CN113317394A - Preparation method of rare earth modified attapulgite feed additive - Google Patents
Preparation method of rare earth modified attapulgite feed additive Download PDFInfo
- Publication number
- CN113317394A CN113317394A CN202110611619.6A CN202110611619A CN113317394A CN 113317394 A CN113317394 A CN 113317394A CN 202110611619 A CN202110611619 A CN 202110611619A CN 113317394 A CN113317394 A CN 113317394A
- Authority
- CN
- China
- Prior art keywords
- attapulgite
- rare earth
- acid
- oxide
- earth element
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229960000892 attapulgite Drugs 0.000 title claims abstract description 93
- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 93
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 61
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 17
- 239000003674 animal food additive Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000001179 sorption measurement Methods 0.000 claims abstract description 29
- 238000007873 sieving Methods 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 18
- 231100000678 Mycotoxin Toxicity 0.000 claims abstract description 17
- 239000002636 mycotoxin Substances 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 230000004048 modification Effects 0.000 claims abstract description 11
- 238000012986 modification Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 230000006870 function Effects 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000003607 modifier Substances 0.000 claims description 24
- 150000002500 ions Chemical class 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 150000007522 mineralic acids Chemical class 0.000 claims description 8
- 235000011054 acetic acid Nutrition 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- OBKXEAXTFZPCHS-UHFFFAOYSA-N 4-phenylbutyric acid Chemical compound OC(=O)CCCC1=CC=CC=C1 OBKXEAXTFZPCHS-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002535 acidifier Substances 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- ZIKATJAYWZUJPY-UHFFFAOYSA-N thulium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tm+3].[Tm+3] ZIKATJAYWZUJPY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- 229910001954 samarium oxide Inorganic materials 0.000 claims description 3
- 229940075630 samarium oxide Drugs 0.000 claims description 3
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 3
- 229910003451 terbium oxide Inorganic materials 0.000 claims description 3
- SCRZPWWVSXWCMC-UHFFFAOYSA-N terbium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tb+3].[Tb+3] SCRZPWWVSXWCMC-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 2
- 229910003440 dysprosium oxide Inorganic materials 0.000 claims description 2
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(iii) oxide Chemical compound O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 claims description 2
- 229910001940 europium oxide Inorganic materials 0.000 claims description 2
- 229940075616 europium oxide Drugs 0.000 claims description 2
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910001938 gadolinium oxide Inorganic materials 0.000 claims description 2
- 229940075613 gadolinium oxide Drugs 0.000 claims description 2
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 2
- JYTUFVYWTIKZGR-UHFFFAOYSA-N holmium oxide Inorganic materials [O][Ho]O[Ho][O] JYTUFVYWTIKZGR-UHFFFAOYSA-N 0.000 claims description 2
- OWCYYNSBGXMRQN-UHFFFAOYSA-N holmium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ho+3].[Ho+3] OWCYYNSBGXMRQN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 229910003443 lutetium oxide Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- MPARYNQUYZOBJM-UHFFFAOYSA-N oxo(oxolutetiooxy)lutetium Chemical compound O=[Lu]O[Lu]=O MPARYNQUYZOBJM-UHFFFAOYSA-N 0.000 claims description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 2
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 2
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 claims description 2
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 229910003454 ytterbium oxide Inorganic materials 0.000 claims description 2
- 229940075624 ytterbium oxide Drugs 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 1
- 244000144972 livestock Species 0.000 abstract description 3
- 244000144977 poultry Species 0.000 abstract description 3
- 239000004094 surface-active agent Substances 0.000 abstract description 3
- 230000007413 intestinal health Effects 0.000 abstract description 2
- 230000004060 metabolic process Effects 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- LINOMUASTDIRTM-QGRHZQQGSA-N deoxynivalenol Chemical compound C([C@@]12[C@@]3(C[C@@H](O)[C@H]1O[C@@H]1C=C(C([C@@H](O)[C@@]13CO)=O)C)C)O2 LINOMUASTDIRTM-QGRHZQQGSA-N 0.000 description 17
- LINOMUASTDIRTM-UHFFFAOYSA-N vomitoxin hydrate Natural products OCC12C(O)C(=O)C(C)=CC1OC1C(O)CC2(C)C11CO1 LINOMUASTDIRTM-UHFFFAOYSA-N 0.000 description 12
- -1 degrading microbe Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 241001465754 Metazoa Species 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 239000003463 adsorbent Substances 0.000 description 6
- 230000000844 anti-bacterial effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000006378 damage Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052706 scandium Inorganic materials 0.000 description 5
- MBMQEIFVQACCCH-UHFFFAOYSA-N trans-Zearalenon Natural products O=C1OC(C)CCCC(=O)CCCC=CC2=CC(O)=CC(O)=C21 MBMQEIFVQACCCH-UHFFFAOYSA-N 0.000 description 5
- MBMQEIFVQACCCH-QBODLPLBSA-N zearalenone Chemical compound O=C1O[C@@H](C)CCCC(=O)CCC\C=C\C2=CC(O)=CC(O)=C21 MBMQEIFVQACCCH-QBODLPLBSA-N 0.000 description 5
- 229910052765 Lutetium Inorganic materials 0.000 description 4
- 241000282887 Suidae Species 0.000 description 4
- 230000003385 bacteriostatic effect Effects 0.000 description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 4
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 4
- 230000001737 promoting effect Effects 0.000 description 4
- 229910052771 Terbium Inorganic materials 0.000 description 3
- 238000009395 breeding Methods 0.000 description 3
- 230000001488 breeding effect Effects 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical compound [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 3
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 3
- 229930195730 Aflatoxin Natural products 0.000 description 2
- XWIYFDMXXLINPU-UHFFFAOYSA-N Aflatoxin G Chemical compound O=C1OCCC2=C1C(=O)OC1=C2C(OC)=CC2=C1C1C=COC1O2 XWIYFDMXXLINPU-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 241000282898 Sus scrofa Species 0.000 description 2
- 239000005409 aflatoxin Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 244000052616 bacterial pathogen Species 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 210000001035 gastrointestinal tract Anatomy 0.000 description 2
- 210000005027 intestinal barrier Anatomy 0.000 description 2
- 230000007358 intestinal barrier function Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 125000005372 silanol group Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 208000031295 Animal disease Diseases 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- 241000283690 Bos taurus Species 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 238000005411 Van der Waals force Methods 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
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000005784 autoimmunity Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 229930002954 deoxynivalenol Natural products 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 102000038379 digestive enzymes Human genes 0.000 description 1
- 108091007734 digestive enzymes Proteins 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000002158 endotoxin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000012041 food component Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000000050 nutritive effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229950009215 phenylbutanoic acid Drugs 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 108700012359 toxins Proteins 0.000 description 1
- 229930013292 trichothecene Natural products 0.000 description 1
- LZAJKCZTKKKZNT-PMNGPLLRSA-N trichothecene Chemical compound C12([C@@]3(CC[C@H]2OC2C=C(CCC23C)C)C)CO1 LZAJKCZTKKKZNT-PMNGPLLRSA-N 0.000 description 1
- 239000000273 veterinary drug Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/20—Inorganic substances, e.g. oligoelements
- A23K20/28—Silicates, e.g. perlites, zeolites or bentonites
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/20—Inorganic substances, e.g. oligoelements
- A23K20/30—Oligoelements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Animal Husbandry (AREA)
- Food Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a preparation method of an attapulgite feed additive with mycotoxin adsorption and bacteriostasis functions, which comprises the steps of carrying out acid modification treatment on attapulgite, adding a prepared compound rare earth element ion surfactant after purifying impurities, reacting for 8 hours at 50-90 ℃, and precipitating, roasting, washing, drying, crushing and sieving a product to obtain the rare earth modified attapulgite feed additive which has mycotoxin adsorption and bacteriostasis functions and can regulate organism metabolism, and can be applied to livestock feed addition and improve the intestinal health of livestock and poultry.
Description
Technical Field
The invention relates to a preparation method of a rare earth modified attapulgite feed additive, belonging to the field of deep processing of economic ores.
Background
The pollution of mycotoxins to feed and raw materials is a global problem, and vomitoxin (also known as deoxynivalenol, DON) is the most representative type B trichothecene type toxins and is easily generated in the growth and storage processes of feed raw materials such as corn, wheat and the like. The vomitoxin has stable chemical property, and the counter measures aiming at the existing pollution problem of the vomitoxin of the feed raw materials mainly comprise the following steps: adding non-nutritive adsorbent, degrading microbe, chemical isomeric modification, deactivating biological enzyme and diluting raw material. Various biodegradation and chemical modification methods have the problems of harsh reaction conditions, unstable effect, change of nutritional components of the feed and the like in the using process. The adsorption rate of the common adsorbent to vomitoxin in the artificial simulated pig digestive tract is only 10-30%. Therefore, the method reduces the potential harm of vomitoxin to the pigs by researching and developing a new technology or an adsorption product, and is one of the fundamental ways for promoting the healthy development of the domestic pig industry and ensuring the national food safety.
The adsorption method is one of effective methods for treating the exceeding of the mycotoxin in the feed and raw materials. The natural aluminum silicate ore has stronger ion exchange capacity and adsorption performance and has application potential in mycotoxin adsorption. Wherein, attapulgite and montmorillonite are nonmetal ore adsorbents widely applied to feed addition at present, and the adsorption capacity of the attapulgite and the montmorillonite to common mycotoxins is generally improved by adopting a surfactant modification mode in the current technical means: chinese patent CN 104888691B (preparation method of attapulgite zearalenone adsorbent with antibacterial function) adopts long-chain imidazolium compound as surfactant to modify attapulgite, and remarkably improves antibacterial property of attapulgite and adsorption capacity of zearalenone; chinese patent CN107243325B (preparation method of attapulgite mycotoxin adsorbent with antibacterial function) adopts inorganic acid, organic acid and betaine to modify attapulgite, and remarkably improves adsorption capacity of attapulgite on zearalenone and aflatoxin; chinese patent CN 102658081A (modified montmorillonite capable of adsorbing zearalenone and preparation method) adopts cetyl trimethyl ammonium bromide to modify activated montmorillonite, and grinding into powder to obtain adsorbent with good zearalenone adsorption capacity.
In 7 months in 2020, the use of feed antibiotics is completely forbidden in China, and the importance of healthy breeding of live pigs is also increased to a new level. The vomitoxin in the feed and raw materials can cause damage to the intestinal barrier of animals, cause pathogenic bacteria and endotoxin in the intestinal tract to carry out blood circulation, cause inflammatory reaction of the animals and damage to the autoimmunity and growth performance of the animals. Therefore, the research and development of the novel feed additive with mycotoxin adsorption and bacteriostasis performance is a safe and effective way for reducing the harm of vomitoxin in the feed and realizing healthy breeding of live pigs.
Rare earth (Rare earth) is a generic name of seventeen metal elements including lanthanoid elements and scandium and yttrium in the periodic table of elements. At present, a large number of animal experiments show that the rare earth elements added into the feed can improve the yield of pigs, poultry, cattle and aquatic products, improve the meat quality and feed reward, and improve the immunity and survival rate of animals. Meanwhile, the rare earth elements have the effects of sterilization and bacteriostasis, and can reduce the usage amount of veterinary drugs and the occurrence of animal diseases. The attapulgite has a microporous structure similar to a molecular sieve and a surface active structure of a silanol group, and has stronger cation exchange and adsorption performances, so that the attapulgite can be used as an ideal carrier of rare earth elements. The adsorption rate of the unmodified attapulgite on mycotoxins with stronger polarity, such as aflatoxin, is usually more than 80%, and the in vitro adsorption rate on vomitoxin is only 10-30%. Therefore, the modification and activation of the rare earth element ions on the attapulgite are a key link for further improving the adsorption capacity and the antibacterial performance of the attapulgite on vomitoxin.
The rare earth element oxide can form stable rare earth element ion aqueous solution after inorganic acid reaction. The attapulgite has a surface active structure of silanol groups, can perform cation exchange with a rare earth element ion aqueous solution, and simultaneously regulates the micellization behavior by changing the types of anions and cations of the attapulgite. The attapulgite has stable intermolecular acting force such as electrostatic action, hydrogen bond, van der waals force, etc., and can form more stable hydrate structure after being roasted at 50-90 ℃, and simultaneously improve the adsorption activity of the product. Owing to the catalytic activity of rare earth elements, rare earth element ion modifiers have been widely used to improve the activity of catalytic products. Although rare earth elements have the characteristics of promoting growth, inhibiting bacteria and the like, no case for improving the adsorption performance of the product on the bacteria inhibiting and vomitoxin by using rare earth element ions to modify the non-metallic ore exists at present.
Disclosure of Invention
The invention provides a preparation method of a rare earth modified attapulgite feed additive, aiming at the key problems of harm of mycotoxin pollution in feed and raw materials to livestock and poultry breeding and feed antibiotic prohibition. The preparation method realizes effective integration of antibacterial and growth promoting properties of rare earth elements and cation exchange and adsorption properties of attapulgite. The product prepared by the invention generally has the performances of bacteriostasis, mycotoxin adsorption, high stability and the like, can be safely applied to animal feed addition, and improves the intestinal health of animals.
The principle of the invention is as follows: the attapulgite powder with certain bacteriostatic performance and adsorption activity is obtained by carrying out acid modification treatment on attapulgite, and then the compound rare earth element ion modifier with bacteriostatic and growth promoting functions is added, and the product is precipitated, roasted, washed, dried, crushed and sieved to obtain the rare earth modified attapulgite feed additive with the performances of mycotoxin adsorption, bacteriostasis, acid stability and the like.
The invention relates to a technical scheme of a preparation method of a rare earth modified attapulgite feed additive, which comprises the following steps:
the method comprises the following steps: weighing a certain amount of attapulgite, crushing the attapulgite into a homogeneous state by using a grinder, adding a proper amount of water to prepare slurry, then adding a sufficient amount of inorganic or organic acid according to a certain proportion for modification, stirring the slurry for 4 to 8 hours at room temperature by using a magnetic stirrer, sieving the slurry by using a 200-mesh sieve to remove impurities, drying the purified attapulgite, roasting the dried attapulgite at the temperature of 200-mesh and 500 ℃ in a low-oxygen environment to obtain acidified modified attapulgite, crushing the attapulgite into a homogeneous state by using a grinder, and sieving the homogenized attapulgite by using a 200-mesh sieve to obtain acid modified attapulgite powder.
Step two: weighing a certain amount of rare earth element oxide, adding inorganic acid according to a certain proportion, fully reacting for 4-8h at 50-90 ℃, and filtering by filter paper to remove unreacted impurities to obtain the compound rare earth element ion modifier.
Step three: and (3) adding the rare earth element ion modifier prepared in the step (II) into the acidified and modified attapulgite powder obtained in the step (I), completely soaking at 50-90 ℃, evaporating to dryness, and roasting at 200-500 ℃ in a low-oxygen environment to obtain the compound rare earth element modified attapulgite.
Step four: sequentially adding deionized water and ethanol into the attapulgite prepared by roasting in the third step for washing, removing the rare earth element ion modifier which is not combined with the attapulgite, drying at 50-90 ℃ for 4-8h, crushing into homogeneity by a grinder, and sieving by a 200-mesh sieve to obtain the novel feed additive with mycotoxin adsorption and bacteriostasis functions.
Wherein, the acid modifier in the step one is one or a compound of sulfuric acid, perchloric acid, phosphoric acid, pyrophosphoric acid, hydrochloric acid, nitric acid, lactic acid, citric acid, acetic acid, propionic acid and phenylbutyric acid, and the mole number of the added acidifier is H+In terms of molar equivalent, the ratio of mol) to attapulgite (kg) is 20: 1 or higher.
Wherein, the rare earth element oxide in the second step is one or a compound of lanthanum oxide, cerium oxide, praseodymium oxide, neodymium oxide, samarium oxide, europium oxide, gadolinium oxide, terbium oxide, dysprosium oxide, holmium oxide, erbium oxide, ytterbium oxide, lutetium oxide, yttrium oxide, scandium oxide and thulium oxide; the inorganic acid is one or a compound of dilute hydrochloric acid, dilute nitric acid and dilute sulfuric acid, and the mole number of the added acidifying agent is H+In terms of molar equivalent, mol) to the rare earth element oxide is 10: 1 or higher.
Wherein the prepared rare earth element modified attapulgite has the general chemical formula characteristics that: mg (magnesium)5Si8O20(OH)2X4·4Y·4H2And O, wherein X is the anion of the acid modifier, and Y is the cation of the rare earth element. Taking the example that the dilute hydrochloric acid and the lanthanum oxide are respectively used as the acid modifier and the rare earth element ion modifier in the second step and the third step of the claim 1, the molecular formula of the obtained rare earth modified attapulgite is Mg5Si8O20(OH)2Cl4·4La·4H2O。
Compared with the existing attapulgite modification method, the method has the following advantages:
1. the rare earth element ion modifier not only has certain ion exchange capacity, but also has the performance of improving the activity of animal digestive enzyme and inhibiting the growth of pathogenic bacteria.
2. The preparation method has simple process and easily controlled and optimized production conditions.
3. The product obtained by the preparation method has relatively stable physical and chemical properties and is easy to store.
4. The product has the performances of bacteriostasis, growth promotion, mycotoxin adsorption and the like, is not easy to generate chemical reaction with other products, and can be compatible with the complex use of other feed additive products.
Drawings
FIG. 1 is a functional diagram of rare earth modified attapulgite
FIG. 2 Infrared Spectrum of rare earth modified Attapulgite (example 1)
FIG. 3 comparison of the adsorption capacity of the rare earth modified attapulgite and the adsorption capacity of the unmodified attapulgite for vomitoxin (example 1)
FIG. 4 comparison of the bacteriostatic ability of rare earth modified attapulgite and unmodified attapulgite (liquid medium, example 1)
FIG. 5 comparison of the bacteriostatic ability of rare earth modified attapulgite and unmodified attapulgite (solid medium, example 1)
Detailed Description
The technical solutions of the present invention are further described below with reference to examples, and the technical solutions related to the present invention are not limited to the following specific embodiments.
Example 1: weighing 100g of attapulgite, crushing the attapulgite into a homogeneous state by using a grinder, sieving the homogeneous state by using a 300-mesh sieve, adding 500mL of water to prepare slurry, then adding 240mL of 10mmol/L citric acid to perform acid modification, stirring the slurry by using a magnetic stirrer at room temperature for 8 hours, sieving the slurry by using a 200-mesh sieve to remove impurities, roasting the mixture at 300 ℃ in a low-oxygen environment to obtain acidified modified attapulgite, and sieving the acidified modified attapulgite by using a 200-mesh sieve to obtain acid modified attapulgite powder. Weighing 30g of lanthanum oxide, cerium oxide and samarium oxide respectively, adding 500mL of 10mmol/L hydrochloric acid, fully reacting for 8h, filtering and removing impurities to obtain the rare earth ion modifier for lanthanum, cerium and samarium. Mixing the attapulgite powder and the rare earth ion modifier according to the proportion of 1: 1, uniformly mixing, evaporating to dryness, roasting at 200-500 ℃ in a low-oxygen environment to obtain the compound rare earth element modified attapulgite, washing 3 times by using sufficient deionized water and ethanol respectively, drying for 8 hours at 50-90 ℃, crushing into a homogeneous state by using a grinder, and sieving by using a 200-mesh sieve to obtain the lanthanum, cerium and samarium rare earth ion modified attapulgite feed additive with mycotoxin adsorption and bacteriostasis functions.
Example 2: weighing 100g of attapulgite, crushing the attapulgite into a homogeneous state by using a grinder, sieving the homogeneous state by using a 300-mesh sieve, adding 500mL of water to prepare slurry, then adding 180mL of 10 mmol/L4-phenylbutyric acid to perform acid modification, stirring the mixture for 8 hours at room temperature by using a magnetic stirrer, sieving the mixture by using a 200-mesh sieve to remove impurities, roasting the mixture at 300 ℃ in a low-oxygen environment to obtain the 4-phenylbutyric acid modified attapulgite, and sieving the roasted product by using a 200-mesh sieve to obtain the acid modified attapulgite powder. Weighing 100g of lanthanum oxide, adding 500mL of 10mmol/L hydrochloric acid, fully reacting for 4h, filtering to remove impurities, and obtaining the lanthanum ion modifier. Mixing the attapulgite powder and the rare earth ion modifier according to the proportion of 1: 1, uniformly mixing, evaporating to dryness, roasting at 200 ℃ in a low-oxygen environment to obtain the lanthanum ion modified attapulgite, then washing 3 times by using sufficient deionized water and ethanol respectively, drying at 50-90 ℃ for 4 hours, grinding into powder, and sieving by a 200-mesh sieve to obtain the lanthanum ion modified attapulgite feed additive with mycotoxin adsorption, intestinal barrier repair promotion and antibacterial performance.
Example 3: weighing 100g of attapulgite, crushing the attapulgite into a homogeneous state by using a grinder, sieving the homogeneous state by using a 300-mesh sieve, adding 500mL of water to prepare slurry, then adding 480mL of 10mmol/L acetic acid to perform acid modification, stirring the slurry by using a magnetic stirrer at room temperature for 8 hours, sieving the slurry by using a 200-mesh sieve to remove impurities, roasting the mixture at 300 ℃ in a low-oxygen environment to obtain acetic acid modified attapulgite, and sieving the acetic acid modified attapulgite by using a 200-mesh sieve to obtain acid modified attapulgite powder. Weighing 30g of terbium oxide, lutetium and scandium respectively, adding 500mL of 10mmol/L sulfuric acid, fully reacting for 4h, and filtering to remove impurities to obtain the terbium, lutetium and scandium ion modifier. Mixing the attapulgite powder and the rare earth ion modifier according to the proportion of 1: 1, uniformly mixing, evaporating to dryness, roasting at 200 ℃ in a low-oxygen environment to obtain the rare earth element modified attapulgite compounded by terbium, lutetium and scandium, then washing 3 times by using sufficient deionized water and ethanol respectively, drying at 50-90 ℃ for 4 hours, grinding into powder, and sieving by using a 200-mesh sieve to obtain the terbium/lutetium/scandium ion modified attapulgite feed additive with strong sterilization and growth promotion performances.
Claims (2)
1. The preparation method of the rare earth modified attapulgite feed additive is characterized by comprising the following four steps:
step one (modification of attapulgite acid): weighing a certain amount of attapulgite, crushing the attapulgite into a homogeneous state by using a grinder, adding a proper amount of water to prepare slurry, then adding a sufficient amount of inorganic or organic acid according to a certain proportion for modification, stirring the slurry for 4 to 8 hours at room temperature by using a magnetic stirrer, sieving the slurry by using a 200-mesh sieve to remove impurities, drying the purified attapulgite, roasting the dried attapulgite at the temperature of 200-mesh and 500 ℃ in a low-oxygen environment to obtain acidified modified attapulgite, crushing the attapulgite into a homogeneous state by using a grinder, and sieving the homogenized attapulgite by using a 200-mesh sieve to obtain acid modified attapulgite powder; the acid modifier in the first step is one or a compound of sulfuric acid, perchloric acid, phosphoric acid, pyrophosphoric acid, hydrochloric acid, nitric acid, lactic acid, citric acid, acetic acid, propionic acid and phenylbutyric acid, and the mole number of the added acidifier is H+In terms of molar equivalent, the ratio of mol) to attapulgite (kg) is 20: 1 or higher;
step two (preparation of composite rare earth element ion modifier): weighing a certain amount of rare earth element oxide, adding inorganic acid according to a certain proportion, fully reacting for 4-8h at 50-90 ℃, and filtering by filter paper to remove unreacted impurities to obtain a compound rare earth element ion modifier; wherein the rare earth element oxide in the second step is one or a compound of lanthanum oxide, cerium oxide, praseodymium oxide, neodymium oxide, samarium oxide, europium oxide, gadolinium oxide, terbium oxide, dysprosium oxide, holmium oxide, erbium oxide, ytterbium oxide, lutetium oxide, yttrium oxide, scandium oxide and thulium oxide; the inorganic acid is one or a compound of dilute hydrochloric acid, dilute nitric acid and dilute sulfuric acid, and the mole number of the added acidifying agent is H+In terms of molar equivalent, mol) to the rare earth element oxide is 10: 1 or higher;
step three (modifying attapulgite by utilizing rare earth element ions): adding the rare earth element ion modifier prepared in the step two into the acidified and modified attapulgite powder obtained in the step one, completely soaking at 50-90 ℃, evaporating to dryness, and roasting at 200-500 ℃ in a low-oxygen environment to obtain the compound rare earth element modified attapulgite;
step four (washing, drying and purifying): sequentially adding deionized water and ethanol into the attapulgite prepared by roasting in the third step for washing, removing the rare earth element ion modifier which is not combined with the attapulgite, drying at 50-90 ℃ for 4-8h, crushing into homogeneity by a grinder, and sieving by a 200-mesh sieve to obtain the novel feed additive with mycotoxin adsorption and bacteriostasis functions.
2. The preparation method of claim 1, wherein the prepared rare earth modified attapulgite has a general chemical formula as follows: mg (magnesium)5Si8O20(OH)2X4·4Y·4H2And O, wherein X is the anion of the acid modifier, and Y is the cation of the rare earth element. Taking the example that the diluted hydrochloric acid and the lanthanum oxide are respectively used as the acid modifier and the rare earth element ion modifier in the second step and the third step of the claim 1, the molecular formula of the obtained rare earth element modified attapulgite is Mg5Si8O20(OH)2Cl4·4La·4H2O。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110611619.6A CN113317394B (en) | 2021-06-02 | Preparation method of rare earth modified attapulgite feed additive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110611619.6A CN113317394B (en) | 2021-06-02 | Preparation method of rare earth modified attapulgite feed additive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113317394A true CN113317394A (en) | 2021-08-31 |
| CN113317394B CN113317394B (en) | 2024-07-09 |
Family
ID=
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040028678A1 (en) * | 2000-11-15 | 2004-02-12 | Norbert Schall | Use of activated layered silicates for the adsorption of mycotoxins |
| CN1823613A (en) * | 2006-03-29 | 2006-08-30 | 浙江大学 | Controlled slow release type rare-earth feed additive and its preparation and use method |
| CN109876766A (en) * | 2019-03-12 | 2019-06-14 | 兰州大学 | A kind of attapulgite loaded rare earth composite material and preparation method thereof |
| CN110193342A (en) * | 2019-06-12 | 2019-09-03 | 明光市飞洲新材料有限公司 | A kind of modified attapulgite earth adsorbing and preparation method thereof |
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040028678A1 (en) * | 2000-11-15 | 2004-02-12 | Norbert Schall | Use of activated layered silicates for the adsorption of mycotoxins |
| CN1823613A (en) * | 2006-03-29 | 2006-08-30 | 浙江大学 | Controlled slow release type rare-earth feed additive and its preparation and use method |
| CN109876766A (en) * | 2019-03-12 | 2019-06-14 | 兰州大学 | A kind of attapulgite loaded rare earth composite material and preparation method thereof |
| CN110193342A (en) * | 2019-06-12 | 2019-09-03 | 明光市飞洲新材料有限公司 | A kind of modified attapulgite earth adsorbing and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| ZHONG, HQ ET.AL: "Preparation of effective carvacrol/attapulgite hybrid antibacterial materials by mechanical milling", JOURNAL OF POROUS MATERIALS, 31 January 2020 (2020-01-31), pages 843 - 853, XP037145780, DOI: 10.1007/s10934-020-00863-7 * |
| 杨磊等: "粉煤灰负载铈吸附剂的制备研究", 《稀土》, pages 83 - 86 * |
| 苗琛琛等: "镧改性凹凸棒土的制备及其对水中磷酸盐的吸附", 《环境工程学报》, 31 December 2016 (2016-12-31), pages 7069 - 7074 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106578418B (en) | Mineral mold remover for feed and preparation method thereof | |
| CA2382449A1 (en) | Metal-containing compositions, preparations and uses | |
| CN104888691A (en) | Preparation method of antibacterial attapulgite zearalenone adsorbent | |
| CN107243325A (en) | The preparation method of attapulgite mold toxin sorbent with antibacterial functions | |
| WO2010028215A1 (en) | Antimicrobial fish and shrimp feed | |
| WO2003077673A1 (en) | A process for producing a feed additive adsorbing the mycotoxin in the animal feed | |
| CN103449539A (en) | Water quality purifier special for aquaculture | |
| CN113100087A (en) | Production process of bentonite crushed cat litter | |
| CN107159140B (en) | Preparation method of organic-inorganic composite attapulgite mycotoxin adsorbent | |
| CN112998147B (en) | Chitosan-loaded copper montmorillonite intercalation composite material and preparation method and application thereof | |
| CN113317394B (en) | Preparation method of rare earth modified attapulgite feed additive | |
| CN113317394A (en) | Preparation method of rare earth modified attapulgite feed additive | |
| JP4995612B2 (en) | Water purification agent | |
| WO2003077674A1 (en) | A feed additive of nanometer size, a process preparing the same and a feed containing the feed additive of nanometer size | |
| CN113443722B (en) | Efficient medicament, preparation process and application of efficient medicament in aquaculture wastewater treatment | |
| CN112841191A (en) | Preparation method of chitosan antibacterial agent | |
| CN103749980B (en) | Improved-type Selenium supplement agent of intestinal mucosa and its production and use | |
| CN1203777C (en) | Universal detoxicant | |
| CN111771905B (en) | Solid hydrogen peroxide and preparation method and application thereof | |
| CN108059253B (en) | Composite modifier for removing water phosphide and preparation method thereof | |
| CN101157710B (en) | Method for preparing iron supplementary carboxymethyl Chitosan oligosaccharide ferrous | |
| CN115737546B (en) | Tinidazole sodium chloride injection and production process thereof | |
| CN117343337B (en) | Preparation method and application of capsaicin-class substance-entrapped metal-organic framework material | |
| CN110124617A (en) | A kind of vitamin B1Modified montmorillonite used compound fungus endotoxin adsorbent and its preparation method and application | |
| CN112655823B (en) | Clay/amino acid compound additive and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |