CN114669326B - Novel magnetic solid acid catalyst and application thereof in extracting saponin from turmeric total saponins - Google Patents
Novel magnetic solid acid catalyst and application thereof in extracting saponin from turmeric total saponins Download PDFInfo
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- CN114669326B CN114669326B CN202210385692.0A CN202210385692A CN114669326B CN 114669326 B CN114669326 B CN 114669326B CN 202210385692 A CN202210385692 A CN 202210385692A CN 114669326 B CN114669326 B CN 114669326B
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- 150000007949 saponins Chemical class 0.000 title claims abstract description 107
- 229930182490 saponin Natural products 0.000 title claims abstract description 102
- 235000017709 saponins Nutrition 0.000 title claims abstract description 102
- 239000011973 solid acid Substances 0.000 title claims abstract description 99
- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 239000001397 quillaja saponaria molina bark Substances 0.000 title claims abstract description 64
- 235000003392 Curcuma domestica Nutrition 0.000 title claims abstract description 26
- 235000003373 curcuma longa Nutrition 0.000 title claims abstract description 26
- 235000013976 turmeric Nutrition 0.000 title claims abstract description 26
- 244000008991 Curcuma longa Species 0.000 title claims abstract 6
- 238000000034 method Methods 0.000 claims abstract description 38
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 36
- -1 mercapto siloxane Chemical class 0.000 claims abstract description 25
- HDXIQHTUNGFJIC-UHFFFAOYSA-N (25R)-spirost-5-en-3beta-ol 3-O-<O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-glucopyranoside> Natural products O1C2(OCC(C)CC2)C(C)C(C2(CCC3C4(C)CC5)C)C1CC2C3CC=C4CC5OC1OC(CO)C(O)C(O)C1OC1OC(C)C(O)C(O)C1O HDXIQHTUNGFJIC-UHFFFAOYSA-N 0.000 claims abstract description 14
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- VNONINPVFQTJOC-ZGXDEBHDSA-N dioscin Chemical compound O([C@@H]1[C@@H](CO)O[C@H]([C@@H]([C@H]1O)O[C@H]1[C@@H]([C@H](O)[C@@H](O)[C@H](C)O1)O)O[C@@H]1CC2=CC[C@H]3[C@@H]4C[C@H]5[C@@H]([C@]4(CC[C@@H]3[C@@]2(C)CC1)C)[C@@H]([C@]1(OC[C@H](C)CC1)O5)C)[C@@H]1O[C@@H](C)[C@H](O)[C@@H](O)[C@H]1O VNONINPVFQTJOC-ZGXDEBHDSA-N 0.000 claims abstract description 14
- CJNUQCDDINHHHD-APRUHSSNSA-N dioscin Natural products C[C@@H]1CC[C@@]2(OC1)O[C@H]3C[C@H]4[C@@H]5CC=C6C[C@H](CC[C@@H]6[C@H]5CC[C@]4(C)[C@H]3[C@@H]2C)O[C@@H]7O[C@H](CO)[C@@H](O[C@@H]8O[C@@H](C)[C@H](O)[C@@H](O)[C@H]8O)[C@H](O)[C@H]7O[C@@H]9O[C@@H](C)[C@H](O)[C@@H](O)[C@H]9O CJNUQCDDINHHHD-APRUHSSNSA-N 0.000 claims abstract description 14
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- 238000002360 preparation method Methods 0.000 claims abstract description 12
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- 238000000605 extraction Methods 0.000 abstract description 32
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 24
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- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 abstract description 5
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- DWCSNWXARWMZTG-UHFFFAOYSA-N Trigonegenin A Natural products CC1C(C2(CCC3C4(C)CCC(O)C=C4CCC3C2C2)C)C2OC11CCC(C)CO1 DWCSNWXARWMZTG-UHFFFAOYSA-N 0.000 description 9
- WQLVFSAGQJTQCK-VKROHFNGSA-N diosgenin Chemical compound O([C@@H]1[C@@H]([C@]2(CC[C@@H]3[C@@]4(C)CC[C@H](O)CC4=CC[C@H]3[C@@H]2C1)C)[C@@H]1C)[C@]11CC[C@@H](C)CO1 WQLVFSAGQJTQCK-VKROHFNGSA-N 0.000 description 9
- WQLVFSAGQJTQCK-UHFFFAOYSA-N diosgenin Natural products CC1C(C2(CCC3C4(C)CCC(O)CC4=CCC3C2C2)C)C2OC11CCC(C)CO1 WQLVFSAGQJTQCK-UHFFFAOYSA-N 0.000 description 9
- 125000003396 thiol group Chemical group [H]S* 0.000 description 9
- VFLDPWHFBUODDF-FCXRPNKRSA-N curcumin Chemical compound C1=C(O)C(OC)=CC(\C=C\C(=O)CC(=O)\C=C\C=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-FCXRPNKRSA-N 0.000 description 8
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
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- 235000014375 Curcuma Nutrition 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 244000281702 Dioscorea villosa Species 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- 241001678283 Dioscorea zingiberensis Species 0.000 description 2
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- 229930182555 Penicillin Natural products 0.000 description 2
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 2
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- 239000007858 starting material Substances 0.000 description 2
- 150000003431 steroids Chemical class 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 241000234272 Dioscoreaceae Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J71/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton is condensed with a heterocyclic ring
- C07J71/0005—Oxygen-containing hetero ring
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a novel magnetic solid acid catalyst and application thereof in extracting saponin from turmeric total saponins. The novel magnetic solid acid catalyst comprises a core layer and a shell layer; the core layer is magnetic Fe 3O4, and the shell layer is the reaction product of SiO 2, mercapto siloxane and sulfonate compound. The preparation method of the novel magnetic solid acid catalyst is simple, and the conventional chlorosulfonic acid sulfonation method is not adopted in the sulfonation method, so that the operation danger caused by chlorosulfonic acid can be avoided; the novel magnetic solid acid catalyst is applied to extracting dioscin by alcoholysis of total saponins of turmeric by a solid acid solvothermal method, and the saponin extraction efficiency is still higher than the traditional 1.5M sulfuric acid hydrolysis efficiency after three continuous cycles; the novel magnetic solid acid catalyst has the advantages that the defect that the common magnetic core-shell structure is easy to erode by acid and cannot be actively regenerated can be overcome, and the prepared magnetic solid acid catalyst is free of corrosion to equipment and environment-friendly.
Description
Technical Field
The invention relates to the technical field of magnetic nano catalysts, in particular to a novel magnetic solid acid catalyst and application thereof in extracting saponin from turmeric total saponins.
Background
Yellow ginger Dioscoreazingiberensis C.H.Wright (DZW) is the main cash crop for producing dioscin in China. Diosgenin is a great demand in the pharmaceutical field as an important pharmaceutical compound, mainly as a starting material for partially synthesizing steroid drugs such as oral contraceptives and sex hormones, wherein about 60% of the steroid sex hormone drugs are produced from diosgenin. At present, 4000t dioscin is needed every year worldwide, while the total yield of saponin in China reaches 3000t and accounts for 75% of the world, and the total yield is still increasing year by year.
At present, two conventional methods exist in industry for extracting diosgenin from turmeric. One of these is usually the direct acid hydrolysis of the starting material with 1.5M H 2SO4 or 2M hydrochloric acid or sulfuric acid. It is reported that at least 130-180t dry turmeric rhizome, 7-8t 98% H 2SO4 (or 15-20t 37% HCl) and 1t 10% NaOH neutralization solution and 120# gasoline 6t extraction solution are required to complete saponin extraction per 1t diosgenin production. The process for producing dioscin is simple and effective, but the saponin is converted into dioscin after acid hydrolysis, starch in plant residues is also degraded into low-molecular-weight sugar by acid, most cellulose remains in the acid residues, and some parts are also degraded into low-molecular-weight sugar. These low molecular weight sugars are soluble in water and in wastewater with other soluble compounds such as proteins, organic acids, fatty acids, these species account for about 60% of the total organic carbon in the wastewater. Another method is to extract steroid saponin from the raw materials, hydrolyze in strong acid, and finally add petroleum ether into the solution to extract dioscin into the organic phase. However, this is not an environmentally friendly process, since acid hydrolysates lead to high concentrations of chemical oxygen demand COD (about 50000-80000 mg/L), SO4 2- (29700-46200 mg/L) and acidic wastewater (H + is 1.1-1.2 mol/L in large amounts of wastewater), which has not been produced with such efficiency as to meet the "emission standards for Water pollutants for Saponin industry" (GB 20425-2006).
Therefore, in order to solve the defects of high acidity, large chromaticity, high salt content and complex composition of high-concentration organic wastewater generated based on the inorganic strong acid hydrolysis technology, the bottleneck restricting the industrial production of saponin is broken, and the development of an efficient and clean saponin production process is very important. The key point of breaking through the problem of the hydrolysis pollution of the saponin and the improvement of the extraction rate of the saponin is that the method has important economic and social benefits.
Disclosure of Invention
The invention aims to overcome the technical defects, provides a novel magnetic solid acid catalyst and application of the novel magnetic solid acid catalyst in extracting saponin from turmeric total saponins, and solves the technical problems of large saponin hydrolysis pollution and low saponin extraction rate in the prior art.
The first aspect of the invention provides a novel magnetic solid acid catalyst comprising a core layer and a shell layer; wherein the core layer is magnetic Fe 3O4, and the shell layer is the reaction product of SiO 2, sulfhydryl siloxane and sulfonate compound.
The second aspect of the present invention provides a method for preparing a novel magnetic solid acid catalyst, comprising the steps of:
Reacting Fe 3O4@SiO2 with a mercaptosiloxane to produce a magnetic precursor containing a mercapto functional group;
And reacting the magnetic precursor containing the sulfhydryl functional group with a sulfonate compound to obtain the novel magnetic solid acid catalyst.
The third aspect of the invention provides the application of the novel magnetic solid acid catalyst, which is applied to the extraction of saponin in the yam plants.
The fourth aspect of the invention provides a process for extracting saponin from turmeric total saponins, which comprises the following steps:
alcoholysis reaction of total saponins of Curcuma rhizome and novel magnetic solid acid catalyst in ethanol to obtain dioscin.
Compared with the prior art, the invention has the beneficial effects that:
The preparation method of the novel magnetic solid acid catalyst is simple, the conventional chlorosulfonic acid sulfonation method is not adopted in the sulfonation method, the operation danger caused by chlorosulfonic acid can be avoided, and the preparation method has the advantages of simplicity in synthetic reaction method, mild reaction conditions and safety in operation;
The novel magnetic solid acid catalyst is applied to extracting dioscin by alcoholysis of total saponins of turmeric by a solid acid solvent method, and the saponin extraction efficiency is still higher than the traditional 1.5M sulfuric acid hydrolysis efficiency after three continuous cycles; the novel magnetic solid acid catalyst has the advantages that the defect that the common magnetic core-shell structure is easy to be corroded by acid and cannot be regenerated (the traditional solid acid structure of the Fe 3O4@SiO2 core-shell structure is easy to be corroded by acid and cannot be subjected to active regeneration in a mode of adding acid again for soaking, and the thiol group loaded with the activity on the surface of the solid acid can restore the circulating activity in a regeneration reaction mode), so that the prepared magnetic solid acid catalyst is free of corrosion to equipment and environment-friendly;
Compared with the traditional sulfuric acid hydrolysis method for extracting the total saponins, the method firstly uses ethanol as a recoverable solvent and extracts the total saponins by a extraction method; and the prepared novel magnetic solid acid is used as a catalyst for alcoholysis of total saponins to extract dioscin, and the solvent used for extraction and the alcoholysis solvent in the whole process can be recycled, so that no acidic waste liquid and pollution are discharged, and the novel magnetic solid acid accords with the environment-friendly concept and has wide industrial application prospect.
Drawings
FIG. 1 is a schematic structural diagram of a novel magnetic solid acid catalyst prepared in example 1 of the present invention;
FIG. 2 is a synthetic route diagram of the novel magnetic solid acid catalyst prepared in example 1 of the present invention;
FIGS. 3a to d are respectively the IR spectra of Fe 3O4、Fe3O4@SiO2、Fe3O4@SiO2 -Pr-SH and Fe 3O4@SiO2-Pr-S-Pr-SO3 H prepared in example 1 of the present invention;
FIG. 4 is a flow chart of the extraction process of total saponins of turmeric in the present invention;
FIG. 5 is a process flow diagram of extracting saponin from rhizoma Dioscoreae Zingiberensis total saponins by using the novel magnetic solid acid catalyst of the present invention;
In FIG. 6, (a) to (b) are respectively the infrared spectrograms of the reference diosgenin standard (purity: 95%) and the refined saponin obtained in application example 1 of the present invention;
FIG. 7 is a graph showing the regeneration and alcoholysis cycle efficiency of the novel magnetic solid acid catalyst of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The first aspect of the invention provides a novel magnetic solid acid catalyst comprising a core layer and a shell layer; wherein the core layer is magnetic Fe 3O4, and the shell layer is the reaction product of SiO 2, sulfhydryl siloxane and sulfonate compound.
In some embodiments of the invention, the reaction product of SiO 2, mercaptosiloxane, sulfonate compound is obtained by preparing a precursor containing a mercapto functional group by reaction of shell SiO 2 with mercaptosiloxane in advance, followed by reacting the precursor with sulfonate compound.
In the invention, the mercaptosiloxane is at least one of 3- (mercaptopropyl) trimethoxysilane (MPTMS) or 3- (mercaptopropyl) triethoxysilane (MPTES); the sulfonate compound is sultone, and further 1,3 propane sultone.
The second aspect of the present invention provides a method for preparing a novel magnetic solid acid catalyst, comprising the steps of:
Reacting Fe 3O4@SiO2 with a mercaptosiloxane to produce a magnetic precursor containing a mercapto functional group;
And reacting the magnetic precursor containing the sulfhydryl functional group with a sulfonate compound to obtain the novel magnetic solid acid catalyst.
The invention uses a magnetic precursor containing mercapto functional groups, which is obtained by reacting magnetic Fe 3O4@SiO2 particles with mercapto siloxane with a core-shell structure, as a raw material, uses mercapto groups as reaction sites, reacts with sulfonate compounds to modify sulfonic acid groups, thus obtaining a novel magnetic solid acid catalyst, and in the process of extracting saponin from turmeric total saponins, the saponin is obtained by using acid sulfonic acid groups to break glycosidic bonds of the saponin structure.
In the invention, the mass ratio of the magnetic precursor containing the mercapto functional group to the sulfonate compound is 1: (0.5 to 2), and further 1: (0.5-1).
Referring to fig. 1-2, in some embodiments of the present invention, the preparation method of the novel magnetic solid acid catalyst includes the following steps:
Obtaining Fe 3O4@SiO2 -Pr-SH nano particles;
The Fe 3O4@SiO2 -Pr-SH nano particles are reacted with 1,3 propane sultone to obtain the novel magnetic solid acid catalyst Fe 3O4@SiO2-Pr-S-Pr-SO3 H.
In the present invention, fe 3O4@SiO2 -Pr-SH nanoparticles can be synthesized by literature, which is a prior art and will not be described herein.
In the present invention, the step of reacting Fe 3O4@SiO2 -Pr-SH nanoparticles with 1,3 propane sultone includes:
And carrying out reflux reaction on the Fe 3O4@SiO2 -Pr-SH nano particles and 1,3 propane sultone under the action of a first organic solvent to obtain the novel magnetic solid acid catalyst Fe 3O4@SiO2-Pr-S-Pr-SO3 H.
Further, the mass ratio of the Fe 3O4@SiO2 -Pr-SH nano-particles to the 1,3 propane sultone is 1: (0.5 to 2), and further 1: (0.7-0.8).
Further, the first organic solvent is toluene.
Further, the dosage ratio of the Fe 3O4@SiO2 -Pr-SH nanoparticles to the first organic solvent was 1g: (10-40) mL.
Further, the temperature of the reflux reaction is 100-120 ℃, and further 110 ℃; the reflux reaction time is 20-24 hours, more 24 hours; the reflux reaction was carried out under nitrogen protection.
In some embodiments of the invention, the step of reacting the Fe 3O4@SiO2 -Pr-SH nanoparticle with 1,3 propane sultone comprises: mixing Fe 3O4@SiO2 -Pr-SH particles with toluene, performing ultrasonic dispersion, adding 1,3 propane sultone in the stirring process, and keeping the temperature of 100-120 ℃ for reaction reflux for 20-24 h under the protection of nitrogen; and cooling after the reaction is finished, collecting a magnetic product by using a magnet, washing until the pH value is neutral, and drying to obtain the novel magnetic solid acid catalyst Fe 3O4@SiO2-Pr-S-Pr-SO3 H.
The third aspect of the invention provides the application of the novel magnetic solid acid catalyst, which is applied to the extraction of saponin in the yam plants.
In the present invention, the Dioscoreaceae plant includes Curcuma rhizome; further applied to the extraction of saponin in the turmeric total saponins.
In the invention, the novel solid acid catalyst can be regenerated after being recovered; the regeneration treatment process comprises the following steps: reacting the recovered novel solid acid catalyst with a sulfonate compound to obtain a novel magnetic solid acid catalyst with recovered activity; wherein the reaction time is 12-24 h. In some specific embodiments of the invention, the saponin extraction efficiency of the traditional 1.5M sulfuric acid hydrolysis saponin is used as a reference index of the solid acid extraction efficiency, and after continuous cyclic alcoholysis, when the test activity is lower than the 1.5M sulfuric acid hydrolysis saponin extraction efficiency, the recovered novel solid acid catalyst is subjected to regeneration treatment.
The fourth aspect of the invention provides a process for extracting saponin from turmeric total saponins, which comprises the following steps:
alcoholysis reaction of total saponins of Curcuma rhizome and novel magnetic solid acid catalyst in ethanol to obtain dioscin.
In the invention, the mass ratio of the total saponins of turmeric to the novel magnetic solid acid catalyst is 1: (0.1 to 10), further 1:5, a step of; the dosage ratio of the total saponins to the ethanol is 1g: (30-100) mL, further 1g:60mL.
In the invention, the alcoholysis reaction is carried out in a hydrothermal reaction kettle, and the temperature of the alcoholysis reaction is 100-120 ℃, and further 120 ℃; the alcoholysis reaction time is 6-8 h, and is further 7h.
In the invention, the extraction process of the saponin further comprises the following steps: after the reaction is finished, a magnet is used for recovering the novel magnetic solid acid catalyst, the reaction liquid after the novel magnetic solid acid catalyst is separated is filtered, the filtrate is alcoholysis reaction liquid, and the alcoholysis reaction liquid is spin-dried to obtain a crude saponin product.
Further, washing the separated solid acid catalyst by using absolute ethyl alcohol, combining washing liquid and alcoholysis reaction liquid, and spin-drying to obtain a crude saponin product. The process is favorable for removing impurities attached to the solid acid catalyst and ensuring the recycling effect of the solid acid catalyst.
In the invention, the crude product of the saponin is added into a second organic solvent to be dissolved and filtered to obtain saponin liquid, the absorbance is measured by a UV-Vis method, the dioscin content is calculated by combining a standard curve, and the residue is a small amount of unreacted saponin and short-chain polysaccharide. Wherein the second organic solvent is at least one of dichloromethane, chloroform and petroleum ether, and more preferably chloroform.
In the invention, the extraction process of the saponin further comprises the following steps: refining the crude saponin product to obtain refined saponin. Further, the refining process comprises the following steps: and (3) carrying out reflux reaction on the crude product and the activated carbon in a third organic solvent, filtering the mixed solution by using a 0.2-micrometer organic filter membrane after the reaction is finished, spin-drying the filtrate, and recrystallizing by using petroleum ether to obtain the refined diosgenin. Wherein the third organic solvent is chloroform or petroleum ether, and further chloroform.
In some embodiments of the present invention, the total saponins of turmeric are obtained by the following steps:
cleaning and crushing the yam, drying, adding ethanol according to the dosage ratio of 1g (5-10) mL, and extracting under a reflux state; filtering after extraction, steaming the filtrate, and oven drying to obtain rhizoma Dioscoreae Zingiberensis total saponins.
Further, the reflux extraction temperature is 80-100 ℃, and the reflux extraction time is 3-6 h.
Further, washing the filter cake with ethanol, mixing the filtrate and the washing liquid, removing the liquid by rotary evaporation, and drying to obtain the turmeric total saponins. The process is beneficial to improving yield of saponin.
Further, the ethanol obtained by rotary evaporation can be recycled for re-extraction of saponins and subsequent alcoholysis steps.
Referring to fig. 4, in an application example of the present invention, total saponins of turmeric are obtained by the following method:
(1) Washing rhizoma Dioscoreae Zingiberensis, removing most root hair, pulverizing, and oven drying;
(2) Taking 100g of crushed and dried yellow ginger, pouring the crushed and dried yellow ginger into 1000mL of absolute ethanol for extraction for 6h, filtering after the extraction is finished at 90 ℃, washing with ethanol, combining washing liquid and filtrate, removing liquid by rotary evaporation, recycling for later use, and drying solid to obtain the total saponins of the yellow ginger.
Example 1
Referring to fig. 1-2, the present embodiment provides a novel magnetic solid acid catalyst, and the preparation method thereof comprises the following steps:
Fe 3O4,Fe3O4@SiO2,Fe3O4@SiO2 -Pr-SH nanoparticles were [1] synthesized stepwise according to literature.
Adding 2.5g of Fe 3O4@SiO2 -Pr-SH particles and 50mL of toluene into a round-bottom flask in sequence, ultrasonically dispersing the mixture at room temperature for 10 minutes to prevent particle aggregation, then injecting 1.38mL of 1,3 propane sultone into a reaction system in the mechanical stirring process, and keeping the temperature of 110 ℃ for reaction reflux for 24 hours under the protection of nitrogen; and after the reaction is finished, naturally cooling the solution to room temperature, collecting a brown-black magnetic product by using a magnet, washing the brown-black magnetic product by using deionized water and absolute ethyl alcohol, and vacuum drying the brown-black solid product at 70 ℃ overnight to obtain the novel magnetic solid acid catalyst.
The products obtained in this example in the sequence were each subjected to infrared spectroscopic analysis, the results of which are shown in FIG. 3.
Fig. 3a to d show the infrared spectra of Fe 3O4、Fe3O4@SiO2 and Fe 3O4@SiO2-Pr-SH、Fe3O4@SiO2-Pr-S-Pr-SO3 H, respectively, prepared in example 1 of the present invention. As can be seen from fig. 3, the strong adsorption band at 589cm -1 was attributable to the ferrite bond stretching vibration in Fe 3O4, which suggests that Fe 3O4 is present in all samples; the tensile vibration of the Si-O-Si bond in numbers b-d corresponds to a characteristic peak at about 1091cm -1, and the apparent absorption peak at about 2927cm -1 in numbers C-d is related to the asymmetric tensile vibration of the C-H bond in the CH 2 group; the characteristic peaks of the-SO 3 H bond in number d are at 3428cm -1, and the peaks at 1234cm -1 and 1043cm -1 are attributable to the asymmetric and symmetric stretching vibrations of o=s=o. The results show that all four samples show characteristic peaks corresponding to the respective functional groups, and demonstrate that the magnetic solid acid Fe 3O4@SiO2-Pr-S-Pr-SO3 H is successfully prepared.
Application example 1
Referring to FIG. 5, weighing 0.10g of saponin, placing in a penicillin bottle, adding 6mL of ethanol, performing ultrasonic treatment at room temperature for 5min, and then adding 0.50g of solid acid catalyst into the penicillin bottle; then placing the mixture into a stainless steel water heating reaction kettle lined with a polytetrafluoroethylene liner, and placing the stainless steel water heating reaction kettle into a baking oven at 120 ℃ for 7h; after the reaction is finished, the solid acid catalyst is adsorbed and separated by a magnet and washed for a plurality of times by ethanol, and the washing liquid is combined into an alcoholysis reaction liquid; obtaining a crude saponin product by rotary evaporation of the solvent; dissolving the crude saponin product with chloroform, filtering, fixing the volume of the filtrate to 50mL to obtain a sample to be tested, and measuring the dioscin content by ultraviolet-visible spectrophotometry.
Refining the crude saponin product, and testing the purity of the saponin obtained by alcoholysis of turmeric saponin with solid acid. The refining process is as follows: adding active carbon into chloroform, heating and refluxing, and filtering the mixture with 0.2 μm organic filter membrane. And (3) spin-drying the filtrate, and recrystallizing with petroleum ether to obtain refined diosgenin.
In FIG. 6, (a) to (b) are respectively infrared spectra of a reference diosgenin standard (purity: 95%) and a purified saponin obtained in application example 1 of the present invention. As can be seen from FIG. 6, the characteristic peaks of the refined saponin and the standard product are completely consistent, and the sample is proved to be diosgenin.
Application example 2
The solid acid preparation example described in application example 2 is the same as the alcoholysis saponin and solid acid amount and the alcoholysis step of application example 1, except that: the alcoholysis temperature is 100 ℃, the solvent consumption is 7mL, and the alcoholysis time is 6h.
Application example 3
The solid acid preparation example described in application example 3 is the same as the alcoholysis saponin and solid acid amount and the alcoholysis conditions and steps of application example 2, except that: the solvent amount was 6mL.
Comparative example 1 was used
In order to better compare the extraction efficiency of the solid acid prepared by the invention. The efficiency of extracting saponin by hydrolyzing yellow ginger by adopting a traditional 1.5M sulfuric acid method is compared, and the preparation method comprises the following steps:
0.10g of total saponins is hydrolyzed with 10mL of 1.5M sulfuric acid solution at 100deg.C for 3 hours; after the hydrolysis process was completed, the mixture was filtered through a buchner funnel and washed with water to neutrality, and the solid residue was Soxhlet extracted with petroleum ether (boiling point 60-90 ℃) at 90℃for 4 hours, and the sample solution was prepared as described above. The results of the detection and calculation of each sample are shown in Table 1.
TABLE 1 results of absorbance measurements of sample solutions obtained in different application examples and comparative examples
Note that: the product yield is obtained by taking a crude product of total saponins as a raw material and calculating through ultraviolet absorbance and a standard curve.
Application cycle example
Four consecutive alcoholysis experiments were performed using application example 1 as the optimal alcoholysis saponin extraction conditions, with the addition of fresh solid acid of 0.02g after each cycle to avoid losses during operation.
When the activity is tested to be lower than the efficiency of extracting saponin by 1.5M sulfuric acid hydrolysis, the novel magnetic solid acid catalyst recovered after circulation is prepared according to the following steps: 1,3 propane sultone was added at a mass ratio of 0.768, and the regeneration treatment was performed in accordance with the preparation conditions of the magnetic solid acid catalyst in example 1. After regeneration, four more consecutive alcoholysis experiments were performed according to the conditions of application example 1, and the test results are shown in fig. 7. The figure shows that the yield of the saponin is still higher than the traditional sulfuric acid hydrolysis efficiency after the solid acid is recycled for three times, and in addition, the catalytic activity of the recycled solid acid can be recovered to the original activity after the solid acid is regenerated for four times.
The above results indicate that: the novel magnetic solid acid catalyst can be used for replacing inorganic acid to hydrolyze total saponins of turmeric, can be recycled, and has good activity; the novel magnetic solid acid catalyst has the advantages of simple synthetic reaction method, higher extraction efficiency of saponin than sulfuric acid hydrolysis efficiency in three continuous cycles, higher extraction yield of saponin (example 1) than hydrolysis efficiency of 1.5M sulfuric acid by 56.20% under the optimal condition, and recovery of cycle activity in a regeneration mode, and the prepared magnetic solid acid catalyst is suitable for popularization and application.
To further highlight the advantages of the present invention, the solid acid catalyst of the present invention was compared with the solid acid catalyst of the prior art in terms of saponin extraction rate under the same conditions, and the results are shown in Table 2. Wherein, the equivalent conditions are: the extraction rate was obtained by solvothermal alcoholysis of 0.1g of saponins with respect to the optimal conditions (solvent amount, reaction time, temperature, solid acid amount) reported for each of the different solid acid experiments.
TABLE 2 literature reports the efficiency of solid acid catalyst saponin extraction for alcoholysis of saponins
[1]Jiang W,Yu X,Hui Y,et al.Catalytic alcoholysis of saponins in D.zingiberensis CH Wright(Curcuma longa L)with magnetic solid acid to prepare diosgenin by response surface methodology[J].Industrial Crops and Products,2021,161:113197.
[2]Shen B,Yu X J,Zhang F,et al.Green production of diosgenin from alcoholysis of Dioscorea zingiberensis CH wright by a magnetic solid acid[J].Journal of Cleaner Production,2020,271:122297.
[3]Shen B,Zhang F,Zhao M,et al.Synthesis and characterization of magnetic solid acid Fe3O4@PEI@SO3H and application for the production of diosgenin by alcoholysis of turmeric saponins[J].Molecular Catalysis,2021,511:111751.
As can be seen from Table 2, under the same conditions, the extraction rate of the solid acid catalyst saponin of the invention is higher than that of the reported magnetic solid acid.
Compared with the prior art, the invention has the beneficial effects that:
(1) Compared with the method for sulfonating chlorosulfonic acid in the preparation method of the magnetic solid acid for alcoholysis of the total saponins of turmeric, which is reported at present, the preparation method of the novel magnetic solid acid catalyst Fe 3O4@SiO2-Pr-S-Pr-SO3 H has milder, safer and more controllable reaction conditions; the novel magnetic solid acid has high catalytic activity and good recycling effect, can recover the catalytic activity in a regeneration mode, and has good implementation possibility; under the same condition, the extraction rate of the solid acid catalyst saponin is higher than that of the reported magnetic solid acid catalyst;
(2) The magnetic solid acid prepared by the method is used as a catalyst for alcoholysis of the total saponins of turmeric, the centrifugal separation step of the solid acid and the reaction liquid can be omitted, the solid acid and the alcoholysis liquid can be separated by externally adding a magnet after the alcoholysis reaction is finished, the solid acid can be recycled, and the activity can be recovered by re-sulfonation and regeneration, so that the structure has the application advantage of long-acting load acidity;
(3) The method takes ethanol as a solvent to extract the total saponins of turmeric in the whole process, and then the solid acid catalyst of the invention is matched to react in ethanol to extract the dioscin; the whole process has no waste liquid, is environment-friendly and pollution-free, and the ethanol solvent can obtain clean ethanol through rotary evaporation and can be recycled, so that the cost is saved, and the method has a good environment-friendly idea and a wide industrial application prospect.
The above-described embodiments of the present invention do not limit the scope of the present invention. Any other corresponding changes and modifications made in accordance with the technical idea of the present invention shall be included in the scope of the claims of the present invention.
Claims (3)
1. The application of the novel magnetic solid acid catalyst in the aspect of extracting saponin from turmeric total saponins is characterized by comprising the following steps: performing alcoholysis reaction on total saponins of rhizoma Dioscoreae Zingiberensis and novel magnetic solid acid catalyst in ethanol to extract dioscin; wherein,
The novel magnetic solid acid catalyst comprises a core layer and a shell layer, wherein the core layer is magnetic Fe 3O4, and the shell layer is the reaction product of SiO 2, mercaptosiloxane and sulfonate compound; the sulfonate compound is 1, 3-propane sultone;
The preparation method of the novel magnetic solid acid catalyst comprises the following steps: obtaining Fe 3O4@SiO2 -Pr-SH nano particles; reflux reaction is carried out on the Fe 3O4@SiO2 -Pr-SH nano particles and 1, 3-propane sultone under the action of a first organic solvent, so as to obtain a novel magnetic solid acid catalyst Fe 3O4@SiO2-Pr-S-Pr-SO3 H; wherein, the mass ratio of the Fe 3O4@SiO2 -Pr-SH nano particles to the 1, 3-propane sultone is 1: (0.5-2); the first organic solvent is toluene; the dosage ratio of the Fe 3O4@SiO2 -Pr-SH nano particles to the first organic solvent is 1 g: (10-40) mL; the temperature of the reflux reaction is 100-120 ℃, the time of the reflux reaction is 20-24 hours, and the reflux reaction is performed under the protection of nitrogen;
The mass ratio of Huang Jiangzong saponin to the novel magnetic solid acid catalyst is 1: (0.5-10), wherein the dosage ratio of Huang Jiangzong saponins to ethanol is 1 g: (60-100) mL; the alcoholysis reaction is carried out in a hydrothermal reaction kettle, the temperature of the alcoholysis reaction is 120 ℃, and the time of the alcoholysis reaction is 7-8 hours.
2. The use of the novel magnetic solid acid catalyst according to claim 1 for extracting saponin from turmeric total saponin, wherein the mercaptosiloxane is at least one of 3- (mercaptopropyl) trimethoxysilane or 3- (mercaptopropyl) triethoxysilane.
3. The use of the novel magnetic solid acid catalyst according to claim 1 for extracting saponin from total saponins of turmeric, wherein the novel magnetic solid acid catalyst can be regenerated after being recovered; the regeneration treatment process comprises the following steps: the recovered novel magnetic solid acid catalyst is reacted with a sulfonate compound to obtain a novel magnetic solid acid catalyst with recovered activity.
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| WO2008123530A1 (en) * | 2007-03-27 | 2008-10-16 | Nippon Oil Corporation | Method for production of solid acid catalyst comprising carbonaceous material having sulfonate group, and use of the solid acid catalyst |
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| WO2008123530A1 (en) * | 2007-03-27 | 2008-10-16 | Nippon Oil Corporation | Method for production of solid acid catalyst comprising carbonaceous material having sulfonate group, and use of the solid acid catalyst |
| CN113181963A (en) * | 2021-05-14 | 2021-07-30 | 安庆精益精化工有限公司 | Preparation method of solid alkyl sulfonic acid catalyst |
| CN113244953A (en) * | 2021-05-14 | 2021-08-13 | 安庆精益精化工有限公司 | Preparation method of solid benzenesulfonic acid catalyst |
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