CN111013653B - Novel solid acid catalyst and preparation method and application thereof - Google Patents
Novel solid acid catalyst and preparation method and application thereof Download PDFInfo
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- CN111013653B CN111013653B CN201911354328.2A CN201911354328A CN111013653B CN 111013653 B CN111013653 B CN 111013653B CN 201911354328 A CN201911354328 A CN 201911354328A CN 111013653 B CN111013653 B CN 111013653B
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- saponin
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- 239000011973 solid acid Substances 0.000 title claims abstract description 49
- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229930182490 saponin Natural products 0.000 claims abstract description 45
- 239000001397 quillaja saponaria molina bark Substances 0.000 claims abstract description 44
- 150000007949 saponins Chemical class 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- BIGOJJYDFLNSGB-UHFFFAOYSA-N 3-isocyanopropyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)CCC[N+]#[C-] BIGOJJYDFLNSGB-UHFFFAOYSA-N 0.000 claims description 4
- 241000234272 Dioscoreaceae Species 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000006277 sulfonation reaction Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- XQSBLCWFZRTIEO-UHFFFAOYSA-N hexadecan-1-amine;hydrobromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[NH3+] XQSBLCWFZRTIEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005543 nano-size silicon particle Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims 1
- 238000005903 acid hydrolysis reaction Methods 0.000 abstract description 12
- 238000006136 alcoholysis reaction Methods 0.000 abstract description 8
- 238000000605 extraction Methods 0.000 abstract description 6
- -1 alkyl glycoside Chemical class 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 229930182470 glycoside Natural products 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 235000017709 saponins Nutrition 0.000 description 28
- 150000007522 mineralic acids Chemical class 0.000 description 6
- 244000163122 Curcuma domestica Species 0.000 description 4
- 235000003392 Curcuma domestica Nutrition 0.000 description 4
- 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 4
- 235000003373 curcuma longa Nutrition 0.000 description 4
- 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 4
- WQLVFSAGQJTQCK-UHFFFAOYSA-N diosgenin Natural products CC1C(C2(CCC3C4(C)CCC(O)CC4=CCC3C2C2)C)C2OC11CCC(C)CO1 WQLVFSAGQJTQCK-UHFFFAOYSA-N 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 235000013976 turmeric Nutrition 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 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 3
- 239000003814 drug Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 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 description 2
- VNONINPVFQTJOC-RXEYMUOJSA-N Collettiside III Natural products O([C@@H]1[C@@H](O)[C@H](O[C@H]2[C@H](O)[C@H](O)[C@@H](O)[C@H](C)O2)[C@H](CO)O[C@@H]1O[C@@H]1CC=2[C@@](C)([C@@H]3[C@H]([C@H]4[C@@](C)([C@H]5[C@H](C)[C@@]6(O[C@H]5C4)OC[C@H](C)CC6)CC3)CC=2)CC1)[C@H]1[C@H](O)[C@H](O)[C@@H](O)[C@H](C)O1 VNONINPVFQTJOC-RXEYMUOJSA-N 0.000 description 2
- 241000407170 Curcuma Species 0.000 description 2
- 235000014375 Curcuma Nutrition 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 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 description 2
- 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 description 2
- 229940088597 hormone Drugs 0.000 description 2
- 239000005556 hormone Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- VNONINPVFQTJOC-UHFFFAOYSA-N polyphyllin III Natural products O1C2(OCC(C)CC2)C(C)C(C2(CCC3C4(C)CC5)C)C1CC2C3CC=C4CC5OC(C(C1O)OC2C(C(O)C(O)C(C)O2)O)OC(CO)C1OC1OC(C)C(O)C(O)C1O VNONINPVFQTJOC-UHFFFAOYSA-N 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 244000062245 Hedychium flavescens Species 0.000 description 1
- XNOPRXBHLZRZKH-UHFFFAOYSA-N Oxytocin Natural products N1C(=O)C(N)CSSCC(C(=O)N2C(CCC2)C(=O)NC(CC(C)C)C(=O)NCC(N)=O)NC(=O)C(CC(N)=O)NC(=O)C(CCC(N)=O)NC(=O)C(C(C)CC)NC(=O)C1CC1=CC=C(O)C=C1 XNOPRXBHLZRZKH-UHFFFAOYSA-N 0.000 description 1
- 101800000989 Oxytocin Proteins 0.000 description 1
- 102100031951 Oxytocin-neurophysin 1 Human genes 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000003433 contraceptive agent Substances 0.000 description 1
- 230000002254 contraceptive effect Effects 0.000 description 1
- 150000001887 cortisones Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003147 glycosyl group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- XNOPRXBHLZRZKH-DSZYJQQASA-N oxytocin Chemical compound C([C@H]1C(=O)N[C@H](C(N[C@@H](CCC(N)=O)C(=O)N[C@@H](CC(N)=O)C(=O)N[C@@H](CSSC[C@H](N)C(=O)N1)C(=O)N1[C@@H](CCC1)C(=O)N[C@@H](CC(C)C)C(=O)NCC(N)=O)=O)[C@@H](C)CC)C1=CC=C(O)C=C1 XNOPRXBHLZRZKH-DSZYJQQASA-N 0.000 description 1
- 229960001723 oxytocin Drugs 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229960004618 prednisone Drugs 0.000 description 1
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 1
- RJKFOVLPORLFTN-UHFFFAOYSA-N progesterone acetate Natural products C1CC2=CC(=O)CCC2(C)C2C1C1CCC(C(=O)C)C1(C)CC2 RJKFOVLPORLFTN-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- 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
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a novel solid acid catalyst and a preparation method and application thereof, wherein the solid acid catalyst takes nano-silica as a carrier, and a plurality of amino sulfonated groups are modified on the surface of the nano-silica; the invention prepares a new solid acid and is used for extracting saponin in saponin by alcoholysis reaction and simultaneously producing nonionic surfactant. Compared with the prior art, the synthetic reaction method is simple, the reaction condition is mild, the operation is safe, no corrosion is caused to equipment, and the alkyl glycoside produced in the alcoholysis process can be used as a nonionic surfactant. In addition, the extraction rate of the saponin by using the solid acid is equivalent to the yield of the saponin by traditional acid hydrolysis, thereby having huge industrial application prospect.
Description
Technical Field
The invention relates to the technical field of solid catalysts, in particular to a novel magnetic solid acid catalyst and a preparation method and application thereof.
Background
Turmeric is an ideal important raw material for extracting hormone medicaments, and various different hormone medicaments, such as saponin, progesterone acetate (monoester), prednisone, cortisone series, as well as intermediates or medicaments such as oxytocin, contraceptive and the like, can be obtained by modifying an initial product saponin extracted from the rhizome of turmeric. Is called 'medicinal gold' in the medical field, and always sells more than 120 countries and regions such as the America, the Germany, the French, the day and the like except for domestic needs.
The diosgenin is mainly in the form of diosgenin in plant, and C3 position of saponin is connected with sugar chain via saponin bond and further connected with plant cell wall tightly. The saponin is wrapped and shielded by a large amount of starch, cellulose, pectin and other substances in the plant. The extraction of diosgenin is carried out by dissociating saponin, and breaking the glycosidic bond between saponin and glycosyl to obtain diosgenin under certain reaction condition. Because of the serious pollution problem of the traditional direct acid hydrolysis method, and from the perspective of clean production process, people develop a great deal of research work aiming at reducing pollution and improving saponin yield, and the traditional direct acid hydrolysis method is divided into an inorganic acid hydrolysis improved process and a non-inorganic acid hydrolysis process according to the existence of acid hydrolysis. The inorganic acid improvement process still needs the step of acid hydrolysis, and the problem of sewage discharge which is difficult to solve still exists. But the non-inorganic acid hydrolysis process also has a plurality of problems, such as the strains with strong specificity and high activity can not be screened out and the traditional process can not be replaced by the biotechnology. The thermal decomposition extraction method has the advantages of simple process, large solvent consumption, more residues, high energy consumption, high cost and limited industrial application. But the non-inorganic acid hydrolysis process provides a reference principle and method for really solving the pollution problem of saponin production.
Disclosure of Invention
The invention aims to provide a novel magnetic solid acid catalyst, a preparation method and application thereof aiming at the defects of the prior art, and the method solves the defects of the traditional organic acid hydrolysis and can avoid environmental pollution and equipment corrosion.
The invention provides a novel magnetic solid acid catalyst, which takes nano silicon dioxide as a carrier, and a plurality of amino sulfonated groups are modified on the surface.
A preparation method of a novel solid acid catalyst comprises the following steps: s11: reacting N- [3- (trimethoxysilyl) propyl-ethylenediamine serving as a raw material in the presence of a surfactant to obtain a white solid product A;
s12: and carrying out sulfonation reaction on the solid product A to obtain the novel solid acid catalyst.
Further, the surfactant in S11 is one or both of sodium lauryl sulfate and cetylammonium bromide.
Further, the reaction in S11 is carried out in water, the mass fraction of N- [3- (trimethoxysilyl) propyl-ethylenediamine is 1% -10%, and the mass fraction of the surfactant is 0-0.07%.
Further, the method can be used for preparing a novel materialThe reaction in S11 needs to add alkali under mechanical stirring, and the alkali is NaOH, KOH or NH 3 H 2 One or more of O and triethylamine.
Further, the reaction temperature in S11 is 50-80 ℃, and the reaction time is 2-8h.
Further, the reaction in S12 is carried out in an organic solvent, which is one or more of chloroform, dichloromethane or and dichloroethane; the ratio of the mass (g) of the solid product A to the volume (mL) of the organic solvent is 1-10.
Further, a sulfonation reagent adopted in the reaction in S12 is concentrated sulfuric acid, fuming sulfuric acid or chlorosulfonic acid; and sulfonating for 2-5h.
A method for extracting and preparing saponin comprises the following steps:
s21: cleaning rhizome of Dioscoreaceae plant, pulverizing, sieving with 100-200 mesh sieve, mixing with hydroxyl-containing substance, extracting at 80-100 deg.C for 4-7 hr, filtering with Buchner funnel, washing with the same solvent, mixing filtrates, and drying the solid obtained by evaporation under reduced pressure to obtain saponin crude product;
s22: placing the saponin crude product in a reactor, adding solid acid catalyst and alcohol, reacting at 80-110 deg.C for 4-7h, cooling to room temperature, vacuum filtering to recover solid acid, and evaporating filtrate for concentration to obtain saponin.
Further, the volume ratio of the mass of the dioscoreaceae plant to the hydroxyl-containing substance in S21 is 1; in S22, the mass ratio of the saponin crude product to the solid acid catalyst is 1-5.
The invention prepares a new solid acid and is used for extracting saponin in saponin by alcoholysis reaction. Compared with the prior art, the synthetic reaction method is simple, the reaction condition is mild, the operation is safe, no corrosion is caused to equipment, and the alkyl glycoside produced in the alcoholysis process can be used as a nonionic surfactant. In addition, the extraction rate of saponin by using the solid acid is higher than that of saponin by traditional acid hydrolysis, so that the method has huge industrial application prospect.
The novel solid acid catalyst, the preparation method and the application thereof have the following beneficial effects:
1) The method for synthesizing the novel solid acid is simple, mild in reaction condition, safe to operate, free of corrosion to equipment, environment-friendly, high in solid acid extraction efficiency, recyclable, free of waste liquid discharge, strong in practicability and suitable for popularization and application.
2) The invention adopts a solid acid alcoholysis mode to extract the dioscin from the turmeric, alcohol substances in alcoholysis can be reused, and no waste liquid is discharged.
Drawings
FIG. 1 is a chemical structural formula of a novel solid acid catalyst of the present invention;
FIG. 2 is an infrared spectrum of a novel solid acid catalyst of the present invention;
FIG. 3 is a thermogravimetric analysis of a novel solid acid catalyst of the present invention.
Detailed Description
The invention will be further illustrated below with reference to specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, various changes or modifications of the present invention may be made by those skilled in the art, and equivalents may fall within the scope of the claims of the present application. The proportion in the embodiment of the invention is by weight.
Preparation of solid acid
Example 1: measuring 140 mL of water, adding 5.06g of aminoethyl triaminopropyl trimethoxy silane and 0.03g of surfactant sodium dodecyl sulfate, reacting at 95 ℃ for 2 hours, and adding a small amount of NH 3 H 2 And O, obtaining a white (yellowish) solid substance after 5 hours of reaction, and drying the solid substance to 2.87g. It was added to 60mL CH 2 Cl 2 In (1), about 2.5ml of LClSO is added with stirring 3 H, sulfonating for 2 hours at room temperature. And (4) carrying out suction filtration, washing the obtained solid with ethanol, carrying out suction filtration, washing with ethanol for multiple times, placing under a lamp, drying and weighing 3.20 g.
Example 2: 170 mL of water is measured, and aminoethyl triaminopropyl trimethoxy is addedSilane 8.13g and surfactant cetyl ammonium bromide 0.06g, reacting at 95 deg.C for 2 hr, adding a small amount of NaOH, reacting for 6 hr, and oven drying the obtained solid matter to 4.02g. This product was added to 20mL of CHCl 3 And CH 2 Cl 2 (1. Suction filtration is carried out, and the obtained solid is washed by hot water and ethanol respectively and is placed under a lamp to be dried and weighed to be 4.21 g.
Please refer to fig. 1. Each silicon atom in the catalyst is interconnected with an adjacent molecule. The solid acid obtained in this example was subjected to infrared spectroscopy and thermogravimetric analysis, and the results are shown in fig. 2 and fig. 3, respectively; in FIG. 2, 344cm -1 Can be attributed to the stretching vibration peak of hydroxyl group, 1051 and 783 are SO 3 601cm of asymmetric and symmetric stretching vibration peak -1 Is SO 3 Moderate absorption peak of (2). 2793 and 2937cm -1 Peak of (A) is CH 2 And the characteristic peaks are consistent with the structure of the solid acid.
FIG. 3 is a thermogravimetric analysis of a solid acid, from which it can be seen that at a temperature of 20-230 ℃ the weight decreases due to the removal of surface adsorbed water. The weight loss observed at 230-800 ℃ in the TGA curve is due to the decomposition of the organic groups grafted on the surface of the sample, -SO 3 Water loss due to condensation of H groups and adjacent Si-OH groups. In addition, the raw material aminoethyltriaminopropyltrimethoxysilane is liquid at normal temperature, and the obtained solid acid is solid, and the analysis is combined to show that the target product is successfully obtained.
Alcoholysis of saponins
Example 3
The solid acid catalyst obtained in the example 1 is applied to the extraction of saponin in yellow ginger, and specifically comprises the following steps: weighing 0.1200g of dioscin and 0.3894g of solid acid, adding 20mL of a mixture of ethanol and isopropanol, reacting at 90 ℃ for 6h, carrying out suction filtration, carrying out rotary evaporation on the obtained filtrate to obtain solid, carrying out reflux soxhlet extraction on the solid by using petroleum ether for 6h, cooling to room temperature, and carrying out constant volume to 50mL. And measuring the content of the saponin in the sample solution according to an ultraviolet-visible spectrophotometry.
Example 4
Weighing dried Curcuma rhizome saponin 0.1203g, solid acid 0.2113g, adding 20mL mixture of methanol and isopropanol, reacting at 90 deg.C for 7h, vacuum filtering, rotary evaporating filtrate to dryness, soxhlet extracting the obtained solid with chloroform for 2 hr, concentrating the liquid under reduced pressure, and diluting to 50mL. The absorbance was measured in the same manner as in example 1, and the percentage of saponin calculated by the standard curve was 106% of that extracted by hydrolysis with 2M sulfuric acid.
Example 5
Weighing dried Curcuma rhizome saponin 0.1201g, adding the solid acid recovered and dried in example 1, adding 20mL ethanol, reacting at 90 deg.C for 6h, filtering, evaporating the filtrate to dryness, soxhlet extracting the obtained solid with dichloromethane for 3 hr, concentrating the liquid under reduced pressure, and diluting to 50mL. The absorbance was measured in the same manner as in example 1, and the percentage of saponin calculated by the standard curve was 102% of that extracted by hydrolysis with 2M sulfuric acid.
The above results show that: the solid acid is used for replacing inorganic acid to carry out alcoholysis on saponin in the turmeric, the yield of extracted saponin is equivalent to that of 2M sulfuric acid hydrolysis, the saponin can be recycled repeatedly, the activity is still good, the synthetic route of the solid acid obtained by the invention is simple, the solid acid is free from corrosion to equipment, environment-friendly, high in recycling activity and low in loss, and the method is suitable for industrial popularization and application.
The embodiments of the present invention have been described above by way of example, but the description is only a preferred embodiment of the present invention and should not be construed as limiting the scope of the invention. All equivalent changes and modifications within the scope of the application of the present invention shall fall within the scope of the patent of the present invention.
Claims (9)
1. A method for extracting saponin by using a solid acid catalyst is characterized by comprising the following steps: the method comprises the following steps: the solid acid catalyst takes nano silicon dioxide as a carrier, and a plurality of amino sulfonated groups are modified on the surface of the nano silicon dioxide;
s21: cleaning rhizome of Dioscoreaceae plant, pulverizing, sieving with 100-200 mesh sieve, mixing with hydroxyl-containing substance, extracting at 80-100 deg.C for 4-7 hr, filtering with Buchner funnel, washing with the same solvent, mixing filtrates, and drying the solid obtained by evaporation under reduced pressure to obtain saponin crude product;
s22: placing the saponin crude product in a reactor, adding solid acid catalyst and alcohol, reacting at 80-110 deg.C for 4-7h, cooling to room temperature, vacuum filtering to recover solid acid, evaporating filtrate, concentrating to separate out saponin, and evaporating the residual liquid to dryness to obtain nonionic surfactant.
2. The method for extracting saponin using solid acid catalyst as claimed in claim 1, wherein: the method comprises the following steps: s11: reacting N- [3- (trimethoxysilyl) propyl-ethylenediamine in the presence of a surfactant to obtain a white solid product A;
s12: and (3) carrying out sulfonation reaction on the solid product A to obtain the solid acid catalyst.
3. The method for extracting saponin using a solid acid catalyst as claimed in claim 2, wherein: the surfactant in S11 is one or two of sodium dodecyl sulfate and hexadecyl ammonium bromide.
4. The method for extracting saponin using a solid acid catalyst as claimed in claim 2, wherein: the reaction in S11 is carried out in water, the mass fraction of the N- [3- (trimethoxysilyl) propyl-ethylenediamine is 1% -10%, and the mass fraction of the surfactant is 0-0.07%.
5. The method for extracting saponin using a solid acid catalyst as claimed in claim 2, wherein: the reaction in S11 requires the addition of a base under mechanical stirring, the base being NaOH, KOH, NH 3 H 2 One or more of O and triethylamine.
6. The method for extracting saponin using a solid acid catalyst as claimed in claim 2, wherein: the reaction temperature in S11 is 50-80 ℃, and the reaction time is 2-8h.
7. The method for extracting saponin using a solid acid catalyst as claimed in claim 2, wherein: the reaction in S12 is carried out in an organic solvent, wherein the organic solvent is one or more of trichloromethane, dichloromethane or dichloroethane; the ratio of the mass (g) of the solid product A to the volume (mL) of the organic solvent is 1-10.
8. The method for extracting saponin using a solid acid catalyst as claimed in claim 2, wherein: the sulfonation reagent adopted in the reaction in S12 is concentrated sulfuric acid, fuming sulfuric acid or chlorosulfonic acid; and sulfonating for 2-5h.
9. The method for extracting saponin using a solid acid catalyst as claimed in claim 1, wherein: in S21, the volume ratio of the mass of the dioscoreaceae plant to the hydroxyl-containing substance is 1-15, wherein the hydroxyl-containing substance is one or more of methanol, ethanol, isopropanol and water; in S22, the mass ratio of the crude saponin to the solid acid catalyst is 1-5, wherein the alcohol is one or more of methanol, ethanol and isopropanol.
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Non-Patent Citations (3)
| Title |
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| Bernard Wiredu等.Synthesis of a silica-immobilized Brönsted acidic ionic liquid catalyst and hydrolysis of cellulose in water under mild conditions.《Catalysis Communications》.2014,41-44. * |
| Hydrolysis extraction of diosgenin from Dioscorea nipponica Makino by sulfonated magnetic solid composites;Farong Zhang等;《J Nanopart Res》;20191207;1-11 * |
| Silica functionalized propyl sulfonic acid (SiO2-Pr-SO3H): An efficient catalyst in organic reactions;Parisa Gholamzadeh等;《Journal of Molecular Catalysis A: Chemical》;20140504;208-222 * |
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