CN103965153A - Method for preparing quercetin and rhamnose through rutin - Google Patents
Method for preparing quercetin and rhamnose through rutin Download PDFInfo
- Publication number
- CN103965153A CN103965153A CN201410192372.9A CN201410192372A CN103965153A CN 103965153 A CN103965153 A CN 103965153A CN 201410192372 A CN201410192372 A CN 201410192372A CN 103965153 A CN103965153 A CN 103965153A
- Authority
- CN
- China
- Prior art keywords
- quercetin
- rhamnosyl
- solution
- rutin
- acid
- 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
- REFJWTPEDVJJIY-UHFFFAOYSA-N Quercetin Chemical compound C=1C(O)=CC(O)=C(C(C=2O)=O)C=1OC=2C1=CC=C(O)C(O)=C1 REFJWTPEDVJJIY-UHFFFAOYSA-N 0.000 title claims abstract description 102
- ZVOLCUVKHLEPEV-UHFFFAOYSA-N Quercetagetin Natural products C1=C(O)C(O)=CC=C1C1=C(O)C(=O)C2=C(O)C(O)=C(O)C=C2O1 ZVOLCUVKHLEPEV-UHFFFAOYSA-N 0.000 title claims abstract description 51
- HWTZYBCRDDUBJY-UHFFFAOYSA-N Rhynchosin Natural products C1=C(O)C(O)=CC=C1C1=C(O)C(=O)C2=CC(O)=C(O)C=C2O1 HWTZYBCRDDUBJY-UHFFFAOYSA-N 0.000 title claims abstract description 51
- MWDZOUNAPSSOEL-UHFFFAOYSA-N kaempferol Natural products OC1=C(C(=O)c2cc(O)cc(O)c2O1)c3ccc(O)cc3 MWDZOUNAPSSOEL-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 235000005875 quercetin Nutrition 0.000 title claims abstract description 51
- 229960001285 quercetin Drugs 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 38
- JMGZEFIQIZZSBH-UHFFFAOYSA-N Bioquercetin Natural products CC1OC(OCC(O)C2OC(OC3=C(Oc4cc(O)cc(O)c4C3=O)c5ccc(O)c(O)c5)C(O)C2O)C(O)C(O)C1O JMGZEFIQIZZSBH-UHFFFAOYSA-N 0.000 title claims abstract description 33
- IVTMALDHFAHOGL-UHFFFAOYSA-N eriodictyol 7-O-rutinoside Natural products OC1C(O)C(O)C(C)OC1OCC1C(O)C(O)C(O)C(OC=2C=C3C(C(C(O)=C(O3)C=3C=C(O)C(O)=CC=3)=O)=C(O)C=2)O1 IVTMALDHFAHOGL-UHFFFAOYSA-N 0.000 title claims abstract description 33
- FDRQPMVGJOQVTL-UHFFFAOYSA-N quercetin rutinoside Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC=2C(C3=C(O)C=C(O)C=C3OC=2C=2C=C(O)C(O)=CC=2)=O)O1 FDRQPMVGJOQVTL-UHFFFAOYSA-N 0.000 title claims abstract description 33
- ALABRVAAKCSLSC-UHFFFAOYSA-N rutin Natural products CC1OC(OCC2OC(O)C(O)C(O)C2O)C(O)C(O)C1OC3=C(Oc4cc(O)cc(O)c4C3=O)c5ccc(O)c(O)c5 ALABRVAAKCSLSC-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 235000005493 rutin Nutrition 0.000 title claims abstract description 33
- 229960004555 rutoside Drugs 0.000 title claims abstract description 33
- IKGXIBQEEMLURG-BKUODXTLSA-N rutin Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@@H]1OC[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](OC=2C(C3=C(O)C=C(O)C=C3OC=2C=2C=C(O)C(O)=CC=2)=O)O1 IKGXIBQEEMLURG-BKUODXTLSA-N 0.000 title claims abstract 9
- SHZGCJCMOBCMKK-UHFFFAOYSA-N D-mannomethylose Natural products CC1OC(O)C(O)C(O)C1O SHZGCJCMOBCMKK-UHFFFAOYSA-N 0.000 title abstract 4
- SHZGCJCMOBCMKK-JFNONXLTSA-N L-rhamnopyranose Chemical compound C[C@@H]1OC(O)[C@H](O)[C@H](O)[C@H]1O SHZGCJCMOBCMKK-JFNONXLTSA-N 0.000 title abstract 4
- PNNNRSAQSRJVSB-UHFFFAOYSA-N L-rhamnose Natural products CC(O)C(O)C(O)C(O)C=O PNNNRSAQSRJVSB-UHFFFAOYSA-N 0.000 title abstract 4
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 35
- 230000007062 hydrolysis Effects 0.000 claims abstract description 34
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 25
- 241000219784 Sophora Species 0.000 claims abstract description 25
- 239000008103 glucose Substances 0.000 claims abstract description 25
- 102000004190 Enzymes Human genes 0.000 claims abstract description 23
- 108090000790 Enzymes Proteins 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 21
- 239000012535 impurity Substances 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 239000008139 complexing agent Substances 0.000 claims abstract description 14
- 239000012452 mother liquor Substances 0.000 claims abstract description 11
- 230000000593 degrading effect Effects 0.000 claims abstract description 9
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- 238000010025 steaming Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000000287 crude extract Substances 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- 230000003472 neutralizing effect Effects 0.000 claims description 23
- 238000007670 refining Methods 0.000 claims description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical group OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 15
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 15
- 238000002386 leaching Methods 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 230000015556 catabolic process Effects 0.000 claims description 14
- 238000006731 degradation reaction Methods 0.000 claims description 14
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 13
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000003112 inhibitor Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- 239000003814 drug Substances 0.000 claims description 10
- 239000000284 extract Substances 0.000 claims description 10
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 9
- 239000001110 calcium chloride Substances 0.000 claims description 9
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 8
- 238000010298 pulverizing process Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical group Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 5
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- 235000017550 sodium carbonate Nutrition 0.000 claims description 4
- 229940095064 tartrate Drugs 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 150000002386 heptoses Chemical class 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- 235000019154 vitamin C Nutrition 0.000 claims description 3
- 239000011718 vitamin C Substances 0.000 claims description 3
- FEXBEKLLSUWSIM-UHFFFAOYSA-N 2-Butyl-4-methylphenol Chemical class CCCCC1=CC(C)=CC=C1O FEXBEKLLSUWSIM-UHFFFAOYSA-N 0.000 claims description 2
- 235000011148 calcium chloride Nutrition 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 238000000605 extraction Methods 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 7
- 238000004128 high performance liquid chromatography Methods 0.000 abstract description 6
- 229930003935 flavonoid Natural products 0.000 abstract description 5
- 235000017173 flavonoids Nutrition 0.000 abstract description 5
- -1 flavonoids compound Chemical class 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 239000000084 colloidal system Substances 0.000 abstract description 3
- 238000001514 detection method Methods 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 229930002875 chlorophyll Natural products 0.000 abstract description 2
- 235000019804 chlorophyll Nutrition 0.000 abstract description 2
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 abstract description 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 2
- 238000007605 air drying Methods 0.000 abstract 1
- 239000003963 antioxidant agent Substances 0.000 abstract 1
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 235000006708 antioxidants Nutrition 0.000 abstract 1
- 230000000536 complexating effect Effects 0.000 abstract 1
- 238000005189 flocculation Methods 0.000 abstract 1
- 230000016615 flocculation Effects 0.000 abstract 1
- 238000006386 neutralization reaction Methods 0.000 abstract 1
- IKGXIBQEEMLURG-NVPNHPEKSA-N rutin Chemical compound O[C@@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@H](OC=2C(C3=C(O)C=C(O)C=C3OC=2C=2C=C(O)C(O)=CC=2)=O)O1 IKGXIBQEEMLURG-NVPNHPEKSA-N 0.000 description 26
- 239000012043 crude product Substances 0.000 description 19
- 241000196324 Embryophyta Species 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- OVSQVDMCBVZWGM-QSOFNFLRSA-N quercetin 3-O-beta-D-glucopyranoside Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=C(C=2C=C(O)C(O)=CC=2)OC2=CC(O)=CC(O)=C2C1=O OVSQVDMCBVZWGM-QSOFNFLRSA-N 0.000 description 5
- OVSQVDMCBVZWGM-IDRAQACASA-N Hirsutrin Natural products O([C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1)C1=C(c2cc(O)c(O)cc2)Oc2c(c(O)cc(O)c2)C1=O OVSQVDMCBVZWGM-IDRAQACASA-N 0.000 description 3
- FVQOMEDMFUMIMO-UHFFFAOYSA-N Hyperosid Natural products OC1C(O)C(O)C(CO)OC1OC1C(=O)C2=C(O)C=C(O)C=C2OC1C1=CC=C(O)C(O)=C1 FVQOMEDMFUMIMO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GXMWXESSGGEWEM-UHFFFAOYSA-N isoquercitrin Natural products OCC(O)C1OC(OC2C(Oc3cc(O)cc(O)c3C2=O)c4ccc(O)c(O)c4)C(O)C1O GXMWXESSGGEWEM-UHFFFAOYSA-N 0.000 description 3
- 244000046101 Sophora japonica Species 0.000 description 2
- 235000010586 Sophora japonica Nutrition 0.000 description 2
- UWFBUSOQLUIUIF-UHFFFAOYSA-N Thujin Natural products C1=C2C(=O)OC(C)(C)C(C)=C2C=C2C1=C(C)C(C)(C)OC2=O UWFBUSOQLUIUIF-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000007071 enzymatic hydrolysis Effects 0.000 description 2
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 2
- 229930182478 glucoside Natural products 0.000 description 2
- 150000008131 glucosides Chemical class 0.000 description 2
- 239000000413 hydrolysate Substances 0.000 description 2
- OXGUCUVFOIWWQJ-HQBVPOQASA-N quercitrin Chemical compound O[C@@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@H]1OC1=C(C=2C=C(O)C(O)=CC=2)OC2=CC(O)=CC(O)=C2C1=O OXGUCUVFOIWWQJ-HQBVPOQASA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 241001116389 Aloe Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 206010006458 Bronchitis chronic Diseases 0.000 description 1
- 206010007191 Capillary fragility Diseases 0.000 description 1
- 244000192528 Chrysanthemum parthenium Species 0.000 description 1
- 235000000604 Chrysanthemum parthenium Nutrition 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- 244000004281 Eucalyptus maculata Species 0.000 description 1
- 235000011201 Ginkgo Nutrition 0.000 description 1
- 244000194101 Ginkgo biloba Species 0.000 description 1
- 235000008100 Ginkgo biloba Nutrition 0.000 description 1
- 240000000950 Hippophae rhamnoides Species 0.000 description 1
- 235000003145 Hippophae rhamnoides Nutrition 0.000 description 1
- 206010062717 Increased upper airway secretion Diseases 0.000 description 1
- 235000000802 Leonurus cardiaca ssp. villosus Nutrition 0.000 description 1
- 244000241838 Lycium barbarum Species 0.000 description 1
- 235000015459 Lycium barbarum Nutrition 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- IKGXIBQEEMLURG-UHFFFAOYSA-N Rutin Chemical compound OC1C(O)C(O)C(C)OC1OCC1C(O)C(O)C(O)C(OC=2C(C3=C(O)C=C(O)C=C3OC=2C=2C=C(O)C(O)=CC=2)=O)O1 IKGXIBQEEMLURG-UHFFFAOYSA-N 0.000 description 1
- 244000044283 Toxicodendron succedaneum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 235000011399 aloe vera Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000001088 anti-asthma Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000036772 blood pressure Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 206010006451 bronchitis Diseases 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940126678 chinese medicines Drugs 0.000 description 1
- 208000007451 chronic bronchitis Diseases 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 208000029078 coronary artery disease Diseases 0.000 description 1
- 210000004351 coronary vessel Anatomy 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 150000002215 flavonoids Chemical class 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 241000411851 herbal medicine Species 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- DFPMSGMNTNDNHN-ZPHOTFPESA-N naringin Chemical compound O[C@@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@H]1O[C@H]1[C@H](OC=2C=C3O[C@@H](CC(=O)C3=C(O)C=2)C=2C=CC(O)=CC=2)O[C@H](CO)[C@@H](O)[C@@H]1O DFPMSGMNTNDNHN-ZPHOTFPESA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 208000026435 phlegm Diseases 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 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 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 229940126680 traditional chinese medicines Drugs 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
- C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
- C07D311/28—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only
- C07D311/30—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only not hydrogenated in the hetero ring, e.g. flavones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
- C07H3/08—Deoxysugars; Unsaturated sugars; Osones
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Molecular Biology (AREA)
- Saccharide Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention belongs to the field of flavonoids compound extraction, and particularly relates to a method for preparing quercetin and rhamnose through rutin. The preparation method comprises the following steps: steaming collected sophora flower buds through steam, air-drying, smashing and seeping the steamed sophora flower buds, removing colloid and chlorophyll impurities through flocculation, performing protection complexing treatment through an antioxidant and a complexing agent, adding a mixed acid to adjust the mixture to be acidic, and heating, pressurizing and hydrolyzing to obtain the quercetin; performing impurity filtration and neutralization on hydrolysis mother liquor subjected to quercetin extraction, degrading glucose through glucose degrading enzyme, and performing decoloring vacuum centrifugal concentration and crystallization after a solution is filtered and separated to obtain a product, namely the rhamnose. Under detection of HPLC (high performance liquid chromatography), the content of the quercetin is over 95 percent; all impurity requirements meet an international standard requirement; in a technical process, rutin hydrolysis mother liquor is also subjected to comprehensive treatment, and rhamnose is obtained through production; the production cost of the production is lowered, and the environmental pollution is alleviated.
Description
Technical field
The invention belongs to flavonoid compound and extract field, specifically a kind of method of utilizing rutin to prepare Quercetin and rhamnosyl.
Background technology
Rutin is a kind of flavonoid compound, and being widely distributed in natural plant all exists in the roots of a lot of plants, stem, leaf, flower, fruit, seed.Some conventional Chinese medicines, as all contained rutin in the various plants such as the sophora bud, rue, foster wheat, sea-buckthorn, ginkgo, matrimony vine, Motherwort Herb, radix bupleuri, Spica Prunellae, aloe, eucalyptus leaves and tobacco leaf, rutin is one of important source material of China's medicine industry.
Quercetin belongs to flavonoid compound, is present in the flower, leaf, fruit of many plants, exist mainly with the form of glucoside, and as rutin (phytomelin), thujin, Hyperosides etc., can obtain Quercetin through acid hydrolysis.Have preferably eliminate the phlegm, the pharmacological action such as cough-relieving, and have certain antiasthmatic effect.In addition reduce blood pressure in addition, strengthen capillary resistance, reduce capillary fragility, reduce the effects such as blood fat, coronary artery dilator, increase coronary flow.Be used for the treatment of chronic bronchitis, coronary heart disease and hyperpietic are also had to auxiliary therapeutic action.
Rhamnosyl is distributed widely in plant as a kind of trace sugar.Can be present in a variety of plant glucosides (as thujin, aurantiin etc.), polysaccharide, particularly pectin and colloid in conjunction with sugared form, also can be present in lacquer tree toxin.Rhamnosyl can be used to measure the perviousness of enteron aisle, can be used as sweeting agent, also can be used for producing essence and flavoring agent, edible.
At present, the preparation method of Quercetin has: 1, separation and Extraction from natural phant, as " reclaiming Quercetol 3-monoglucoside from the Vitamin P complex " method such as (CN1355797), but these class methods will be used a large amount of organic solvents, be unfavorable for cleaner production, and productive rate is low, cost is high, is difficult to realize industrialization and produces.2, prepare isoquercitrin and Quercetin with enzymatic hydrolysis rutin, such as " enzymatic hydrolysis is prepared the method for Quercetol 3-monoglucoside and Quercetin " (CN03133636.1), " from plant biomass extraction, purifying and conversion flavonoids " (CN1685053A), these class methods need to be used expensive biological enzyme formulation, processing unit is also more complicated, and production cost is higher.3, the suitability for industrialized production of Quercetin generally adopt strong acid hydrolyzing rutin technique (referring to Liu Yaping, Quercetin preparation method's research, time precious traditional Chinese medical science traditional Chinese medicines, 2004,15 (10): 657-658; He Qin, Xu Xiongliang etc., the extraction process of the preferred analysis of quercetin in bud of Sophora japonica of orthogonal experiment, herbal medicine, 2003,34 (5): 409-412), higher to the requirement for anticorrosion of production unit, and produce the three wastes, be unfavorable for environment protection.4, the method (CN200610065217.6) of preparing Quercetin and isoquercitrin with rutin, the method is utilized in autoclave and is added suitable quantity of water, is heated to boil; Take rutin, join in the distilled water of 2～3 times of rutin parts by weight and be stirred into slurries, slurries are placed on the dividing plate of boiling water top in aforementioned autoclave; Continue reacting by heating still, utilize water vapor to drain in still enclosed high pressure still after air, controlling Saturated water vapor pressure in still is 0.2～0.8Mpa, is hydrolyzed 10 minutes～5 hours, can make mixture of hydrolysate; Stop heating, cooling steam discharge, takes out mixture of hydrolysate and is cooled between 5～20 DEG C, with the distilled water centrifuge washing between 10～20 DEG C of 3～5 times of weight 2～4 times, and the vacuum-drying again of gained throw out; With ordinary method separating-purifying isoquercitrin and Quercetin from throw out.
At present, for the research of Quercetin and rhamnosyl, patent CN201210424952.7, announce a kind of method of utilizing the sophora bud to prepare Quercetin and rhamnosyl, employing following steps complete: A, to get the sophora bud appropriate, pulverizes, and utilizes the limewater extraction rutin of saturated clarification; B, utilize the rutin hydrolysis of extracting in steps A to produce Quercetin; C, the waste liquid fermentation in step B is produced to rhamnosyl crude product; D, utilize the glucose in rhamnosyl crude product in separating methanol step C, make rhamnosyl fine work.Though the method is produced byproduct rhamnosyl, but its preparation method product yield is not high, acidolysis process is too single, acidolysis efficiency is low, rhamnosyl needs repeatedly purification repeatedly, and its preparation process only limits to, and sophora bud raw material extracts, whole leaching process energy consumption is high.
Summary of the invention
The object of the invention is to overcome the existing method of preparing Quercetin and rhamnosyl and have that complex process is loaded down with trivial details, long reaction time, product purity is low does not reach international standard, exist pollute, resource can not get the problems such as comprehensive utilization, and a kind of method of utilizing rutin to prepare Quercetin and rhamnosyl is provided.
The solution of the present invention is by such realization: a kind of method of utilizing rutin to prepare Quercetin and rhamnosyl, the method comprises the steps.
Step a: the sophora flower flower bud collecting is eliminated to degrading enzyme at the middle steaming 10～15min of 100～120 DEG C of water vapour, take out that steamed bud dries successively, pulverizing, diacolation, to the solution filter slagging-off obtaining after diacolation, obtain crude extract.
Step b: add flocculate and clarify agent in the crude extract obtaining at step a, the ratio of flocculate and clarify agent and crude extract is 1～5g:100L, after adding flocculate and clarify agent, stir flocculate and clarify agent is uniformly distributed in crude extract gently, leave standstill again 20～40min, make impurity separate out and remove precipitate, in solution, add after oxidation inhibitor, complexing agent, add mixed acid solution to adjust pH to 3.0～5.0, obtain acid hydrolysis solution.
Step c: the acid hydrolysis solution that step b is obtained is 150～200 DEG C, the pressure Water Under solution that is 0.05～0.75Mpa 0.5～2.5 hour in temperature, obtain mixed hydrolysis liquid, its temperature is cooled to after 20～30 DEG C, ratio according to mixed hydrolysis liquid: water=1L:20～30L pours water, make Quercetin Precipitation, separation obtains Quercetin product and hydrolysising mother liquid, and hydrolysising mother liquid further extracts rhamnosyl.
Steps d: step c is obtained carrying out neutralizing treatment after hydrolysising mother liquid filtering and impurity removing, according to the ratio of glucose degradation enzyme: hydrolysising mother liquid=50～100U:1L, glucose degradation enzyme is joined in the hydrolysising mother liquid after neutralizing treatment, glucose is degraded 12～24 hours, solution after degraded separates decolouring by activated carbon filtration, obtains rhamnosyl refining liquid.
Step e: the refining liquid that steps d is obtained is concentrated centrifugal, crystallization in 25～30 DEG C, the rotating speed vacuum environment that is 300～800rpm in temperature, obtains rhamnosyl crude product, and refining rhamnosyl crude product obtains rhamnosyl content > 98%.
As a further improvement on the present invention, the leaching solution that diacolation in described step a is used is the mixing solutions of sodium carbonate, sodium bisulfite, calcium chloride, and sodium carbonate, sodium bisulfite, the content of calcium chloride in leaching solution are respectively 15～30%, 15～30%, 10～40%; The flocculate and clarify agent of using in described step b is natural traditional Chinese medicine finings KBT-ZTC, and natural traditional Chinese medicine finings KBT-ZTC is the natural traditional Chinese medicine finings that Ke Lier Bioisystech Co., Ltd produces, is made up of main solidifying agent A and auxiliary agent B.
As a further improvement on the present invention, the mixing acid of using in described step b is any two or the mixing of three kinds in hydrochloric acid HCl, sulfuric acid H2SO4, Glacial acetic acid.
As a further improvement on the present invention, described oxidation inhibitor citric acid, 2, tri-grades of butyl-4-methylphenols of 6-, double thioether (3, tri-grades of butyl-4-hydroxy phenyls of 5-), any in pentaerythritol tetrathioglycollate (β-(tri-grades of butyl-4-hydroxy phenyls of 3,5-) propionic acid), vitamins C, S-WAT, sodium bisulfite.
As a further improvement on the present invention, described complexing agent is any or their mixture in tartrate, heptose hydrochlorate, Sunmorl N 60S, sodium alginate, ethylenediamine tetraacetic acid (EDTA) (EDTA).
As a further improvement on the present invention, the neutralizing treatment in described steps d is the H in any neutralizing hydrolysis mother liquor in the sodium hydroxide that is 0.05～0.2mol/L by concentration, potassium hydroxide, hydrated barta
+, to pH be 6.5～7.0.
The know-why that the present invention realizes is: taking Chinese scholar tree extract rutin as starting raw material, under acidic conditions, glucose and rhamanopyranosyl are removed in heating and pressurizing hydrolysis, high performance liquid chromatography for Quercetin (HPLC) detection level obtaining can reach more than 95%, every impurity requires to have reached international standard requirement, in technological process, rutin hydrolysising mother liquid obtains comprehensive treating process simultaneously, production has obtained rhamnosyl, separate out the recycling of the hydrolysising mother liquid after Quercetin, not only reduce products production cost, and stop to cause the possibility of environmental pollution, realize the environmental protection and energy saving effect of producing.
The present invention possesses following good result:
(1) first rear operation in the process of sophora bud extraction rutin of the present invention, directly the rutin intermediate extracting is carried out to removal of impurities processing, remove the impurity such as colloid and chlorophyll in rutin, without the operation of re-refining of pressure-filteration drying treatment process and rutin crude product, shorten technical process, reduced production cost, and produce finished product reached international standard through an one-step hydrolysis content, high performance liquid chromatography for Quercetin (HPLC) detection level can reach more than 95%.And traditional technology is the first rutin crude product that proposes from the sophora bud, after the pulverizing of rutin crude product drying, regeneration is produced to be hydrolyzed and is first obtained Quercetin crude product, and Quercetin crude product just can meet international standards after dissolution filter again.
(2) the present invention adopts under high-temperature high-pressure state and is hydrolyzed with mixing acid, has reduced sour consumption, makes hydrolysis reaction thoroughly complete.Greatly shorten the production cycle, hydrolysis time shortened to about 2 hours above from traditional 12 hours, traditional technology is for adopting single acid, High Temperature High Pressure is hydrolyzed, the consumption of acid is 10 times of consumption of the present invention, hydrolysis time is the more than 6 times of hydrolysis time of the present invention, and the control of hydrolysis difficult quality.
(3) comprehensive reutilization of hydrolysising mother liquid of the present invention not only makes product cost obtain significantly reducing, and the rhamnosyl purity > 98% producing, fill up the blank of like product, simultaneously because the possibility of environmental pollution has fundamentally been stopped in the recycling of mother liquor, than directly having discarded qualitative leap after traditional mother liquor simple process.
(4) the present invention is by after the improvement of Technology, and Product Process is tending towards simply, production cycle shortening, and product cost reduces, feed stock conversion improves, minimizing is polluted, and has saved to greatest extent the energy, meets the energy-conservation requirement of national environmental protection.
Brief description of the drawings
Fig. 1. Quercetin of the present invention and rhamnosyl preparation method schema.
Embodiment
Describe a kind of method of utilizing rutin to prepare Quercetin and rhamnosyl of the present invention below in conjunction with embodiment and accompanying drawing, these descriptions are not that content of the present invention is further limited.The reagent of using in following examples if no special instructions, all can buy by commercial means.Operation in following examples if no special instructions, all can realize by producing conventional means.
Embodiment 1
Step a: gather sophora flower flower bud 10kg (weight in wet base), the sophora flower flower bud collecting is eliminated to degrading enzyme at the middle steaming 12min of 100 DEG C of water vapour, take out that steamed bud dries successively, pulverizing, diacolation, diacolation is used the leaching solution that contains 18% sodium carbonate, 20% sodium bisulfite, calcium chloride 30%, the ratio of leaching solution and sophora flower flower bud (weight in wet base) is 2.5L:1kg, to the solution filter slagging-off obtaining after diacolation, obtain crude extract.
Step b: add natural traditional Chinese medicine finings KBT-ZTC in the crude extract obtaining at step a, the ratio of flocculate and clarify agent and crude extract is 3.0g:100L, after adding flocculate and clarify agent, stir flocculate and clarify agent is uniformly distributed in crude extract gently, leave standstill again 25min, make impurity separate out and remove precipitate, in solution, add oxidation inhibitor, complexing agent makes its concentration be respectively 0.5g/L, 0.6g/L, oxidation inhibitor is that citric acid and S-WAT mix according to weight 1:1, complexing agent is that tartrate and EDTA mix according to weight 1:1, add mixed acid solution to adjust pH to 3.0, mixing acid is 20% hydrochloric acid HCl, 20% sulfuric acid H
2sO
4mix according to volume 1:1, obtain acid hydrolysis solution.
Step c: the acid hydrolysis solution that step b is obtained is 150 DEG C, the pressure Water Under solution that is 0.75Mpa 2.0 hours in temperature, obtain mixed hydrolysis liquid, its temperature is cooled to after 25 DEG C, ratio according to mixed hydrolysis liquid: water=1L:20L pours water, make Quercetin Precipitation, separation obtains Quercetin product and hydrolysising mother liquid, and hydrolysising mother liquid further extracts rhamnosyl.
Steps d: step c is obtained carrying out after hydrolysising mother liquid filtering and impurity removing neutralizing treatment: the sodium hydroxide neutralizing hydrolysis mother liquor that is 0.1mol/L by concentration to pH be 6.5, according to the ratio of glucose degradation enzyme: hydrolysising mother liquid=60U:1L, glucose degradation enzyme is joined in the hydrolysising mother liquid after neutralizing treatment, glucose is degraded 12 hours, solution after degraded separates decolouring by activated carbon filtration, obtains rhamnosyl refining liquid.
Step e: the refining liquid that steps d is obtained is concentrated centrifugal, crystallization in 25 DEG C, the rotating speed vacuum environment that is 300rpm in temperature, obtains rhamnosyl crude product, and refining rhamnosyl crude product obtains rhamnosyl content > 98%.
Embodiment 2
Step a: gather sophora flower flower bud 10kg (weight in wet base), the sophora flower flower bud collecting is eliminated to degrading enzyme at the middle steaming 10min of 120 DEG C of water vapour, take out that steamed bud dries successively, pulverizing, diacolation, diacolation is used the leaching solution that contains 15% sodium carbonate, 30% sodium bisulfite, calcium chloride 40%, the ratio of leaching solution and sophora flower flower bud (weight in wet base) is 3.0L:1kg, to the solution filter slagging-off obtaining after diacolation, obtain crude extract.
Step b: add natural traditional Chinese medicine finings KBT-ZTC in the crude extract obtaining at step a, the ratio of flocculate and clarify agent and crude extract is 2.5g:100L, after adding flocculate and clarify agent, stir flocculate and clarify agent is uniformly distributed in crude extract gently, leave standstill again 30min, make impurity separate out and remove precipitate, in solution, add oxidation inhibitor, EDTA complexing agent to make its concentration be respectively 0.4g/L, 0.3g/L, oxidation inhibitor is that sodium bisulfite and S-WAT mix according to weight 1:1, add mixed acid solution to adjust pH to 4.0, mixing acid is 30% hydrochloric acid HCl, 30% sulfuric acid H
2sO
4mix according to volume 1:1, obtain acid hydrolysis solution.
Step c: the acid hydrolysis solution that step b is obtained is 200 DEG C, the pressure Water Under solution that is 0.65Mpa 2.5 hours in temperature, obtain mixed hydrolysis liquid, its temperature is cooled to after 30 DEG C, ratio according to mixed hydrolysis liquid: water=1L:30L pours water, make Quercetin Precipitation, separation obtains Quercetin product and hydrolysising mother liquid, and hydrolysising mother liquid further extracts rhamnosyl.
Steps d: step c is obtained carrying out after hydrolysising mother liquid filtering and impurity removing neutralizing treatment: the potassium hydroxide neutralizing hydrolysis mother liquor that is 0.2mol/L by concentration to pH be 7.0, according to the ratio of glucose degradation enzyme: hydrolysising mother liquid=50U:1L, glucose degradation enzyme is joined in the hydrolysising mother liquid after neutralizing treatment, glucose is degraded 20 hours, solution after degraded separates decolouring by activated carbon filtration, obtains rhamnosyl refining liquid.
Step e: the refining liquid that steps d is obtained is concentrated centrifugal, crystallization in 30 DEG C, the rotating speed vacuum environment that is 500rpm in temperature, obtains rhamnosyl crude product, and refining rhamnosyl crude product obtains rhamnosyl content > 98%.
Embodiment 3
Step a: gather sophora flower flower bud 10kg (weight in wet base), the sophora flower flower bud collecting is eliminated to degrading enzyme at the middle steaming 13min of 115 DEG C of water vapour, take out that steamed bud dries successively, pulverizing, diacolation, diacolation is used the leaching solution that contains 30% sodium carbonate, 15% sodium bisulfite, calcium chloride 30%, the ratio of leaching solution and sophora flower flower bud (weight in wet base) is 2.0L:1kg, to the solution filter slagging-off obtaining after diacolation, obtain crude extract.
Step b: add natural traditional Chinese medicine finings KBT-ZTC in the crude extract obtaining at step a, the ratio of flocculate and clarify agent and crude extract is 5.0g:100L, after adding flocculate and clarify agent, stir flocculate and clarify agent is uniformly distributed in crude extract gently, leave standstill again 20min, make impurity separate out and remove precipitate, in solution, add citric acid oxidation inhibitor, complexing agent to make its concentration be respectively 0.7g/L, 0.8g/L, complexing agent is that Sunmorl N 60S and tartrate mix according to weight 1:1, add mixed acid solution to adjust pH to 3.5, mixing acid is 20% hydrochloric acid HCl, 20% sulfuric acid H
2sO
4, Glacial acetic acid according to volume 1:1:1 mix, obtain acid hydrolysis solution.
Step c: the acid hydrolysis solution that step b is obtained is 180 DEG C, the pressure Water Under solution that is 0.5Mpa 0.5 hour in temperature, obtain mixed hydrolysis liquid, its temperature is cooled to after 20 DEG C, ratio according to mixed hydrolysis liquid: water=1L:25L pours water, make Quercetin Precipitation, separation obtains Quercetin product and hydrolysising mother liquid, and hydrolysising mother liquid further extracts rhamnosyl.
Steps d: step c is obtained carrying out after hydrolysising mother liquid filtering and impurity removing neutralizing treatment: the hydrated barta neutralizing hydrolysis mother liquor that is 0.05mol/L by concentration to pH be 7.0, according to the ratio of glucose degradation enzyme: hydrolysising mother liquid=100U:1L, glucose degradation enzyme is joined in the hydrolysising mother liquid after neutralizing treatment, glucose is degraded 24 hours, solution after degraded separates decolouring by activated carbon filtration, obtains rhamnosyl refining liquid.
Step e: the refining liquid that steps d is obtained is concentrated centrifugal, crystallization in 27 DEG C, the rotating speed vacuum environment that is 300rpm in temperature, obtains rhamnosyl crude product, and refining rhamnosyl crude product obtains rhamnosyl content > 98%.
Embodiment 4
Step a: gather sophora flower flower bud 10kg (weight in wet base), the sophora flower flower bud collecting is eliminated to degrading enzyme at the middle steaming 15min of 105 DEG C of water vapour, take out that steamed bud dries successively, pulverizing, diacolation, diacolation is used the leaching solution that contains 20% sodium carbonate, 30% sodium bisulfite, calcium chloride 10%, the ratio of leaching solution and sophora flower flower bud (weight in wet base) is 3.0L:1kg, to the solution filter slagging-off obtaining after diacolation, obtain crude extract.
Step b: add natural traditional Chinese medicine finings KBT-ZTC in the crude extract obtaining at step a, the ratio of flocculate and clarify agent and crude extract is 4.0g:100L, after adding flocculate and clarify agent, stir flocculate and clarify agent is uniformly distributed in crude extract gently, leave standstill again 40min, make impurity separate out and remove precipitate, in solution, add oxidation inhibitor, complexing agent makes its concentration be respectively 0.8g/L, 0.5g/L, oxidation inhibitor is that vitamins C and S-WAT mix according to weight 1:1, complexing agent is that heptose hydrochlorate and sodium alginate mix according to weight 1:1, add mixed acid solution to adjust pH to 5.0, mixing acid is 25% hydrochloric acid HCl, 25% sulfuric acid H
2sO
4mix according to volume 1:1, obtain acid hydrolysis solution.
Step c: the acid hydrolysis solution that step b is obtained is 160 DEG C, the pressure Water Under solution that is 0.4Mpa 1.5 hours in temperature, obtain mixed hydrolysis liquid, its temperature is cooled to after 25 DEG C, ratio according to mixed hydrolysis liquid: water=1L:22L pours water, make Quercetin Precipitation, separation obtains Quercetin product and hydrolysising mother liquid, and hydrolysising mother liquid further extracts rhamnosyl.
Steps d: step c is obtained carrying out after hydrolysising mother liquid filtering and impurity removing neutralizing treatment: the sodium hydroxide neutralizing hydrolysis mother liquor that is 0.15mol/L by concentration to pH be 6.0, according to the ratio of glucose degradation enzyme: hydrolysising mother liquid=80U:1L, glucose degradation enzyme is joined in the hydrolysising mother liquid after neutralizing treatment, glucose is degraded 15 hours, solution after degraded separates decolouring by activated carbon filtration, obtains rhamnosyl refining liquid.
Step e: the refining liquid that steps d is obtained is concentrated centrifugal, crystallization in 25 DEG C, the rotating speed vacuum environment that is 800rpm in temperature, obtains rhamnosyl crude product, and refining rhamnosyl crude product obtains rhamnosyl content > 98%.
Embodiment 5
Step a: gather sophora flower flower bud 10kg (weight in wet base), the sophora flower flower bud collecting is eliminated to degrading enzyme at the middle steaming 10min of 110 DEG C of water vapour, take out that steamed bud dries successively, pulverizing, diacolation, diacolation is used the leaching solution that contains 20% sodium carbonate, 25% sodium bisulfite, calcium chloride 35%, the ratio of leaching solution and sophora flower flower bud (weight in wet base) is 2.0L:1kg, to the solution filter slagging-off obtaining after diacolation, obtain crude extract.
Step b: add natural traditional Chinese medicine finings KBT-ZTC in the crude extract obtaining at step a, the ratio of flocculate and clarify agent and crude extract is 1.0g:100L, after adding flocculate and clarify agent, stir flocculate and clarify agent is uniformly distributed in crude extract gently, leave standstill again 35min, make impurity separate out and remove precipitate, in solution, add sodium bisulfite oxidation inhibitor, complexing agent makes its concentration be respectively 0.7g/L, 0.8g/L, complexing agent is that Sunmorl N 60S and EDTA mix and mix according to weight 1:1 according to weight 1:1, add mixed acid solution to adjust pH to 4.0, mixing acid is 25% hydrochloric acid HCl, 25% sulfuric acid H
2sO
4mix according to volume 1:1, obtain acid hydrolysis solution.
Step c: the acid hydrolysis solution that step b is obtained is 190 DEG C, the pressure Water Under solution that is 0.05Mpa 2.0 hours in temperature, obtain mixed hydrolysis liquid, its temperature is cooled to after 30 DEG C, ratio according to mixed hydrolysis liquid: water=1L:30L pours water, make Quercetin Precipitation, separation obtains Quercetin product and hydrolysising mother liquid, and hydrolysising mother liquid further extracts rhamnosyl.
Steps d: step c is obtained carrying out after hydrolysising mother liquid filtering and impurity removing neutralizing treatment: the potassium hydroxide neutralizing hydrolysis mother liquor that is 0.2mol/L by concentration to pH be 6.5, according to the ratio of glucose degradation enzyme: hydrolysising mother liquid=100U:1L, glucose degradation enzyme is joined in the hydrolysising mother liquid after neutralizing treatment, glucose is degraded 18 hours, solution after degraded separates decolouring by activated carbon filtration, obtains rhamnosyl refining liquid.
Step e: the refining liquid that steps d is obtained is concentrated centrifugal, crystallization in 30 DEG C, the rotating speed vacuum environment that is 600rpm in temperature, obtains rhamnosyl crude product, and refining rhamnosyl crude product obtains rhamnosyl content > 98%.
The above embodiment of the present invention scheme is only can not limit the present invention to explanation of the present invention, in claim, point out the scope of product moiety of the present invention, component proportions, preparation method's parameter, and the scope of parameter of the present invention is not pointed out in above-mentioned explanation, therefore, any change in implication and the scope suitable with claims of the present invention, is all considered to be in the scope that is included in claims.
The present invention prepares researchist's long term operation experience accumulation of Quercetin and rhamnosyl technique with rutin through multidigit, and create by creative work.The present invention has shortened the production cycle, hydrolysis time shortened to about 2 hours above from traditional 12 hours, traditional technology is for adopting single acid, High Temperature High Pressure is hydrolyzed, the consumption of acid is 10 times of consumption of the present invention, hydrolysis time is the more than 6 times of hydrolysis time of the present invention, and the control of hydrolysis difficult quality; The comprehensive reutilization of hydrolysising mother liquid not only makes product cost obtain significantly reducing, and the rhamnosyl purity > 98% producing, and has filled up the blank of like product; To sum up, the present invention has marked improvement and substantive distinguishing features.
Claims (6)
1. utilize rutin to prepare a method for Quercetin and rhamnosyl, it is characterized in that, the method step comprises:
Step a: the sophora flower flower bud collecting is eliminated to degrading enzyme at the middle steaming 10 ~ 15min of 100 ~ 120 DEG C of water vapour, take out that steamed bud dries successively, pulverizing, diacolation, to the solution filter slagging-off obtaining after diacolation, obtain crude extract;
Step b: add flocculate and clarify agent in the crude extract obtaining at step a, the ratio of flocculate and clarify agent and crude extract is 1 ~ 5g:100L, after adding flocculate and clarify agent, stir flocculate and clarify agent is uniformly distributed in crude extract gently, leave standstill again 20 ~ 40min, make impurity separate out and remove precipitate, in solution, add after oxidation inhibitor, complexing agent, add mixed acid solution to adjust pH to 3.0 ~ 5.0, obtain acid hydrolysis solution;
Step c: the acid hydrolysis solution that step b is obtained is 150 ~ 200 DEG C, the pressure Water Under solution that is 0.05～0.75Mpa 0.5 ~ 2.5 hour in temperature, obtain mixed hydrolysis liquid, its temperature is cooled to after 20 ~ 30 DEG C, ratio according to mixed hydrolysis liquid: water=1L:20 ~ 30L pours water, make Quercetin Precipitation, separation obtains Quercetin product and hydrolysising mother liquid, and hydrolysising mother liquid further extracts rhamnosyl;
Steps d: step c is obtained carrying out neutralizing treatment after hydrolysising mother liquid filtering and impurity removing, according to the ratio of glucose degradation enzyme: hydrolysising mother liquid=50 ~ 100U:1L, glucose degradation enzyme is joined in the hydrolysising mother liquid after neutralizing treatment, glucose is degraded 12 ~ 24 hours, solution after degraded separates decolouring by activated carbon filtration, obtains rhamnosyl refining liquid;
Step e: the refining liquid that steps d is obtained is concentrated centrifugal, crystallization in 25 ~ 30 DEG C, the rotating speed vacuum environment that is 300 ~ 800rpm in temperature, then through the refining rhamnosyl that obtains.
2. the method for utilizing rutin to prepare Quercetin and rhamnosyl according to claim 1, it is characterized in that, the leaching solution that diacolation in described step a is used is the mixing solutions of sodium carbonate, sodium bisulfite, calcium chloride, and sodium carbonate, sodium bisulfite, the content of calcium chloride in leaching solution are respectively 15 ~ 30%, 15 ~ 30%, 10 ~ 40%; The flocculate and clarify agent of using in described step b is natural traditional Chinese medicine finings KBT-ZTC.
3. prepare the method for Quercetin and rhamnosyl according to the rutin that utilizes described in right 1 ~ 2 any one, it is characterized in that, the mixing acid of using in described step b is hydrochloric acid HCl, sulfuric acid H
2sO
4, any two or the mixing of three kinds in Glacial acetic acid.
4. the method for utilizing rutin to prepare Quercetin and rhamnosyl according to claim 3, it is characterized in that, described oxidation inhibitor is citric acid, 2, any in tri-grades of butyl-4-methylphenols of 6-, double thioether, pentaerythritol tetrathioglycollate, vitamins C, S-WAT, sodium bisulfite.
5. the method for utilizing rutin to prepare Quercetin and rhamnosyl according to claim 4, is characterized in that, described complexing agent is any or their mixture in tartrate, heptose hydrochlorate, Sunmorl N 60S, sodium alginate, ethylenediamine tetraacetic acid (EDTA).
6. prepare the method for Quercetin and rhamnosyl according to the rutin that utilizes described in claim 4 ~ 5 any one, it is characterized in that, the neutralizing treatment in described steps d for any neutralizing hydrolysis mother liquor in the sodium hydroxide that is 0.05 ~ 0.2mol/L by concentration, potassium hydroxide, hydrated barta to pH be 6.5 ~ 7.0.
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| CN104292281A (en) * | 2014-09-22 | 2015-01-21 | 右玉县安德益源生物科技有限公司 | Method for preparing high-purity rutin by using integrated technique |
| CN105315317A (en) * | 2015-10-29 | 2016-02-10 | 南京中医药大学 | Product prepared by heating quercetin and rhamnose as well as preparation method and application thereof |
| CN111500661A (en) * | 2020-04-23 | 2020-08-07 | 江南大学 | Method for simultaneously preparing L-rhamnose and isoquercetin |
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| CN1483825A (en) * | 2003-08-01 | 2004-03-24 | 金凤燮 | Method for preparing isoquercetin and quercetin by enzymatic method and hydrolyzing rutin |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104292281A (en) * | 2014-09-22 | 2015-01-21 | 右玉县安德益源生物科技有限公司 | Method for preparing high-purity rutin by using integrated technique |
| CN105315317A (en) * | 2015-10-29 | 2016-02-10 | 南京中医药大学 | Product prepared by heating quercetin and rhamnose as well as preparation method and application thereof |
| CN111500661A (en) * | 2020-04-23 | 2020-08-07 | 江南大学 | Method for simultaneously preparing L-rhamnose and isoquercetin |
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| CN103965153B (en) | 2016-05-04 |
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