CN114680234B - Methionine hydroxy analogue isopropyl ester compound and preparation method and production system thereof - Google Patents
Methionine hydroxy analogue isopropyl ester compound and preparation method and production system thereof Download PDFInfo
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- CN114680234B CN114680234B CN202210356754.5A CN202210356754A CN114680234B CN 114680234 B CN114680234 B CN 114680234B CN 202210356754 A CN202210356754 A CN 202210356754A CN 114680234 B CN114680234 B CN 114680234B
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- China
- Prior art keywords
- hydroxy analogue
- methionine hydroxy
- calcium
- isopropyl ester
- methionine
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- 229930182817 methionine Natural products 0.000 title claims abstract description 190
- -1 Methionine hydroxy analogue isopropyl ester compound Chemical class 0.000 title claims abstract description 113
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 85
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000007787 solid Substances 0.000 claims abstract description 41
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 36
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 33
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011575 calcium Substances 0.000 claims abstract description 28
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 235000019691 monocalcium phosphate Nutrition 0.000 claims abstract description 27
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 claims abstract description 22
- 239000001506 calcium phosphate Substances 0.000 claims abstract description 20
- 238000005886 esterification reaction Methods 0.000 claims abstract description 18
- 229940043430 calcium compound Drugs 0.000 claims abstract description 17
- 150000001674 calcium compounds Chemical class 0.000 claims abstract description 17
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 229910000150 monocalcium phosphate Inorganic materials 0.000 claims abstract description 9
- 239000013638 trimer Substances 0.000 claims abstract description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 91
- 229960005069 calcium Drugs 0.000 claims description 27
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 238000001694 spray drying Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 14
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 12
- 239000000920 calcium hydroxide Substances 0.000 claims description 12
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 12
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 claims description 10
- 235000019739 Dicalciumphosphate Nutrition 0.000 claims description 9
- 229910000390 dicalcium phosphate Inorganic materials 0.000 claims description 9
- 229940038472 dicalcium phosphate Drugs 0.000 claims description 9
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- NEFBYIFKOOEVPA-UHFFFAOYSA-K dicalcium phosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])([O-])=O NEFBYIFKOOEVPA-UHFFFAOYSA-K 0.000 claims description 7
- 235000019700 dicalcium phosphate Nutrition 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 3
- 229910001385 heavy metal Inorganic materials 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 abstract description 25
- 239000000203 mixture Substances 0.000 abstract description 16
- 239000007788 liquid Substances 0.000 abstract description 15
- 210000004767 rumen Anatomy 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 6
- 241000282849 Ruminantia Species 0.000 abstract description 5
- 230000032050 esterification Effects 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 210000003298 dental enamel Anatomy 0.000 description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000011259 mixed solution Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 18
- PICCHNWCTUUCAQ-UHFFFAOYSA-N 2-hydroxypentanethioic s-acid Chemical compound CCCC(O)C(O)=S PICCHNWCTUUCAQ-UHFFFAOYSA-N 0.000 description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- 238000004128 high performance liquid chromatography Methods 0.000 description 14
- 239000000178 monomer Substances 0.000 description 13
- 230000009969 flowable effect Effects 0.000 description 12
- 238000010992 reflux Methods 0.000 description 12
- 238000007873 sieving Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 241000283690 Bos taurus Species 0.000 description 9
- 239000000539 dimer Substances 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 7
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 241001465754 Metazoa Species 0.000 description 4
- 238000007605 air drying Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000001727 in vivo Methods 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000013589 supplement Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000004060 metabolic process Effects 0.000 description 3
- 230000008979 phosphorus utilization Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- SRMCAKWGHOOMDV-ZETCQYMHSA-N (2s)-4-methylsulfanyl-2-(propan-2-ylamino)butanoic acid Chemical compound CSCC[C@@H](C(O)=O)NC(C)C SRMCAKWGHOOMDV-ZETCQYMHSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 235000015278 beef Nutrition 0.000 description 2
- 229960001714 calcium phosphate Drugs 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- RPHZRUDLEUBFCM-UHFFFAOYSA-L calcium;methanedisulfonate Chemical class [Ca+2].[O-]S(=O)(=O)CS([O-])(=O)=O RPHZRUDLEUBFCM-UHFFFAOYSA-L 0.000 description 2
- MWKXCSMICWVRGW-UHFFFAOYSA-N calcium;phosphane Chemical compound P.[Ca] MWKXCSMICWVRGW-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 210000002381 plasma Anatomy 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- KFSJYZYQSZKRRQ-BYPYZUCNSA-N (2s)-2-(hydroxyamino)-4-methylsulfanylbutanoic acid Chemical class CSCC[C@H](NO)C(O)=O KFSJYZYQSZKRRQ-BYPYZUCNSA-N 0.000 description 1
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- VWWOJJANXYSACS-UHFFFAOYSA-N 2-hydroxy-4-methylsulfanylbutanenitrile Chemical compound CSCCC(O)C#N VWWOJJANXYSACS-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 210000000981 epithelium Anatomy 0.000 description 1
- 239000003797 essential amino acid Substances 0.000 description 1
- 235000020776 essential amino acid Nutrition 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000014075 nitrogen utilization Effects 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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
- A23K20/10—Organic substances
- A23K20/142—Amino acids; Derivatives thereof
-
- 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
- A23K20/26—Compounds containing phosphorus
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K50/00—Feeding-stuffs specially adapted for particular animals
- A23K50/10—Feeding-stuffs specially adapted for particular animals for ruminants
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23N—MACHINES OR APPARATUS FOR TREATING HARVESTED FRUIT, VEGETABLES OR FLOWER BULBS IN BULK, NOT OTHERWISE PROVIDED FOR; PEELING VEGETABLES OR FRUIT IN BULK; APPARATUS FOR PREPARING ANIMAL FEEDING- STUFFS
- A23N17/00—Apparatus specially adapted for preparing animal feeding-stuffs
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Organic Chemistry (AREA)
- Animal Husbandry (AREA)
- Zoology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Birds (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fodder In General (AREA)
Abstract
The invention relates to the technical field of organic synthesis and preparation, in particular to a methionine hydroxy analogue isopropyl ester compound, a preparation method and a production system thereof, wherein the methionine hydroxy analogue isopropyl ester compound is a compound of methionine hydroxy analogue isopropyl ester, methionine hydroxy analogue dimer isopropyl ester, methionine hydroxy analogue trimer isopropyl ester, methionine hydroxy analogue calcium salt and calcium phosphate salt, and is in a solid powder form. In the preparation method, phosphoric acid, calcium hydrophosphate or monocalcium phosphate and a composition thereof are adopted as esterification catalysts, calcium compounds are used for neutralization, and then the reaction solution is directly concentrated, so that the steps that the catalysts need to be separated from the reaction solution and the isopropyl methionine hydroxy analogue product does not need to be washed and rectified for purification, the energy consumption for purifying the product and the residual liquid incineration treatment process are saved, and the utilization rate of methionine sources is improved. The solid powdery methionine hydroxy analogue isopropyl ester compound has high stability and high rumen bypass rate of ruminants.
Description
Technical Field
The invention relates to the technical field of organic synthesis and preparation, in particular to an isopropyl methionine hydroxy analogue compound, a preparation method and a production system thereof.
Background
Methionine hydroxy analogue is intermediate of methionine metabolism, and does not have amino group, so deamination can not occur in metabolism, free ammonia in rumen and blood can be utilized when methionine is formed by in vivo metabolism, nitrogen deposition in vivo is increased, nitrogen utilization efficiency is improved, nitrogen excretion is reduced, and pollution to environment is further reduced. Although methionine hydroxy analogue can promote fiber degradation and acetic acid growth, it is easier to be degraded by microorganisms in vivo, and has short residence time and low utilization rate in vivo, so that it is necessary to protect it. The protection of methionine hydroxy analogue mainly adopts esterification reaction of methionine hydroxy analogue and alcohol to prepare protective methionine hydroxy analogue ester compound. The hydroxy analogue isopropyl methionine, also called hydroxy isopropyl methionine, is one of basic units of protein, is the only sulfur-containing amino acid in essential amino acid, is rumen protected methionine, can be quickly absorbed in rumen epithelium, so as to avoid degradation of microorganisms, is hydrolyzed into hydroxy analogue methionine and isopropanol, is then converted into methionine and acetone, is a methionine source with higher biological titer, and can increase milk yield and milk quality of cows and increase concentration of free amino acid in blood plasma when the cows are raised. The structural formula of the hydroxy analogue isopropyl ester of methionine is as follows:
The existing synthetic process routes of the hydroxy analogue isopropyl ester of methionine have three routes: 1) 2-hydroxy-4-methylthiobutyrate is used as a raw material for preparation; 2) The patent CN104860855 discloses a scheme for preparing high-purity D, L-2-hydroxy-4-methylthiobutyrate by using 2-hydroxy-4-methylthiobutyronitrile synthesized by oneself and hydrochloric acid alcohol (methanol, ethanol, isopropanol and isobutanol) as raw materials; 3) The method is characterized in that methionine hydroxy analogue is used as a raw material, concentrated sulfuric acid, phosphoric acid or acid resin is used as a catalyst, toluene, carbon tetrachloride, benzene, tetrahydrofuran and the like are used as organic solvents, esterification reaction is directly carried out with alcohol, and D, L-2-hydroxy-4-methylthiobutyrate is obtained through rectification and purification.
Patent US6660880B uses a third method, using isopropanol and liquid methionine as raw materials (68% monomer, 20% oligomer, 12% water), alkyd ratio 2-10:1, using concentrated sulfuric acid or acid resin Amberlyst15 as a catalyst, carrying out intermittent reaction at the reaction temperature of 80-100 ℃ for 5h, wherein the reaction product contains unreacted liquid methionine, unreacted isopropanol, liquid methionine monomer ester and liquid methionine oligomer ester. And neutralizing, distilling to remove water and alcohol, and rectifying the reaction product to obtain the monomer ester. The method separately introduces the catalyst, and a neutralization treatment step is needed in the product purification process. In the recycling process of byproduct streams or heavy recycle streams mentioned in the examples, the reaction and catalyst recycling steps still need to be carried out again, which is not beneficial to industrial continuous production.
U.S. Pat. nos. 3761518 and 3850987 disclose the preparation of high purity D, L-2-hydroxy-4-methylthiobutyrate by reacting D, L-2-hydroxy-4-methylthiobutyrate (calcium salt, sodium salt, potassium salt, ammonium salt, etc.) with alkyl alcohols (methanol, ethanol, isopropanol, butanol, etc.) under the catalytic action of hydrogen chloride; the process is complicated in operation, and particularly, the raw material D, L-2-hydroxy-4-methylthiobutyrate is prepared, namely D, L-2-hydroxy-4-methylthiobutyrate is subjected to sulfuric acid hydrolysis, ammonia neutralization and desalination to obtain 88% of aqueous solutions of monomers, dimers and polymers of D, L-2-hydroxy-4-methylthiobutyrate, wherein the monomers content is 65%, the dimers and polymers content is 23% and the water content is 12%, and in order to obtain the monomers D, L-2-hydroxy-4-methylthiobutyrate, the polymers are required to be hydrolyzed by adding alkali to obtain D, L-2-hydroxy-4-methylthiobutyrate, and the D, L-2-hydroxy-4-methylthiobutyrate is converted into D, L-2-hydroxy-4-methylthiobutyrate under the action of hydrogen chloride, and the D, L-2-hydroxy-4-methylthiobutyrate is partially polymerized to form dimers and polymers, which can lead to low purity of the product, and low yield of D, L-2-hydroxy-4-methylthiobutyrate compared with low yield of D, L-2-hydroxy-4-methylthiobutyrate.
Through prior art analysis, the following problems exist: the method adopts any mode to obtain the final product which is the high-purity D, L-2-hydroxy-4-methylthiobutyrate monomer and is a viscous brown yellow liquid. In order to obtain high-purity monomers, a large amount of acid-containing and salt-containing wastewater is inevitably generated, and because the reactivity of the esterification reaction of the dimer and the multimer in the methionine hydroxy analogue is low, even if the obtained esterified product can be esterified, the boiling point of the esterified product of the dimer and the multimer is high because the molecular mass is large (more than 300), the esterified product of the dimer and the multimer cannot be obtained in a rectification mode, and the esterified product of the dimer and the multimer is remained in rectification residual liquid, and the final treatment can only be subjected to incineration treatment; furthermore, the raffinate after the esterification of the methionine hydroxy analogue of the rectification monomer not only contains dimer and polymer esterification products, but also contains catalyst inorganic acid, aiming at the inorganic acid liquid treatment, mainly the esterification reaction of the methionine hydroxy analogue recycled to the next batch is carried out, or the evaporation concentration treatment is carried out after the neutralization by adding alkali, but in any way, the biggest problem is that: the monomer methionine hydroxy analogue ester has low yield, high energy consumption for processing products and residual liquid, and large material consumption, while dimers and multimers in the residual liquid, even unreacted methionine hydroxy analogue monomer and the like are high-quality methionine sources which can be digested and absorbed by animals, and the incineration treatment not only causes resource waste, but also causes environmental pollution, and generates a large amount of carbon emission and sulfur oxides.
Calcium hydrogen phosphate, calcium dihydrogen phosphate and dicalcium phosphate are common mineral feeds for supplementing calcium and phosphorus to cows and beef cattle. The feed-grade standard of calcium hydrophosphate in China specifies: phosphorus is not less than 16%, calcium is not less than 21%, and fluorine is not more than 0.18%. In different physiological stages, the calcium level in the concentrate of dairy cows and beef cattle is controlled to be 0.9-1.2%, and the phosphorus level is controlled to be 0.5-0.7%.
The organic combination of isopropyl methionine hydroxy analogue, liquid methionine calcium salt and calcium phosphate salt not only supplements high-quality methionine source for ruminant animals and increases rumen bypass of methionine, but also can supplement high-quality organic calcium and phosphorus for animals, and has almost no relevant report at present.
Disclosure of Invention
In view of the above, the invention aims to provide the methionine hydroxy analogue isopropyl ester compound, the preparation method and the production system thereof, and the prepared methionine hydroxy analogue isopropyl ester compound has the advantages of high stability, high rumen bypass rate of ruminants, convenient addition and convenient transportation and storage.
The invention solves the technical problems by the following technical means:
In one aspect, the present invention provides a methionine hydroxy analogue isopropyl ester complex, wherein the methionine hydroxy analogue isopropyl ester complex is in a solid powder form, and the methionine hydroxy analogue isopropyl ester complex is a complex of methionine hydroxy analogue isopropyl ester, methionine hydroxy analogue dimer isopropyl ester, methionine hydroxy analogue trimer isopropyl ester, methionine hydroxy analogue calcium salt and calcium phosphate salt.
Preferably, the calcium phosphate salt is at least one of calcium hydrogen phosphate, calcium dihydrogen phosphate and dicalcium phosphate.
Preferably, the calcium phosphate salt accounts for 21-57% of the weight of the methionine hydroxy analogue isopropyl ester compound.
Preferably, in the methionine hydroxy analogue isopropyl ester compound, the mass percentage of the methionine hydroxy analogue isopropyl ester is 33% -63% based on the methionine hydroxy analogue.
Preferably, the chemical formula of the methionine hydroxy analogue isopropyl ester complex is as follows:
Wherein n=1, 2,3 … …; x+y=1.0, x=0.01 to 1.0, y=0.01 to 1.0.
The invention also provides a preparation method of the methionine hydroxy analogue isopropyl ester compound, which comprises the following steps:
mixing and stirring methionine hydroxy analogue, isopropanol and a catalyst, heating to 55-110 ℃, carrying out esterification reaction for 1-6 h to obtain methionine hydroxy analogue-isopropyl ester mixed solution, wherein the catalyst is one or two of calcium hydrophosphate and calcium dihydrogen phosphate, and concentrating the mixed solution under reduced pressure to a solvent-free state after the reaction is finished to obtain solid powdery methionine hydroxy analogue-isopropyl ester compound;
Or mixing and stirring methionine hydroxy analogue, isopropanol and a catalyst, heating to 55-110 ℃, carrying out esterification reaction for 1-6 h to obtain methionine hydroxy analogue-isopropyl ester mixed liquor, wherein the catalyst is one or two of phosphoric acid, calcium hydrophosphate and monocalcium phosphate, stirring and adding a calcium compound into the cooled mixed liquor after the reaction is finished, neutralizing, and concentrating under reduced pressure to a solvent-free state after the neutralization reaction is finished to obtain the solid powdery methionine hydroxy analogue-isopropyl ester compound.
Preferably, the mass percentage of the methionine hydroxy analogue is 40% -99% and the water content is 0.85% -60%; the mass percentage of the isopropanol is 50% -99.9%.
Preferably, the mass percentage of the phosphoric acid is 35-85%, the mass ratio of phosphorus pentoxide to fluoride ions in the phosphoric acid is more than or equal to 300, and the heavy metal content is less than 8ppm.
Preferably, the molar ratio of the methionine hydroxy analogue to the isopropanol to the catalyst is 1:2-10:0.2-1.5.
Preferably, the calcium compound is at least one of calcium oxide, calcium hydroxide or calcium carbonate, the pH value end point of the neutralization of the calcium compound is 3.5-6.5, and the neutralization reaction temperature is 40-60 ℃.
In still another aspect, the invention provides a production system for producing the methionine hydroxy analogue isopropyl ester compound, the production system comprises a first reaction kettle, a second reaction kettle and a spray drying tower, wherein the outlet of the first reaction kettle is connected with the inlet of the second reaction kettle, the outlet of the second reaction kettle is connected with the inlet of the spray drying tower, the bottom of the spray drying tower is provided with a product outlet, the top outlet is connected with a condenser, the condenser is used for cooling hot gas discharged from the spray drying tower, the hot gas discharged from the top of the spray drying tower is condensed by the condenser and then is used for recovering isopropyl alcohol and water, and the condensed gas is directly exhausted; the second reaction kettle is provided with a feed inlet and an online pH meter.
In the preparation method of the methionine hydroxy analogue isopropyl ester compound, phosphoric acid, calcium hydrophosphate or calcium biphosphate and a composition thereof are adopted as esterification catalysts, calcium compounds are used for neutralization, and then the unreacted isopropyl alcohol is recovered by direct concentration, so that the steps that the catalyst needs to be separated from reaction liquid and the product of the methionine hydroxy analogue isopropyl ester does not need to be washed and rectified for purification are omitted, the purification energy consumption of the product and the residual liquid incineration treatment process are greatly saved, the carbon emission and the sulfur oxide emission are greatly reduced, and the utilization rate of methionine sources is improved. According to the invention, a production system is optimized, after the reaction is finished, calcium compound neutralization is carried out, then spray drying is directly carried out, isopropanol is cooled and recycled, the obtained product is solid powdery methionine hydroxy analogue isopropyl ester compound, the compound is completely different from the existing high-purity methionine hydroxy analogue isopropyl ester monomer, and the powdery solid is the compound of methionine hydroxy analogue isopropyl ester, methionine hydroxy analogue dimer isopropyl ester, methionine hydroxy analogue trimer isopropyl ester, methionine hydroxy analogue calcium salt and calcium phosphate salt, and the production system has the advantages of simple device, low production cost, high yield, mild reaction condition, simple process, easiness in product separation and the like.
The methionine hydroxy analogue isopropyl ester compound organically combines the methionine hydroxy analogue isopropyl ester, liquid methionine calcium salt and calcium phosphate salt, not only supplements high-quality methionine sources for ruminants and increases rumen bypass of methionine, but also can supplement high-quality organic calcium and phosphorus for the animals. Compared with the traditional single methionine hydroxy analogue isopropyl ester, the solid powdery methionine hydroxy analogue isopropyl ester compound has the advantages of high stability, high rumen bypass rate of ruminants, convenient addition, convenient transportation and storage and mixing with other feed raw materials.
Drawings
FIG. 1 is a schematic flow chart of the production system of isopropyl methionine hydroxy analogue of the present invention;
wherein, the first reaction kettle 1, the second reaction kettle 2, the spray drying tower 3 and the condenser 4;
FIG. 2 is a reaction scheme of esterification of hydroxy methionine analog with isopropanol according to the present invention;
FIG. 3 is a reaction scheme of the unesterified methionine hydroxy analogue with calcium compound of the present invention;
FIG. 4 is a reaction formula of the catalyst of the present invention with calcium compounds.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The methionine hydroxy analogue isopropyl ester compound is solid powder, and the methionine hydroxy analogue isopropyl ester compound is a compound of methionine hydroxy analogue isopropyl ester, methionine hydroxy analogue dimer isopropyl ester, methionine hydroxy analogue trimer isopropyl ester, methionine hydroxy analogue calcium salt and calcium phosphate salt. Wherein the calcium phosphate salt is at least one of calcium hydrophosphate, monocalcium phosphate and dicalcium phosphate, and the mass percentage of the calcium phosphate salt in the methionine hydroxy analogue isopropyl ester compound is 21-57%; in the methionine hydroxy analogue isopropyl ester compound, the mass percentage of the methionine hydroxy analogue isopropyl ester is 33% -63% based on the methionine hydroxy analogue. The chemical formula of the methionine hydroxy analogue isopropyl ester compound is as follows:
Wherein n=1, 2,3 … …; x+y=1.0, x=0.01 to 1.0, y=0.01 to 1.0.
The preparation method of the methionine hydroxy analogue isopropyl ester compound of the invention can be roughly divided into two kinds, and one preparation method is as follows:
Mixing and stirring methionine hydroxy analogue, isopropanol and a catalyst, heating to 55-110 ℃, carrying out esterification reaction for 1-6 h to obtain methionine hydroxy analogue-isopropyl ester mixed liquor, wherein the catalyst is one or two of calcium hydrophosphate and calcium biphosphate, and concentrating the mixed liquor under reduced pressure to a solvent-free state after the reaction is finished to obtain solid powdery methionine hydroxy analogue isopropyl ester compound.
The other preparation method is as follows:
Mixing and stirring methionine hydroxy analogue, isopropanol and a catalyst, heating to 55-110 ℃, carrying out esterification reaction for 1-6 h to obtain methionine hydroxy analogue-isopropyl ester mixed liquor, wherein the catalyst is one or two of phosphoric acid, calcium hydrophosphate and monocalcium phosphate, stirring and adding a calcium compound into the cooled mixed liquor after the reaction is finished for neutralization, and concentrating under reduced pressure to a solvent-free state after the neutralization reaction is finished to obtain solid powdery methionine hydroxy analogue-isopropyl ester compound.
In the above two preparation methods, the methionine hydroxy analogue used is 40% -99%, preferably 70% -99%, particularly preferably 88% -99%, water content is 0.85% -60%, preferably 1% -30%, particularly preferably 1% -12%, the methionine hydroxy analogue may be a methionine hydroxy analogue of commercial grade, the main content of which is 88%, or a methionine hydroxy analogue subjected to concentration treatment, the main content of which is 90% -99%, or a semi-finished product after desalting in the production process of the methionine hydroxy analogue, the main content of which is 95% -99%. The mass percentage of the isopropanol is 50-99.9%, preferably 70-99.9%, particularly preferably 70-99.9%. The phosphoric acid is wet phosphoric acid, the wet phosphoric acid is phosphoric acid, sulfuric acid extraction is carried out, phosphogypsum is filtered, the obtained crude phosphoric acid aqueous solution is defluorinated, dearsenated and calcium, magnesium, aluminum and other ions are removed, and the crude phosphoric acid aqueous solution is concentrated, wherein the phosphoric acid is prepared by concentrating, the mass percentage of the phosphoric acid is 35% -85%, preferably 50% -85%, particularly preferably 65% -85%, the mass ratio of phosphorus pentoxide to fluorine ion is more than or equal to 300, the heavy metal content is less than 8ppm, and the phosphoric acid aqueous solution can be directly used for producing feed-grade calcium phosphate salt compounds; both calcium hydrogen phosphate and calcium dihydrogen phosphate are feed-grade; the molar ratio of the methionine hydroxy analogue to the isopropanol to the catalyst is 1:2-10:0.2-1.5, preferably 1:5-8:0.4-1.5; the esterification reaction temperature is 55 to 110 ℃, preferably 80 to 120 ℃, particularly preferably 85 to 110 ℃, and the reaction time is 1 to 6 hours, preferably 2 to 4 hours, particularly preferably 2.5 to 3 hours. The calcium compound is one or more of calcium oxide, calcium hydroxide or calcium carbonate, preferably calcium oxide or calcium hydroxide; the pH value end point of the neutralization of the calcium compound is 3.5-6.5; the neutralization reaction temperature is 40℃to 60℃and preferably 40℃to 50℃and particularly preferably 40℃to 45 ℃.
In the two preparation methods, the reaction formula of esterification reaction of methionine hydroxy analogue and isopropanol is shown in figure 2, the reaction formula of esterification reaction of non-methionine hydroxy analogue and calcium compound is shown in figure 3, the reaction formula of catalyst and calcium compound is shown in figure 4, x+y=1.0, x=0.01-1.0, y=0.01-1.0 in figure 4.
The production system of the methionine hydroxy analogue isopropyl ester compound is shown in figure 1, and comprises a first reaction kettle 1, a second reaction kettle 2 and a spray drying tower 3, wherein the outlet of the first reaction kettle 1 is connected with the inlet of the second reaction kettle 2, the outlet of the second reaction kettle 2 is connected with the inlet of the spray drying tower 3, the bottom of the spray drying tower 3 is provided with a product outlet, the top outlet is connected with a condenser 4, the condenser 4 is used for cooling hot gas discharged from the spray drying tower, the hot gas discharged from the top of the spray drying tower 3 is condensed by the condenser 4 and then is used for recovering isopropyl alcohol and water, and the condensed gas is directly exhausted; the second reaction kettle 2 is provided with a feed inlet and an online pH meter, and the feed inlet is used for adding calcium compounds. The production process operating method using the above production system may be one or more of batch, semi-continuous or continuous, preferably semi-continuous or continuous.
In order to better understand the technical solution of the present invention, the following experiments were performed:
Example 1
To a 1000 ml reaction flask were added 151.15 g (1.0 mol) of a methionine hydroxy analogue having a mass% of 99%, 150.76 g (1.0 mol) of phosphoric acid having a mass% of 65%, and 484.85 g (8.0 mol) of isopropyl alcohol having a mass% of 99%, and the mixture was stirred and heated to 110℃to keep a reflux state and reacted for 2.5 hours, and the increase of isopropyl ester of the methionine hydroxy analogue during the reaction was monitored by HPLC analysis. After the reaction is finished, cooling the obtained mixed solution to 45 ℃, slowly adding 38.54 g of calcium hydroxide powder with the mass percent of 96% under the stirring state, controlling the neutralization reaction temperature to be 40-45 ℃, controlling the pH value at the end point of the neutralization reaction to be 3.5, directly concentrating under reduced pressure to be in a solvent-free state, transferring the obtained solid into an enamel tray, putting the enamel tray into a blast drying box, drying at 80 ℃ to constant weight, obtaining 315.20 g of off-white solid, grinding and sieving to obtain the dispersible flowable off-white isopropyl methionine hydroxy analogue phosphate monocalcium complex with the bulk density of 0.86 g/ml, the isopropyl methionine hydroxy analogue (calculated by methionine hydroxy analogue) with the mass percent of 47.59%, and the calcium dihydrogen phosphate with the mass percent of 39.98%.
Example 2
To a 1000 ml reaction flask were added 170.45 g (1.0 mol) of 88% by mass methionine hydroxy analogue, 46.12 g (0.4 mol) of 85% by mass phosphoric acid and 303.54 g (5.0 mol) of 99% by mass isopropyl alcohol, and the mixture was stirred and heated to 85℃to keep a slightly boiling state and reacted for 3 hours, and the increase of isopropyl ester of methionine hydroxy analogue during the reaction was monitored by HPLC analysis during the reaction. After the reaction is finished, the obtained mixed solution is cooled to 40 ℃, 22.85 g of calcium oxide powder is slowly added under the stirring state, the neutralization reaction temperature is controlled to be 40-45 ℃, the pH value at the end point of the neutralization reaction is controlled to be 6.0, then the mixed solution is directly decompressed and concentrated to be in a solvent-free state, the obtained solid is transferred into an enamel tray, the enamel tray is put into an air drying box and dried to be constant weight at 80 ℃ to obtain 265.80 g of off-white solid, after grinding and sieving, the obtained dispersible and flowable off-white methionine hydroxy analogue isopropyl ester calcium hydrophosphate compound has the bulk density of 0.9 g/ml, the weight percentage of the methionine hydroxy analogue isopropyl ester (calculated by the methionine hydroxy analogue) is 56.43%, and the weight percentage of the calcium hydrophosphate is 25.88%.
Example 3
To a 1000 ml reaction flask were added 157.89 g (1.0 mol) of a methionine hydroxy analogue having a mass% of 95%, 226.15 g (1.5 mol) of phosphoric acid having a mass% of 65%, and 484.85 g (5.0 mol) of isopropyl alcohol having a mass% of 99%, and the mixture was stirred and heated to 100℃to be maintained in a reflux state, and reacted for 3.0 hours, and the increase of the methionine hydroxy analogue isopropyl ester during the reaction was monitored by high performance liquid chromatography. After the reaction is finished, the obtained mixed solution is cooled to 45 ℃, 118.5 g of calcium hydroxide powder with the mass percent of 96% is slowly added under the stirring state, the neutralization reaction temperature is controlled to be 40-45 ℃, the pH value at the end point of the neutralization reaction is controlled to be 6.5, then the mixed solution is directly decompressed and concentrated to be in a solvent-free state, the obtained solid is transferred into an enamel tray, the enamel tray is put into a blast drying box and dried to be constant weight at 80 ℃ to obtain 452.82 g of off-white solid, after grinding and sieving, the obtained dispersible and flowable off-white methionine hydroxy analogue isopropyl ester calcium hydrophosphate compound with the bulk density of 0.95 g/ml is obtained, the mass percent of the methionine hydroxy analogue isopropyl ester (calculated by the methionine hydroxy analogue) is 33.13%, and the mass percent of the calcium hydrophosphate is 56.98%.
Example 4
To a 1000 ml reaction flask were added 170.45 g (1.0 mol) of 88% by mass methionine hydroxy analogue, 46.12 g (0.4 mol) of 85% by mass phosphoric acid and 303.54 g (5.0 mol) of 99% by mass isopropyl alcohol, and the mixture was stirred and heated to 100℃to keep a slightly boiling state and reacted for 3 hours, and the increase of isopropyl ester of methionine hydroxy analogue during the reaction was monitored by HPLC analysis during the reaction. After the reaction is finished, the obtained mixed solution is cooled to 40 ℃, 12.31 g of calcium oxide powder is slowly added under the stirring state, the neutralization reaction temperature is controlled to be 40-45 ℃, the end pH value of the neutralization reaction is controlled to be 3.5, then the mixed solution is directly decompressed and concentrated to be in a solvent-free state, the obtained solid is transferred into an enamel tray, the enamel tray is put into an air drying box and dried to be constant weight at 85 ℃ to obtain 238.41 g of off-white solid, after grinding and sieving, the obtained dispersible and flowable off-white methionine hydroxy analogue isopropyl ester calcium dihydrogen phosphate compound has the bulk density of 0.84 g/ml, the isopropyl methionine hydroxy analogue (calculated by methionine hydroxy analogue) mass percentage of 62.92% and the calcium dihydrogen phosphate mass percentage of 21.15%.
Example 5
To a 1000 ml reaction flask were added 151.15 g (1.0 mol) of a methionine hydroxy analogue having a mass% of 99%, 150.76 g (1.0 mol) of phosphoric acid having a mass% of 65%, and 484.85 g (8.0 mol) of isopropyl alcohol having a mass% of 99%, and the mixture was stirred and heated to 110℃to keep a reflux state and reacted for 2.5 hours, and the increase of isopropyl ester of the methionine hydroxy analogue during the reaction was monitored by HPLC analysis. After the reaction is finished, cooling the obtained mixed solution to 45 ℃, slowly adding 48.54 g of calcium hydroxide powder with the mass percent of 96% under the stirring state, controlling the neutralization reaction temperature to be 40-45 ℃, controlling the pH value at the end point of the neutralization reaction to be 4.5, directly concentrating under reduced pressure to be in a solvent-free state, transferring the obtained solid into an enamel tray, putting the enamel tray into a blast drying box, drying at 80 ℃ to constant weight, obtaining 323.50 g of off-white solid, grinding and sieving to obtain the dispersible flowable off-white methionine hydroxy analogue isopropyl ester calcium biphosphate compound with the bulk density of 0.88 g/ml, the mass percent of methionine hydroxy analogue isopropyl ester (calculated by methionine hydroxy analogue) is 46.37%, and the mass percent of dicalcium phosphate is 46.06%.
Example 6
To a 1000 ml reaction flask were added 157.89 g (1.0 mol) of a methionine hydroxy analogue having a mass% of 95%, 120.62 g (0.8 mol) of phosphoric acid having a mass% of 65%, and 514.28 g (6.0 mol) of isopropyl alcohol having a mass% of 70%, and the mixture was stirred and heated to 110℃to keep a reflux state and reacted for 3.0 hours, and the increase of the methionine hydroxy analogue isopropyl ester during the reaction was monitored by high performance liquid chromatography. After the reaction is finished, the obtained mixed solution is cooled to 45 ℃, 48.5 g of calcium hydroxide powder with the mass percent of 96% is slowly added under the stirring state, the neutralization reaction temperature is controlled to be 40-45 ℃, the pH value at the end point of the neutralization reaction is controlled to be 4.6, then the mixed solution is directly decompressed and concentrated to be in a solvent-free state, the obtained solid is transferred into an enamel tray, the enamel tray is put into a blast drying box and dried to be constant weight at 85 ℃ to obtain 315.23 g of off-white solid, after grinding and sieving, the obtained dispersible and flowable off-white methionine hydroxy analogue isopropyl ester dicalcium phosphate compound with the bulk density of 0.90 g/ml, the mass percent of the methionine hydroxy analogue isopropyl ester (calculated by the methionine hydroxy analogue) is 47.58%, and the mass percent of the dicalcium phosphate is 38.07%.
Example 7
To a 1000 ml reaction flask were added 166.67 g (1.0 mol) of methionine hydroxy analogue having a mass percentage of 90%, 73.5 g (0.6 mol) of phosphoric acid having a mass percentage of 80% and 300.30 g (5.0 mol) of isopropyl alcohol having a mass percentage of 99.9%, and the mixture was stirred and heated to 105℃to keep a reflux state and reacted for 3.0 hours, and the increase of isopropyl ester of methionine hydroxy analogue during the reaction was monitored by high performance liquid chromatography. After the reaction is finished, the obtained mixed solution is cooled to 40 ℃, 48.25 g of calcium hydroxide powder with the mass percent of 96% is slowly added under the stirring state, the neutralization reaction temperature is controlled to be 40-45 ℃, the pH value at the end point of the neutralization reaction is controlled to be 6.0, then the mixed solution is directly decompressed and concentrated to be in a solvent-free state, the obtained solid is transferred into an enamel tray, the enamel tray is put into a blast drying box and dried to be constant weight at 80 ℃ to obtain 305.55 g of off-white solid, after grinding and sieving, the obtained dispersible and flowable off-white methionine hydroxy analogue isopropyl ester calcium hydrophosphate compound with the bulk density of 0.92 g/ml is obtained, the mass percent of the methionine hydroxy analogue isopropyl ester (calculated by the methionine hydroxy analogue) is 49.10%, and the mass percent of the calcium hydrophosphate is 33.77%.
Example 8
151.15 G (1.0 mol) of methionine hydroxy analogue with the mass percent of 99%, 101.84 g (0.4 mol) of feed-grade monocalcium phosphate with the mass percent of 99% and 484.85 g (8.0 mol) of isopropyl alcohol with the mass percent of 99% are added into a 1000 ml reaction bottle, stirred and heated to 110 ℃, kept in a reflux state and reacted for 2.5 hours, and the increase of isopropyl ester of the methionine hydroxy analogue in the reaction process is monitored by high performance liquid chromatography analysis in the reaction process. After the reaction is finished, directly concentrating under reduced pressure to a solvent-free state, transferring the obtained solid into an enamel tray, putting the enamel tray into an air drying oven, drying the enamel tray at 85 ℃ to constant weight, obtaining 288.42 g of off-white solid, grinding and sieving the off-white solid to obtain the dispersible and flowable off-white methionine hydroxy analogue isopropyl ester calcium biphosphate compound, wherein the bulk density is 0.88 g/ml, the mass percentage of the methionine hydroxy analogue isopropyl ester (calculated by the methionine hydroxy analogue) is 52.01%, and the mass percentage of the calcium biphosphate is 35.31%.
Example 9
To a 1000 ml reaction flask were added 151.15 g (1.0 mol) of methionine hydroxy analogue with a mass percentage of 99%, 69.53 g (0.4 mol) of feed-grade calcium hydrogen phosphate with a mass percentage of 99%, 46.12 g (0.4 mol) of phosphoric acid with a mass percentage of 85% and 484.85 g (8.0 mol) of isopropyl alcohol with a mass percentage of 99%, and the mixture was stirred and heated to 110℃to keep a reflux state and reacted for 2.5 hours, and during the reaction, the increase of isopropyl ester of methionine hydroxy analogue was monitored by HPLC analysis. After the reaction is finished, the obtained mixed solution is cooled to 40 ℃, 15.50 g of calcium hydroxide powder with the mass percent of 96% is slowly added under the stirring state, the neutralization reaction temperature is controlled to be 40-45 ℃, the pH value at the end point of the neutralization reaction is controlled to be 4.5, then the mixed solution is directly decompressed and concentrated to be in a solvent-free state, the obtained solid is transferred into an enamel tray, the enamel tray is put into a blast drying box and dried to be constant weight at 80 ℃ to obtain 306.94 g of off-white solid, after grinding and sieving, the obtained dispersible and flowable off-white methionine hydroxy analogue isopropyl ester dicalcium phosphate compound with the bulk density of 0.87 g/ml, the mass percent of the methionine hydroxy analogue isopropyl ester (calculated by the methionine hydroxy analogue) is 48.87%, and the mass percent of the dicalcium phosphate is 39.08%.
Example 10
To a 1000 ml reaction flask were added 151.15 g (1.0 mol) of methionine hydroxy analogue with a mass percentage of 99%, 69.54 g (0.4 mol) of feed-grade calcium hydrogen phosphate with a mass percentage of 99%, 46.12 g (0.4 mol) of phosphoric acid with a mass percentage of 85% and 484.85 g (8.0 mol) of isopropyl alcohol with a mass percentage of 99%, and the mixture was stirred and heated to 110℃to keep a reflux state and reacted for 2.5 hours, and during the reaction, the increase of isopropyl ester of methionine hydroxy analogue was monitored by HPLC analysis. After the reaction is finished, the obtained mixed solution is cooled to 40 ℃, 32.80 g of calcium hydroxide powder with the mass percent of 96% is slowly added under the stirring state, the neutralization reaction temperature is controlled to be 40-45 ℃, the pH value at the end point of the neutralization reaction is controlled to be 6.5, then the mixed solution is directly decompressed and concentrated to be in a solvent-free state, the obtained solid is transferred into an enamel tray, the enamel tray is put into a blast drying box and dried to be constant weight at 85 ℃ to obtain 333.60 g of off-white solid, after grinding and sieving, the obtained dispersible and flowable off-white methionine hydroxy analogue isopropyl ester calcium hydrophosphate compound with the bulk density of 0.89 g/ml is obtained, the mass percent of the methionine hydroxy analogue isopropyl ester (calculated by the methionine hydroxy analogue) is 44.96%, and the mass percent of the calcium hydrophosphate is 41.25%.
Example 11
To a 1000 ml reaction flask were added 151.15 g (1.0 mol) of methionine hydroxy analogue with a mass percentage of 99%, 86.87 g (0.5 mol) of feed-grade calcium hydrogen phosphate with a mass percentage of 99%, 75.38 g (0.5 mol) of phosphoric acid with a mass percentage of 65% and 484.85 g (8.0 mol) of isopropyl alcohol with a mass percentage of 99%, and the mixture was stirred and heated to 110℃to keep a reflux state for 2.5 hours, and the increase of isopropyl ester of methionine hydroxy analogue during the reaction was monitored by HPLC analysis during the reaction. After the reaction is finished, directly concentrating under reduced pressure to a solvent-free state, transferring the obtained solid into an enamel tray, putting the enamel tray into an air drying oven, drying the enamel tray at 80 ℃ to constant weight, obtaining 315.03 g of off-white solid, grinding and sieving the off-white solid to obtain the dispersible and flowable off-white methionine hydroxy analogue isopropyl ester calcium biphosphate compound, wherein the bulk density is 0.95 g/ml, the mass percentage of the methionine hydroxy analogue isopropyl ester (calculated by the methionine hydroxy analogue) is 47.61%, and the mass percentage of the calcium biphosphate is 40.0%.
Example 12
To a 1000 ml reaction flask were added 151.15 g (1.0 mol) of methionine hydroxy analogue with a mass percentage of 99%, 50.41 g (0.2 mol) of feed-grade monocalcium phosphate with a mass percentage of 99%, 23.06 g (0.2 mol) of phosphoric acid with a mass percentage of 85% and 423.53 g (6.0 mol) of isopropyl alcohol with a mass percentage of 85%, and the mixture was stirred and heated to 110℃to keep a reflux state and reacted for 3.0 hours, and during the reaction, the increase of isopropyl ester of methionine hydroxy analogue was monitored by HPLC analysis. After the reaction is finished, the obtained mixed solution is cooled to 40 ℃, 8.70 g of calcium hydroxide powder with the mass percent of 96% is slowly added under the stirring state, the neutralization reaction temperature is controlled to be 40-45 ℃, the pH value at the end point of the neutralization reaction is controlled to be 3.7, then the mixed solution is directly decompressed and concentrated to be in a solvent-free state, the obtained solid is transferred into an enamel tray, the enamel tray is put into a blast drying box and dried to be constant weight at 85 ℃ to obtain 260.61 g of off-white solid, after grinding and sieving, the obtained dispersible and flowable off-white methionine hydroxy analogue isopropyl ester calcium dihydrogen phosphate compound with the bulk density of 0.85 g/ml, the mass percent of the methionine hydroxy analogue isopropyl ester (calculated by methionine hydroxy analogue) is 57.56%, and the mass percent of the calcium dihydrogen phosphate is 29.01%.
Comparative example 1 95% sulfuric acid as catalyst, toluene as solvent
To a 1000 ml reaction flask were added 170.45 g (1.0 mol) of 88% by mass methionine hydroxy analogue, 41.26 g (0.4 mol) of 95% by mass phosphoric acid, 303.54 g (5.0 mol) of 300 ml toluene and 99% by mass isopropyl alcohol, and the mixture was stirred and heated to 110℃to keep a reflux state and reacted for 3 hours, and during the reaction, the increase of isopropyl ester of methionine hydroxy analogue was monitored by HPLC analysis. After the reaction, cooling to 50 ℃, standing and layering, separating out the toluene aqueous solution containing isopropyl methionine hydroxy analogue as the upper organic phase and the aqueous solution containing sulfuric acid as the lower organic phase. The upper organic phase obtained was concentrated to give 125.21 g of a viscous yellow oily liquid, the main content of isopropyl methionine hydroxy analogue was 92% and the yield of isopropyl methionine hydroxy analogue was 60%. The lower layer sulfuric acid aqueous solution contains methionine hydroxy analogue, then sodium hydroxide is added to adjust the pH value to 6.0, and the concentration and crystallization are carried out to obtain sodium sulfate crystals, wherein the crystals contain about 2% of methionine hydroxy analogue.
Comparative example 2 85% phosphoric acid as catalyst and toluene as solvent
To a 1000 ml reaction flask were added 170.45 g (1.0 mol) of 88% by mass methionine hydroxy analogue, 46.12 g (0.4 mol) of 85% by mass phosphoric acid, 300 ml of toluene and 303.54 g (5.0 mol) of 99% by mass isopropyl alcohol, and the mixture was stirred and heated to 110℃to keep a reflux state and reacted for 3 hours, and during the reaction, the increase of isopropyl ester of methionine hydroxy analogue was monitored by HPLC analysis. After the reaction, cooling to 50 ℃, standing and layering, separating out the toluene aqueous solution containing isopropyl methionine hydroxy analogue as the upper organic phase and the aqueous solution containing sulfuric acid as the lower organic phase. The resulting upper organic phase was concentrated to give 132.76 g of a viscous yellow oily liquid, the main content of isopropyl methionine hydroxy analogue was 94%, and the yield of isopropyl methionine hydroxy analogue was 65%. The lower layer sulfuric acid aqueous solution contains methionine hydroxy analogue, then sodium hydroxide is added to adjust the pH value to 6.0, and the mixture is concentrated and crystallized to obtain disodium hydrogen phosphate crystal, wherein the content of methionine hydroxy analogue in the crystal is about 1.8 percent.
Application examples
With the product obtained in the above example, 2 cows were given the same dose of isopropyl methionine hydroxy analogue as prepared in the above example as 57 g methionine hydroxy analogue, the methionine concentration in the plasma of the cows was measured for 27 hours, the measured results were plotted, the area under the curve was calculated to obtain the bioavailability results, and the calcium and phosphorus content in the urine and feces discharged from the cows were analyzed by collecting them, thereby converting the calcium and phosphorus utilization rate of the product. The following table shows the bioavailability results of the methionine hydroxy analogue isopropyl ester series products.
The data in the table show that the solid powdery isopropyl methionine hydroxy analogue calcium phosphate compound obtained by the method of the invention has good methionine utilization rate and calcium phosphorus utilization rate in animal feeding experiments, and the compound has the bioavailability of monomer isopropyl methionine hydroxy analogue, and the product contains high-quality organic calcium such as calcium methionine hydroxy analogue, and the like, compared with single calcium phosphate (calcium hydrophosphate, monocalcium phosphate and monocalcium phosphate), the calcium phosphorus utilization rate is improved.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by the scope of the claims of the present invention. The technology, shape, and construction parts of the present invention, which are not described in detail, are known in the art.
Claims (5)
1. The preparation method of the methionine hydroxy analogue isopropyl ester compound is characterized by comprising the following steps:
Mixing and stirring methionine hydroxy analogue, isopropanol and a catalyst, heating to 55-110 ℃, carrying out esterification reaction for 1-6 h to obtain methionine hydroxy analogue-isopropyl ester mixed liquor, wherein the catalyst is one or two of calcium hydrophosphate and calcium biphosphate, concentrating the mixed liquor under reduced pressure to a solvent-free state after the reaction is finished, and drying and grinding to obtain solid powdery methionine hydroxy analogue isopropyl ester compound;
or mixing and stirring methionine hydroxy analogue, isopropanol and a catalyst, heating to 55-110 ℃, carrying out esterification reaction for 1-6 h to obtain methionine hydroxy analogue-isopropyl ester mixed liquor, wherein the catalyst is one or two of phosphoric acid, calcium hydrophosphate and monocalcium phosphate, stirring and adding a calcium compound into the cooled mixed liquor after the reaction is finished, neutralizing, concentrating under reduced pressure to a solvent-free state after the neutralization reaction is finished, and drying and grinding to obtain solid powdery methionine hydroxy analogue-isopropyl ester compound;
The molar ratio of the methionine hydroxy analogue to the isopropanol to the catalyst is 1:2-10:0.2-1.5; the calcium compound is at least one of calcium oxide, calcium hydroxide or calcium carbonate, the pH value end point of the neutralization of the calcium compound is 3.5-6.5, and the neutralization reaction temperature is 40-60 ℃;
The methionine hydroxy analogue isopropyl ester compound is solid powder, and the methionine hydroxy analogue isopropyl ester compound is a compound of methionine hydroxy analogue isopropyl ester, methionine hydroxy analogue dimer isopropyl ester, methionine hydroxy analogue trimer isopropyl ester, methionine hydroxy analogue calcium salt and calcium phosphate salt; in the methionine hydroxy analogue isopropyl ester compound, the mass percentage of the methionine hydroxy analogue isopropyl ester is 33% -63% based on the methionine hydroxy analogue; the calcium phosphate salt is at least one of calcium hydrogen phosphate, calcium dihydrogen phosphate and dicalcium phosphate.
2. The method for preparing the isopropyl methionine hydroxy analogue compound according to claim 1, wherein the calcium phosphate salt accounts for 21-57% of the isopropyl methionine hydroxy analogue compound by mass.
3. The method for preparing the isopropyl methionine hydroxy analogue compound according to claim 1, wherein the mass percentage of the methionine hydroxy analogue is 40-99% and the water content is 0.85-60%; the mass percentage of the isopropanol is 50% -99.9%.
4. The method for preparing the isopropyl methionine hydroxy analogue compound according to claim 1, wherein the mass percentage of phosphoric acid is 35% -85%, the mass ratio of phosphorus pentoxide to fluoride ion in the phosphoric acid is 300 or more, and the heavy metal content is less than 8ppm.
5. The preparation method according to any one of claims 1 to 4, wherein the production system used in the preparation method comprises a first reaction kettle, a second reaction kettle and a spray drying tower, an outlet of the first reaction kettle is connected with an inlet of the second reaction kettle, an outlet of the second reaction kettle is connected with an inlet of the spray drying tower, a product outlet is arranged at the bottom of the spray drying tower, a condenser is connected with a top outlet for cooling hot gas discharged from the spray drying tower, and a feed inlet and an online pH meter are arranged on the second reaction kettle.
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