CN107335430A - A kind of catalyst and the application in selective catalysis prepares rare ginsenoside - Google Patents
A kind of catalyst and the application in selective catalysis prepares rare ginsenoside Download PDFInfo
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- CN107335430A CN107335430A CN201710583335.4A CN201710583335A CN107335430A CN 107335430 A CN107335430 A CN 107335430A CN 201710583335 A CN201710583335 A CN 201710583335A CN 107335430 A CN107335430 A CN 107335430A
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract
A kind of application the invention discloses catalyst and in selective catalysis prepares rare ginsenoside, the catalyst are Mn Ce composite oxides, are made as follows：First cerous nitrate, manganese nitrate and urea are dissolved in ethanol water, then carry out hydro-thermal reaction, reaction temperature is 180 200 DEG C, and the time is 18 22h, finally centrifuges, washs, drying, calcining, grinding；Manganese nitrate molar concentration is 0.015 0.035mol/L, and cerous nitrate molar concentration is 24 times of manganese nitrate molar concentration, and urea molar concentration is cerous nitrate, 35 times of manganese nitrate molar concentration sum.Mn Ce composite oxides provided by the invention can be used for the C20 positions hydroxyl being catalyzed on ginsenoside and C22 positions hydrogen dehydration generation E type double bond dehydration products, E-isomer is set to account for more than 90% (accounting for 50% in the prior art) of three kinds of dehydration product total contents, so as to improve the interference that raw material availability is low, and reduction end ene-type, Z-type isomers purify to E-isomer.
Description
Technical field
The invention belongs to selective catalysis field, the beam system for being related to isomers is standby, and in particular to a kind of catalyst and
Selective catalysis prepares the application in rare ginsenoside.
Background technology
The C20 positions of dammarane type ginsenoside have hydroxyl more, are widely present in panax species, and content is more.Through
After heating, dehydration easily occurs for the C20 positions hydroxyl of dammarane type saponin(e and its aglycon, forms double bond, and generation double bond is different
Serial the C20 positions dehydroxylation dammarane type rare ginsenoside and its aglycon of structure.
But during C20 positions hydroxyl generation dehydration, isomer 1-3 (belonging to rare saponin(e) can be generated, it is different with point
The double bond of structure body 1 is formed between C20, C21, and the double bond of isomer 2,3 is formed between C20, C22 (end ene-type), but
It is that isomer 2,3 one is E types, another is Z-type.Referring to CN 102911238A and CN 103193846A.
Applicant's early-stage Study finds that E-isomer is the most stable, and antitumor activity preferably (to liver cancer, breast cancer and
The lethality of colorectal cancer tumour cell is 3-5 times of other two kinds of isomers).Therefore, it is also more urgent to the demand of E-isomer
Cut.Before technical solution of the present invention is obtained, applicant is the mixture by producing three kinds of isomers to raw material dehydration, then
Carry out separation and E-isomer is prepared.Although the content of E-isomer accounts for three kinds of isomers total contents in mixture
50% or so, but still have two deficiencies：First, end ene-type, the generation of Z-type isomers are inevitable, and raw material availability is low；The
Two, end ene-type, Z-type isomers total content account for 50%, it is necessary to the E of high-purity could be obtained using the extra high method of separating degree
Type isomers.The two deficiencies improve the time cost and human cost that applicant obtains E-isomer.
The content of the invention
Can be with selective catalysis dammarane type saponin(e it is an object of the invention to overcome the deficiencies of the prior art and provide one kind
And its solid catalyst and catalysis preparation method of the C20 positions hydroxyl of aglycon and C22 positions hydrogen dehydration generation E-isomer.
The present invention is achieved by following technical scheme
A kind of catalyst, it is Mn-Ce composite oxides, is made as follows：First by cerous nitrate, manganese nitrate and urea
It is dissolved in ethanol water, then carries out hydro-thermal reaction, reaction temperature is 180-200 DEG C, time 18-22h, finally centrifugation,
Washing, dry, calcine, grinding；Manganese nitrate molar concentration is 0.015-0.035mol/L, and cerous nitrate molar concentration is rubbed for manganese nitrate
2-4 times of that concentration, urea molar concentration is cerous nitrate, 3-5 times of manganese nitrate molar concentration sum.
Preferably, ethanol volumetric concentration is 50-60% in ethanol water.
Preferably, successively with absolute ethyl alcohol and water washing 2-4 times.
Preferably, 100-120 DEG C of dry 8-12h after washing.
Preferably, 450-550 DEG C of calcining 3-5h after drying.
Above-mentioned Mn-Ce composite oxides are used for the C20 positions hydroxyl being catalyzed on the ginsenoside of following chemical constitution and C22 positions
The purposes of hydrogen dehydration generation E type double bond dehydration products, chemical constitution and reaction equation are as follows：
Preferably, R1 is-OH, and R2 is-OGlc (2-1) Rha.
R1 is-OH, R2 when being-OGlc (2-1) Rha, and dewatering is：Using ginsenoside Rg2 as raw material, with methanol volume
The methanol aqueous solution (containing the formic acid that concentration expressed in percentage by volume is 0.05%) that percentage concentration is 50% is reaction system, with Mn-Ce
Composite oxides are catalyst in 80 DEG C of hot back flow reactions 2 hours, and reaction terminates rear filtering and concentrating.
Preferably, R1For-OGlc, R2For-H.
R1For-OGlc, R2For-H when, dewatering is：Using ginseng saponin Rh 2 as raw material, using methanol concentration expressed in percentage by volume as
50% methanol aqueous solution (containing the formic acid that concentration expressed in percentage by volume is 0.05%) is reaction system, with Mn-Ce composite oxides
It is catalyst in 85 DEG C of hot back flow reactions 2 hours, reaction terminates rear filtering and concentrating.
Advantages of the present invention：
Mn-Ce composite oxides provided by the invention can be used for the C20 positions hydroxyl being catalyzed on ginsenoside and C22 positions hydrogen
Dehydration generation E type double bond dehydration products, make E-isomer account for more than the 90% of three kinds of dehydration product total contents (in the prior art
Account for 50%), so as to improve the interference that raw material availability is low, and reduction end ene-type, Z-type isomers purify to E-isomer.
Brief description of the drawings
Fig. 1 is the TEM transmission electron microscope pictures of Mn-Ce composite oxides, it is seen that obvious double-decker.
Embodiment
Technical scheme is further described with reference to specific embodiment.
The preparation of embodiment 1Mn-Ce composite oxides
First cerous nitrate, manganese nitrate and urea are dissolved in ethanol water (ethanol volumetric concentration is 55%), then carried out
Hydro-thermal reaction, reaction temperature are 190 DEG C, time 20h, finally centrifuge, wash (first washed, be washed with water with ethanol, repeatedly 3
All over), dry (110 DEG C of drys 10h), calcining (500 DEG C calcining 4h), grind；Manganese nitrate molar concentration is 0.025mol/L, nitric acid
Cerium molar concentration is 3 times of manganese nitrate molar concentration, and urea molar concentration is cerous nitrate, 4 times of manganese nitrate molar concentration sum.
Fig. 1 is the TEM transmission electron microscope pictures of Mn-Ce composite oxides, it is seen that obvious double-decker.
The preparation of the Mn-Ce composite oxides of embodiment 2
First cerous nitrate, manganese nitrate and urea are dissolved in ethanol water (ethanol volumetric concentration is 50%), then carried out
Hydro-thermal reaction, reaction temperature are 180 DEG C, time 22h, finally centrifuge, wash and (first washed, be washed with water with ethanol, so repeatedly
2 times), dry (100 DEG C of drys 12h), calcining (450 DEG C calcining 5h), grind；Manganese nitrate molar concentration is 0.015mol/L, nitre
Sour cerium molar concentration is 2 times of manganese nitrate molar concentration, and urea molar concentration is cerous nitrate, 3 times of manganese nitrate molar concentration sum.
The pattern of Mn-Ce composite oxides prepared by the embodiment is consistent with embodiment 1.
The preparation of embodiment 3Mn-Ce composite oxides
First cerous nitrate, manganese nitrate and urea are dissolved in ethanol water (ethanol volumetric concentration is 60%), then carried out
Hydro-thermal reaction, reaction temperature are 200 DEG C, time 18h, finally centrifuge, wash and (first washed, be washed with water with ethanol, so repeatedly
4 times), dry (120 DEG C of drys 8h), calcining (550 DEG C calcining 3h), grind；Manganese nitrate molar concentration is 0.035mol/L, nitric acid
Cerium molar concentration is 4 times of manganese nitrate molar concentration, and urea molar concentration is cerous nitrate, 5 times of manganese nitrate molar concentration sum.
The pattern of Mn-Ce composite oxides prepared by the embodiment is consistent with embodiment 1.
Embodiment 4 orients dehydration as raw material using ginsenoside Rg2 and prepares ginsenoside (E)-F4
Taking 500mg ginsenoside Rg2s, (95%) self-control, purity are more than, the methanol aqueous solution (first of formic acid is contained with 200mL
For alcohol concentration expressed in percentage by volume 50%) to dissolve, formic acid addition volume is the 0.05% of methanol water volume.After dissolving, in reaction system
Mn-Ce composite oxides prepared by middle addition 50mg embodiments 1-3,80 DEG C of hot back flow reactions 2 hours.It is natural after reaction terminates
Room temperature is cooled to, is filtered off except Mn-Ce composite oxide particles, filtrate is condensed into the aqueous solution for being substantially free of methanol, and freezing is dry
It is dry to obtain freeze-dried powder.Freeze-dried powder is purified into obtain 385-396mg ginsenosides (E)-F4 using high-speed counter-current, purity is more than 98%.
High speed adverse current chromatogram purification process is as follows：
Prepare ethyl acetate, alcohol and water-acetic acid (volume ratio 4 within 12 hours before separation:1:5:0.08) solvent system, specifically
Compound method is：Four kinds of solvents are mixed in proportion, acutely after concussion, standing 12 hours makes it be layered completely, will in funnel
Upper and lower phase separation, upper phase are used as stationary phase, and lower phase is used as mobile phase, with preceding ultrasonic half an hour.
Phase 5mL and lower phase 5mL are taken respectively, and by above-mentioned freeze-dried powder, all dissolving (needs ultrasonic wave added wherein after mixing
Dissolving) sample solution as high-speed counter-current.
The upper phase (stationary phase) of ultrasound degassing in two phase solvent system is pumped into HSCCC separation with 20mL/min flow velocity
In pipe (35 ± 2 DEG C of separation temperature), after upper phase is full of whole separating pipe, regulation engine speed reaches 800r/min, dextrorotation
Turn, after stabilization of speed, lower phase (mobile phase), Detection wavelength 254nm are pumped into 1.4mL/min flow velocitys.When mobile phase is from master
When machine mouth flows out, explanation system has reached fluid dynamic equilibrium, and the 10mL sample solutions being ready for now are injected into HSCCC
Instrument, gathered data is started simultaneously at, target component is collected according to chromatogram.
Embodiment 5 orients dehydration as raw material using ginseng saponin Rh 2 and prepares ginsenoside (E)-Rh3
Taking 500mg ginseng saponin Rh 2s, (95%) self-control, purity are more than, the methanol aqueous solution (first of formic acid is contained with 200mL
For alcohol concentration expressed in percentage by volume 50%) to dissolve, formic acid addition volume is the 0.05% of methanol water volume.After dissolving, in reaction system
Mn-Ce composite oxides prepared by middle addition 50mg embodiments 1-3,85 DEG C of hot back flow reactions 2 hours.It is natural after reaction terminates
Room temperature is cooled to, is filtered off except Mn-Ce composite oxide particles, filtrate is condensed into the solution for being substantially free of methanol, freeze-drying
Obtain freeze-dried powder.Freeze-dried powder is purified into obtain 383-397mg ginsenosides (E)-Rh3 with high-speed counter-current, purity is more than 98%.
Prepare ethyl acetate, alcohol and water-acetic acid (volume ratio 4 within 12 hours before separation:1:6:0.08) solvent system, specifically
Compound method is：Four kinds of solvents are mixed in proportion, acutely after concussion, standing 12 hours makes it be layered completely, will in funnel
Upper and lower phase separation, upper phase are used as stationary phase, and lower phase is used as mobile phase, with preceding ultrasonic half an hour.
Phase 5mL and lower phase 5mL are taken respectively, and by above-mentioned freeze-dried powder, all dissolving (needs ultrasonic wave added wherein after mixing
Dissolving) sample solution as high-speed counter-current.
The upper phase (stationary phase) of ultrasound degassing in two phase solvent system is pumped into HSCCC separation with 20mL/min flow velocity
In pipe (35 ± 2 DEG C of separation temperature), after upper phase is full of whole separating pipe, regulation engine speed reaches 800r/min, dextrorotation
Turn, after stabilization of speed, lower phase (mobile phase), Detection wavelength 254nm are pumped into 1.4mL/min flow velocitys.When mobile phase is from master
When machine mouth flows out, explanation system has reached fluid dynamic equilibrium, and the 10mL sample solutions being ready for now are injected into HSCCC
Instrument, gathered data is started simultaneously at, target component is collected according to chromatogram.
Mn-Ce composite oxides provided by the invention can be used for the C20 positions hydroxyl being catalyzed on ginsenoside and C22 positions hydrogen
Dehydration generation E type double bond dehydration products, make E-isomer account for more than the 90% of three kinds of dehydration product total contents (in the prior art
Account for 50%), so as to improve the interference that raw material availability is low, and reduction end ene-type, Z-type isomers purify to E-isomer.
Claims (10)
1. a kind of catalyst, it is Mn-Ce composite oxides, it is characterised in that be made as follows：First by cerous nitrate, nitre
Sour manganese and urea are dissolved in ethanol water, then carry out hydro-thermal reaction, and reaction temperature is 180-200 DEG C, time 18-22h,
Finally centrifuge, wash, drying, calcining, grinding；Manganese nitrate molar concentration is 0.015-0.035mol/L, cerous nitrate molar concentration
For 2-4 times of manganese nitrate molar concentration, urea molar concentration is cerous nitrate, 3-5 times of manganese nitrate molar concentration sum.
2. catalyst according to claim 1, it is characterised in that：Ethanol volumetric concentration is 50-60% in ethanol water.
3. catalyst according to claim 1, it is characterised in that：Successively with absolute ethyl alcohol and water washing 2-4 times.
4. catalyst according to claim 1, it is characterised in that：100-120 DEG C of dry 8-12h after washing.
5. catalyst according to claim 1, it is characterised in that：450-550 DEG C of calcining 3-5h after drying.
6. any Mn-Ce composite oxides of claim 1-5 are used for the C20 being catalyzed on the ginsenoside of following chemical constitution
The purposes of position hydroxyl and C22 positions hydrogen dehydration generation E type double bond dehydration products, chemical constitution and reaction equation are as follows：
7. purposes according to claim 6, it is characterised in that：R1For-OH, R2For-OGlc (2-1) Rha.
8. purposes according to claim 7, it is characterised in that dewatering is：Using ginsenoside Rg2 as raw material, with first
The methanol aqueous solution that alcohol concentration expressed in percentage by volume is 50% is reaction system, and it is 0.05% that reaction system, which contains concentration expressed in percentage by volume,
Formic acid, it is catalyst in 80 DEG C of hot back flow reactions 2 hours using Mn-Ce composite oxides, reaction terminates rear filtering and concentrating.
9. purposes according to claim 6, it is characterised in that：R1For-OGlc, R2For-H.
10. purposes according to claim 9, it is characterised in that dewatering is：Using ginseng saponin Rh 2 as raw material, with first
The methanol aqueous solution (containing the formic acid that concentration expressed in percentage by volume is 0.05%) that alcohol concentration expressed in percentage by volume is 50% is reaction system, with
Mn-Ce composite oxides are catalyst in 85 DEG C of hot back flow reactions 2 hours, and reaction terminates rear filtering and concentrating.
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| CN201710583335.4A CN107335430B (en) | 2017-07-18 | 2017-07-18 | A kind of catalyst and the application in rare ginsenoside is prepared in selective catalysis |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105344359A (en) * | 2015-11-03 | 2016-02-24 | 广西大学 | Preparation method and use of CuO/Ce-Mn-O catalyst |
| CN106268783A (en) * | 2016-07-19 | 2017-01-04 | 中国矿业大学 | Mn Ce/Al2o3the preparation of catalyst and the method for catalytic ozonation organic wastewater with difficult degradation thereby |
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- 2017-07-18 CN CN201710583335.4A patent/CN107335430B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105344359A (en) * | 2015-11-03 | 2016-02-24 | 广西大学 | Preparation method and use of CuO/Ce-Mn-O catalyst |
| CN106268783A (en) * | 2016-07-19 | 2017-01-04 | 中国矿业大学 | Mn Ce/Al2o3the preparation of catalyst and the method for catalytic ozonation organic wastewater with difficult degradation thereby |
Non-Patent Citations (1)
| Title |
|---|
| XINXIN XING等: "Synthesis of mixed Mn-Ce-O-x one dimensional nanostructures and their catalytic activity for CO oxidation", 《CERAMICS INTERNATIONAL》 * |
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Effective date of registration: 20191008 Address after: 164300 Third Committee of Jinhe farm, Aihui District, Heihe City, Heilongjiang Province Applicant after: Heilongjiang Bei'an Nongken Tianyun Mountain Products Co., Ltd. Address before: 211198 No. 1009 Tianyuan East Road, High-tech Park, Jiangning District, Nanjing City, Jiangsu Province Applicant before: Nanjing Profluoro Bioassay Technology Co., Ltd. |
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