preferred that fresh Enteromorpha is soaked using fresh water.The fresh Enteromorpha of freshwater soaking can be with
Effective desalination, greatly reduce the salt content of product.
In the present invention, preferably Enteromorpha is soaked 2~5 times in water, can effective desalination, more preferably immersion 3~4
It is secondary.It is preferred that the time soaked every time is 5~30min, more preferably 10~20min.
The present invention is not particularly limited to the mode of fresh Enteromorpha defibrination, and fresh Enteromorpha can be processed into the property of Enteromorpha slurry
Processing mode is managed all within protection scope of the present invention.In the present invention, it is preferred to after fresh Enteromorpha is smashed, utilization is large-scale
Refining equipment carries out defibrination.
In the present invention, it is preferred to use large-scale pasture and water pulverizer smashes to fresh Enteromorpha.In order to handle collection in a short time
A large amount of Enteromorphas of middle salvaging, the processing capacity for the large-scale pasture and water pulverizer that the present invention uses is preferably greater than 50t/h, to avoid fresh waterside
Tongue is rotted.
In the present invention, fresh Enteromorpha is preferably ground into below 10cm chips, more preferably below 7cm with large-scale pasture and water pulverizer
Chip.
Enteromorpha chip after crushing is subjected to physics defibrination.
Because the Enteromorpha after smashing easily rots at normal temperatures, it requires Enteromorpha chip needs, defibrination is complete in a short time
Finish.In the present invention, it is preferred to carry out defibrination using large-scale fiberizer.Large-scale fiberizer is generally used in paper-making industry, by immersion
Most of lignin, protein in unseasoned lumber piece, fat are ground from cellulose parcel, realize lignin, protein,
The separation of fat and cellulose.Because Enteromorpha is single cropping water plant, growth period is shorter, and cellulose, hemicellulose level are low, divide
Son amount is smaller, and protein, polyoses content are higher, intermolecular containing substantial amounts of water, with fiberizer physics defibrination, can quickly abolish waterside
The macrostructure of tongue, break parcel of the cellulose cell wall to nutritional ingredient, the nutriments such as protein, polypeptide, polysaccharide are taken off
From cellulose cell wall, and quickly dissociate, be distributed in water, form Enteromorpha slurry.In the present invention, for plane mill, preferably adopt
It is more than 500mm, more preferably higher than 600mm with grinding wheel diameter, for taper rubbing disc, it is preferred to use mill maximum gauge is more than
300mm, more preferably higher than 400mm high-density paste mill extract Nutrition Composition of Entermorpha prolifera, system to the Enteromorpha chip defibrination after crushing
Obtain Enteromorpha slurry.
Because Enteromorpha slurry is formed by the direct defibrination of fresh Enteromorpha, wherein containing substantial amounts of moisture.In order to improve Enteromorpha slurry
Concentration, the present invention are concentrated Enteromorpha slurry.
The mode that the present invention starches Enteromorpha concentration is not particularly limited, using the Conventional concentration mode in this area.
In the specific embodiment of the invention, it is preferred to use be evaporated under reduced pressure concentration mode remove Enteromorpha slurry in moisture.
In the present invention, the temperature that Enteromorpha slurry is evaporated under reduced pressure concentration is preferably 30~105 DEG C, more preferably 50~90 DEG C, is entered
One step is preferably 60~80 DEG C.In the present invention, by Enteromorpha slurry be concentrated into its solids content more than 20%, more preferably 30% with
On, terminate concentration.
In the present invention, preferably citric acid is added in Enteromorpha starches concentration process.Citric acid has sterilization, except raw meat, sterilization work(
Can, deodorization, sterilization, sterilization are played in Enteromorpha processing procedure, reduces the effect of smell pollution, concentration Enteromorpha slurry is improved and uses waterside
The bin stability of compoiste fertilizer prepared by tongue.The addition of optimization citric acid for concentration after Enteromorpha starch quality 0.05~
5%, more preferably 1~3%.
Enteromorpha after concentration is starched into separation of solid and liquid, the Enteromorpha slurry and cellulose residue concentrated.
The present invention is not particularly limited to the mode of separation of solid and liquid, after being concentrated using the conventional separation methods in this area
Enteromorpha slurry separation of solid and liquid.In the specific embodiment of the invention, it is preferred to use centrifuge.
The Enteromorpha slurry being prepared can be directly used for making selenium-enriched organic fertilizer.Or preparation selenium-rich has after hydrolysis by Enteromorpha slurry
Machine fertilizer.
In the present invention, obtained Enteromorpha slurry is hydrolyzed.The macromolecular organic nutrient substance such as protein, polypeptide in Enteromorpha slurry
Matter can be hydrolyzed to small molecular protein, polypeptide, amino acid, reduce molecular weight, to improve dissolubility, improve plant absorption effect.
The present invention hydrolyzes Enteromorpha slurry by the way of acid or alkali catalyzed hydrolysis or enzymatic hydrolysis.Acid or alkali have to Enteromorpha slurry
Machine nutritional ingredient catalyzing hydrolysis scope is wide in range, but has certain destructive rate to nutritional ingredient.Enzymatic hydrolysis reaction mild condition, You Jiying
Foster material damage rate is low, and hydrolysate has been sufficiently reserved the nutritional ingredients such as amino acid, polypeptide, polysaccharide and trace element, hydrolysate
Dissolubility it is high, plant absorption utilization rate is high.
In the present invention, Enteromorpha is starched using protease and carries out enzymatic hydrolysis.Species and source of the present invention to protease
It is not particularly limited, using commercial protein enzyme, such as acid protease, neutral proteinase and alkali protease.The present invention is excellent
Choosing is digested using vegetable protein hydrolase to Enteromorpha slurry, the vegetable protein hydrolysis more preferably more than 200,000 enzyme activity
Enzyme.In the present invention, the solid gauge in being starched with Enteromorpha, the addition of the protease is preferably 0.05%~5%, more preferably
0.1~3%, it is further 0.5~2%.Suitable protease hydrolytic pH value and enzyme water are set according to the species of selection protease
Solve temperature.Preferable ph is between 1.5~12.0.When from neutral proteinase, the pH value preferably digested is 7.0~9.0；When
When selecting alkali protease, the pH value preferably digested is 8.0~12.0, more preferably 9.0~11.0.When selection acid protease
When, the pH value preferably digested is 1.5~6.5, more preferably 2.0~6.0.In the present invention, preferably adjusted with the acid or alkali that have fertilizer efficiency
The pH value of reaction solution is saved to the appropriate pH of protease.In the present invention, the reaction temperature of albumen enzymatic hydrolysis is 20 DEG C~80 DEG C,
More preferably 30~60 DEG C.The time of protease hydrolytic is 2~72h, more preferably 12~48h.In the present invention, preferably digesting
During be constantly evaporated under reduced pressure, steam moisture, concentrating hydrolysate, to promote the progress of enzyme digestion reaction, improve enzymolysis efficiency, increase
The concentration of organic fertilizer.When the present invention is preferably concentrated into hydrolyzate solids content more than 20%, more preferably higher than 30%, terminate dense
Contracting.
After hydrolysis terminates, by hydrolyzate enzyme deactivation.The present invention is not particularly limited to the mode of enzyme deactivation, it is preferred to use high temperature goes out
Enzyme process.Hydrolyzate is warming up into 80~100 DEG C inactivates enzyme, is then down to normal temperature.
In the present invention, citric acid is added in the hydrolyzate after enzyme deactivation, to prevent the nutritional ingredient in hydrolyzate from rotting to become
Matter.The addition of optimization citric acid of the present invention is that enzyme hydrolysis Enteromorpha starches 0.05~5%, more preferably the 0.1~3% of quality.
The present invention can also use acid or alkali catalyzed hydrolysis Enteromorpha to starch.Enteromorpha slurry is mixed with sour or alkali be hydrolyzed it is dense
Contracting, prepare acid or basic hydrolysis Enteromorpha slurry.
In the present invention, the acid or alkali of starching the catalyzing hydrolysis Enteromorpha reaction are not particularly limited, preferably with to plant
Acid or alkali of the growth with fertilizer efficiency；The addition of the acid or alkali is preferably the 0.05%~5% of the Enteromorpha slurry quality, more excellent
Elect 0.1~3% as, be further 0.5~2%.
In the present invention, citric acid preferably is added in the reaction solution of acid or alkali catalyzed hydrolysis Enteromorpha slurry, the citric acid adds
Dosage is preferably the 0.05%~5% of Enteromorpha slurry quality, and more preferably 0.1~3%.
In the present invention, the reaction temperature of acid or alkali catalyzed hydrolysis concentration is preferably 50 DEG C~105 DEG C, more preferably 60~
100℃.The time of hydrolysis concentration is preferably 2~48h, more preferably 8~24h.
Preferred pair enzyme, acid or alkaline hydrolyzate of the present invention centrifuge, and obtain hydrolyzing Enteromorpha slurry and cellulose residue.
Gained enteromorpha fiber element residue can be used as soil conditioner, be directly applied to farmland, can also be with animal wastes one
Rise and decomposed produce organic fertilizer.
The Enteromorpha being prepared is starched and/or hydrolyzed Enteromorpha slurry and carries out phosphorylation reaction with phosphoroselenoate agent by the present invention,
Prepare selenium-enriched organic fertilizer.Control 0~100 DEG C of the temperature of phosphorylation reaction, 30~60 DEG C of preferable temperature；Control phosphorylation reaction
PH value is 7~12, more preferably 8~11.Enteromorpha slurry is starched and/or hydrolyzes by Enteromorpha to mix with phosphoroselenoate agent, in above-mentioned bar
Phosphorylation reaction is carried out under part.
In the present invention, the method for adjusting phosphorylation reaction liquid pH value is not particularly limited, preferably had with to plant growth
There are the acid of fertilizer efficiency or alkali to adjust phosphorylation reaction liquid to required pH value.
In the present invention, alkali, phosphoroselenoate agent synchronously can be starched and/or hydrolyzed with Enteromorpha Enteromorpha slurry and mix, can also
Enteromorpha slurry is first starched and/or hydrolyzed with Enteromorpha by alkali to mix, then is mixed with phosphoroselenoate agent, and the present invention is not limited specifically this
It is fixed.In the specific embodiment of the invention, it is preferred to use preceding kind of mode.
In the present invention, the dosage of phosphoroselenoate agent starches and/or hydrolyzed Enteromorpha starches amount of solid 2%~500% for Enteromorpha,
Preferably 10%~300%, more preferably 20%~200%.
In the present invention, the phosphoroselenoate agent is phosphoroselenoate and its salt, seleno polyphosphoric acid and its salt, seleno ten aoxidize
The one or more of four phosphorus and seleno POCl3.In the present invention, the seleno polyphosphoric acid is seleno tripolyphosphate, seleno four is poly-
Phosphoric acid, seleno polyphosphoric acids or seleno cyclic polyphosphoric acid.Wherein, seleno polyphosphoric acids refers to the five poly- and its above the poly- phosphorus of seleno
Acid.Cyclic polyphosphoric acid refers to ring-type tripolyphosphate and the polyphosphoric acid of ring-type four.Big ring polyphosphoric acid typically regards the model of polyphosphoric acids as
Farmland.In the present invention, the salt is the water soluble salts such as ammonium salt, sylvite or sodium salt.
In the present invention, the phosphoric acid agent of non-seleno and phosphoroselenoate agent can also be used to be provided commonly for phosphorylation Enteromorpha
Slurry, to reduce the probability of phosphoroselenoate agent hydrolysis generation selenium anion.The phosphoric acid agent is polyphosphoric acid and its salt, ten oxidations
The one or more of four phosphorus and POCl3；The polyphosphoric acid is tripolyphosphate, four polyphosphoric acids, polyphosphoric acids or the poly- phosphorus of ring-type
Acid.It is further preferred that be ten tetraphosphine oxides, POCl3, polyphosphoric acid.
In the present invention, the dosage of the phosphoric acid agent is the 0%~200% of phosphoroselenoate agent dosage, preferably 10%
~100%.
The phosphoroselenoate agent and phosphoric acid agent can be used directly, and can also be used in the form of phosphoric acid solution.It is right
In strong water suction, can be with water, the phosphoric acid agent such as POCl3 and ten tetraphosphine oxides and their seleno of amino vigorous reaction
Thing, it is preferred to use used in the form of phosphoric acid solution.Mass percent concentration of the phosphoroselenoate agent in phosphoric acid solution
For 5~75%, preferably 20~70%, more preferably 30~60%.Quality percentage of the phosphoric acid agent in phosphoric acid solution
Specific concentration is 5~50%, preferably 25~45%.In the present invention, the preferably time of phosphorylation reaction is 2~6h, more preferably 3
~5h.After reaction terminates, obtained phosphoroselenoate Enteromorpha slurry non-oxidative, in, stable in alkaline solution, and containing a large amount of
Phosphorus, potassium and trace elements of selenium, there is good fertilizer efficiency.
The present invention is also added into urea during phosphorylation reaction.Addition opportunity of the present invention to urea be not special
Limitation, Enteromorpha can be starched and/or hydrolyzed to urea and Enteromorpha starch and mixed before phosphorylation reaction, then with phosphoroselenoate
Agent carries out phosphorylation reaction.In the present invention, it can also be added after the completion of phosphorylation reaction in obtained phosphorylation Enteromorpha slurry
Urea.In the present invention, the addition of urea starches and/or hydrolyzed Enteromorpha starches solid masses part 0~300% for Enteromorpha, is preferably
10%~200%, more preferably 20%~100%.
The pH value for adjusting phosphorylation Enteromorpha slurry is 7~9, and selenium-enriched organic fertilizer is obtained after centrifugal filtration.
In the present invention, the method for regulation phosphorylation Enteromorpha slurry pH value is not particularly limited, preferably with to plant growth
Acid or alkali regulation phosphorylation Enteromorpha with fertilizer efficiency are starched to required pH value.
In the present invention, the acid with fertilizer efficiency is preferably phosphoric acid and sulfuric acid, and the alkali with fertilizer efficiency is preferably to contain potassium
Alkali, the alkali containing potassium is preferably the salt of weak acid of potassium oxide, potassium hydroxide or potassium, and the salt of weak acid of the potassium is the inorganic weak of potassium
Hydrochlorate, such as potassium carbonate, saleratus, dipotassium tetraborate, potassium metaborate or borax.All acid or alkali can be selected a kind of or several
Kind.Preferably, all acid or alkali concentration are more than 30%.
The selenium-enriched organic fertilizer that the present invention is prepared can also be made as granular fertilizer.By the selenium-enriched organic fertilizer of liquid through being granulated
Technique is granulated, you can prepares granular pattern selenium-enriched organic fertilizer.During granulation, other kinds of fertilizer can also be added, such as
With preparing selenium-rich urea together with urea mother liquor.The present invention is not particularly limited to the technique of granulation, using the routine in this area
Prilling.Such as by after gained liquid selenium-enriched organic fertilizer further concentration, granulation is dried by the way of spray drying, is made
Take granular selenium-enriched organic fertilizer.
The selenium-enriched organic fertilizer that the present invention is prepared can be used as the outer fertilizer of base fertilizer, top dressing and root.It is diluted with water 100~10000
It is used for the administration of low selenium crop again, the particularly administration of crop, obtains Se-rich farm products for poor selenium.Fertilization mode uses cave
Mode, pick ditch fertilising burial mode, the mode of drip irrigation and the foliage spray mode that fertilising is buried.For Different Crop, using most
Good fertilization mode is applied.Any fertilization mode can be used to include leaf for the fruit tree of growth period length, Chinese yam, green onion, ginger and garlic, tealeaves etc.
The mode of face sprinkling is applied fertilizer.Present invention preferably employs the mode of drip irrigation to apply fertilizer.Especially for tealeaves, using continuous drip irrigation side
Formula, the stable selenium-rich organic tea of Se content can be obtained.According to the selenium of crop difference, soil Se content and gained selenium-enriched organic fertilizer
Content, selenium-enriched organic fertilizer mu dosage of the present invention are 2~20kg/ times, preferably 5~15kg/ times, can effectively improve these crops
Se content, yield and quality.
For the object, technical solutions and advantages of the present invention are more clearly understood, the present invention is entered with reference to embodiment
Row detailed description, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
By fresh Enteromorpha freshwater soaking four times, each 20min, below 7cm segments are ground into pasture and water pulverizer, use is highly concentrated
Fiberizer physics defibrination, Enteromorpha Organic nutrient is extracted, Enteromorpha is liquefied, prepares Enteromorpha mixing slurry.Gained Enteromorpha mixing slurry
The citric acid of Enteromorpha mixing slurry quality 2.5% is added, is centrifuged, obtains Enteromorpha slurry and cellulose residue.
Gained Enteromorpha is starched, and is evaporated under reduced pressure at 65~75 DEG C and is concentrated into solids content more than 30%, must concentrate Enteromorpha slurry.
Gained Enteromorpha is starched and concentration Enteromorpha slurry stable storing, nutritious.Gained Enteromorpha is starched and concentration Enteromorpha slurry can be used as
Feed addictive, it can also be used to which food additives and organic fertilizer make.
Embodiment 2
By gained concentration Enteromorpha slurry 1000kg in embodiment 1, under conditions of keeping reacting liquid temperature to be not higher than 40 DEG C, add
Enter the saturated solution of 480kg potassium hydroxide, add 100kg urea, fully after dissolving, be slowly added into the selenizing four of six oxygen of 200kg four
60% phosphoric acid solution of phosphorus (tetraphosphine oxide of four seleno ten), reacting liquid pH value 10~12, reaction temperature is kept to be not higher than 40 DEG C
Under the conditions of react 6h.Reacting liquid pH value is adjusted to 7 with phosphoric acid, centrifugal filtration obtains Enteromorpha selenium-rich organic composite fertilizer.
Embodiment 3
By fresh Enteromorpha freshwater soaking 3 times, each 15min, with grinding wheel diameter 600mm high-density paste mill, physics defibrination,
Enteromorpha Organic nutrient is extracted, prepares Enteromorpha slurry.Refining concentration is 15%.
Gained Enteromorpha starches 1000kg, and pH to 10~11 is adjusted with unsaturated carbonate potassium solution, adds 1.5kg alkali proteases, control
Hydrolysis 48h at 45~55 DEG C of reaction temperature processed.Hydrolysis reaction is evaporated under reduced pressure, and concentration of reaction solution solids content is extremely
40%.Being warming up to 85 DEG C inactivates enzyme, is cooled to normal temperature, centrifugal filtration, obtains enzyme hydrolysis Enteromorpha slurry.
500kg urea, fully dissolving are added in gained enzyme hydrolysis Enteromorpha slurry, is more than 10, reaction temperature not keeping pH value
Under conditions of 40 DEG C, 50% phosphoric acid of synchronous addition 613.5kg saturated solution of potassium carbonate and 500kg seleno POCl3s is molten
Liquid, it is 8~10 to keep reacting liquid pH value, reacts 3h.Citric acid 10kg is added into obtained phosphorylation reaction liquid, uses potassium carbonate
Reacting liquid pH value is adjusted to 8 by saturated solution, and centrifugal filtration removes cellulose residue, obtains selenium-rich organic composite fertilizer.
Content of each nutritional ingredient in compoiste fertilizer solids is respectively in gained liquid Enteromorpha compoiste fertilizer：Ammonia
Base acid content of peptides 4.3%, potassium content 25.1%, nitrogen content 16.9%, phosphorus content 2.6%, Se content 6.6%, remain waterside
The a variety of nutriments of tongue and trace element, it is high-quality and efficient organic Se-rich composite fertilizer.
Embodiment 4
By fresh Enteromorpha freshwater soaking four times, each 20min, crushed after desanding of desalting, with high-density paste mill, physics mill
Slurry, Enteromorpha Organic nutrient is extracted, Enteromorpha is liquefied, prepare Enteromorpha slurry.
Gained Enteromorpha is starched, and adds 2% phosphoric acid, 2% sulfuric acid, 0.8% citric acid, 12h is hydrolyzed at 85~95 DEG C.
Course of reaction is evaporated under reduced pressure and is concentrated into solids content 30%, must hydrolyze Enteromorpha slurry.
The saturated solution of 403kg potassium hydroxide is added in gained hydrolysis Enteromorpha slurry 1000kg, is keeping reacting liquid temperature 50
Under conditions of~60 DEG C, the phosphorus of ten selenizings of 150kg four, 45% phosphoric acid solution of the tetraphosphine oxides of 80kg ten are slowly added into, adjusts and protects
It is 9~10 to hold reacting liquid pH value, and it is at 60 DEG C to keep reaction temperature, reacts 5h.Reaction is finished, and reacting liquid pH value is adjusted into 9, from
The heart is filtered off except cellulose residue, liquid material are granulated Hou get selenium-rich organics composite fertilizer.
Embodiment 5
In embodiment 3 in gained Enteromorpha slurry, 3.5% potassium hydroxide saturated solution is added, is hydrolyzed at 90~100 DEG C
10h.It is 40% that course of reaction, which is evaporated under reduced pressure and is concentrated into solids content, must hydrolyze Enteromorpha slurry.
Added in gained hydrolysis Enteromorpha slurry under conditions of 80~90 DEG C of reacting liquid temperature, pH value is kept as 8~12, it is synchronous
Potassium hydroxide saturated solution, 100kg seleno tripolyphosphates are added, charging finishes, and holding reacting liquid temperature is 90 DEG C, pH value 8
2h is reacted under conditions of~12.Afterwards under same operation conditions, synchronous addition potassium hydroxide saturated solution and 50kg ten aoxidize
45% phosphoric acid solution of four phosphorus, charging finish, and holding reacting liquid temperature is 90 DEG C, pH value reacts 5h under conditions of being 8~12.Will
Reacting liquid pH value is adjusted to 9, and centrifugal filtration obtains selenium-rich organic composite fertilizer.
Embodiment 6
In June, 2015 is sub in sunshine mountain and sea day tourism and resort zone by gained organic Se-rich composite fertilizer in embodiment 3 to September
Young tea leaves leaf Specialty Co-operative Organization Tea planting carries out effect test.Tealeaves fertilizing method：Every mu of tealeaves composite fertilizer's consumption 20kg, water are dilute
500 times are released, in tea row fertigation, is picked tea-leaves after 5 days.Blank control drip irrigation same amount water, the same period pick tea-leaves.After testing, fertilization area
Tealeaves Se content is 9.8mg/kg dry teas, and check plot tealeaves Se content is 0.56mg/kg dry teas.The more preferably strong sweet smell of tealeaves fragrance
Virtue.Illustrate that using organic selenium-rich fertilizer produced by the invention tealeaves Se content can be effectively improved, energy improving quality, is high-quality selenium-rich
Compoiste fertilizer.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (12)
- A kind of 1. method that Enteromorpha fast liquefying is produced to selenium-enriched organic fertilizer, it is characterised in that comprise the following steps：(1) fresh Enteromorpha desalination is removed into defibrination after sand, Enteromorpha slurry is obtained after concentrating and separating；(2) the phosphoroselenoate agent that Enteromorpha slurry is starched to solid masses 2~500% with the Enteromorpha mixes, temperature for 0~ 100 DEG C and pH value carry out phosphorylation reaction under conditions of 7~12, and the reaction time is 2~6h, distillation and concentration in course of reaction, Obtain phosphorylation Enteromorpha slurry；(3) pH value for adjusting the phosphorylation Enteromorpha slurry is 7~9, centrifugal filtration, removes residue and obtains selenium-enriched organic fertilizer.
- 2. according to the method for claim 1, it is characterised in that the phosphoroselenoate agent is phosphoroselenoate and its salt, selenium For the one or more of polyphosphoric acid and its salt, the tetraphosphine oxide of seleno ten and seleno POCl3；The seleno polyphosphoric acid is seleno Tripolyphosphate, the polyphosphoric acid of seleno four, seleno polyphosphoric acids or seleno cyclic polyphosphoric acid；The salt is ammonium salt, sylvite or sodium salt.
- 3. according to the method for claim 2, it is characterised in that the phosphoroselenoate agent replace with phosphoroselenoate agent and The mixture of phosphoric acid agent, wherein, the phosphoric acid agent be polyphosphoric acid and its salt, ten tetraphosphine oxides and POCl3 one kind or It is several；The polyphosphoric acid is tripolyphosphate, four polyphosphoric acids, polyphosphoric acids or cyclic polyphosphoric acid.
- 4. according to the method for claim 1, it is characterised in that be additionally added in the Enteromorpha slurry and/or phosphorylation Enteromorpha slurry There is citric acid, the addition of the citric acid is starched for the Enteromorpha or phosphorylation Enteromorpha starches the 0.05%~5% of quality.
- 5. according to the method for claim 1, it is characterised in that molten before phosphorylation reaction and/or after phosphorylation reaction Urea is additionally added in liquid, the quality of the urea independently is the 0 of the Enteromorpha slurry or phosphorylation Enteromorpha slurry solid masses ~300%.
- 6. according to the method for claim 1, it is characterised in that：Also include after the centrifugal filtration：By the centrifugal filtration Obtained liquid material drying-granulating.
- 7. according to the method described in claim 1~6 any one, it is characterised in that：The Enteromorpha slurry replaces with the Enteromorpha Starch the hydrolysis Enteromorpha slurry obtained after hydrolysis concentrates.
- 8. according to the method for claim 7, it is characterised in that the hydrolysis includes acid, alkali or enzyme hydrolysis.
- 9. according to the method for claim 8, it is characterised in that the step of acid or basic hydrolysis Enteromorpha are starched includes：By institute The acid or alkali for stating Enteromorpha slurry and Enteromorpha slurry quality 0.05%~5% mix, 2~48h of hydrolysis concentration at 50~105 DEG C, Obtain acid or basic hydrolysis Enteromorpha slurry.
- 10. according to the method for claim 8, it is characterised in that the step of enzyme hydrolysis Enteromorpha is starched includes：By the waterside Tongue is starched mix with the protease of Enteromorpha slurry solid masses 0.05%~5%, is 1.5~12.0 in pH value, temperature for 20~ At 80 DEG C, hydrolysis 2~72h of concentration, enzyme hydrolysis Enteromorpha slurry is obtained.
- 11. the selenium-enriched organic fertilizer being prepared according to claim 1~10 any one methods described.
- 12. the application of selenium-enriched organic fertilizer described in claim 11, it is characterised in that：The selenium-enriched organic fertilizer is diluted with water 100~ 10000 times use, fertilizer outside base fertilizer, top dressing or root as crop.
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| US5843762A (en) * | 1995-03-02 | 1998-12-01 | Desert Energy Research, Inc. | Method for the high yield, agricultural production of enteromorpha clathrata |
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| CN103570445A (en) * | 2012-08-02 | 2014-02-12 | 青岛海大生物集团有限公司 | Preparation method of phosphorylation enteromorpha oligosaccharide powder fertilizer |
| CN104671973A (en) * | 2014-12-12 | 2015-06-03 | 青岛中天信达生物技术研发有限公司 | Selenium-rich vegetable compound fertilizer |
| CN106748581A (en) * | 2016-12-31 | 2017-05-31 | 成都育芽科技有限公司 | A kind of preparation method of selenium-rich mixed fertilizer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5843762A (en) * | 1995-03-02 | 1998-12-01 | Desert Energy Research, Inc. | Method for the high yield, agricultural production of enteromorpha clathrata |
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| CN103570445A (en) * | 2012-08-02 | 2014-02-12 | 青岛海大生物集团有限公司 | Preparation method of phosphorylation enteromorpha oligosaccharide powder fertilizer |
| CN104671973A (en) * | 2014-12-12 | 2015-06-03 | 青岛中天信达生物技术研发有限公司 | Selenium-rich vegetable compound fertilizer |
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