CN111548334A - Synthesis process of ethyl maltol - Google Patents
Synthesis process of ethyl maltol Download PDFInfo
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- CN111548334A CN111548334A CN202010352693.6A CN202010352693A CN111548334A CN 111548334 A CN111548334 A CN 111548334A CN 202010352693 A CN202010352693 A CN 202010352693A CN 111548334 A CN111548334 A CN 111548334A
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- 238000000034 method Methods 0.000 title claims abstract description 38
- YIKYNHJUKRTCJL-UHFFFAOYSA-N Ethyl maltol Chemical compound CCC=1OC=CC(=O)C=1O YIKYNHJUKRTCJL-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229940093503 ethyl maltol Drugs 0.000 title claims abstract description 26
- 230000008569 process Effects 0.000 title claims abstract description 21
- 230000015572 biosynthetic process Effects 0.000 title abstract description 10
- 238000003786 synthesis reaction Methods 0.000 title abstract description 10
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 41
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 23
- 239000013067 intermediate product Substances 0.000 claims abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- 239000000945 filler Substances 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 238000011068 loading method Methods 0.000 claims abstract description 10
- 230000007062 hydrolysis Effects 0.000 claims abstract description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 33
- 239000011259 mixed solution Substances 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 230000008707 rearrangement Effects 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- MWXWHUXLVXOXBZ-UHFFFAOYSA-N 1-(furan-2-yl)propan-1-ol Chemical compound CCC(O)C1=CC=CO1 MWXWHUXLVXOXBZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 2
- 239000002048 multi walled nanotube Substances 0.000 claims description 2
- 239000002109 single walled nanotube Substances 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- XPCTZQVDEJYUGT-UHFFFAOYSA-N 3-hydroxy-2-methyl-4-pyrone Chemical compound CC=1OC=CC(=O)C=1O XPCTZQVDEJYUGT-UHFFFAOYSA-N 0.000 abstract description 4
- HYMLWHLQFGRFIY-UHFFFAOYSA-N Maltol Natural products CC1OC=CC(=O)C1=O HYMLWHLQFGRFIY-UHFFFAOYSA-N 0.000 abstract description 2
- 229940043353 maltol Drugs 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 238000006359 acetalization reaction Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 29
- 230000001276 controlling effect Effects 0.000 description 14
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 9
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- LEHBURLTIWGHEM-UHFFFAOYSA-N pyridinium chlorochromate Chemical compound [O-][Cr](Cl)(=O)=O.C1=CC=[NH+]C=C1 LEHBURLTIWGHEM-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- MIDXCONKKJTLDX-UHFFFAOYSA-N 3,5-dimethylcyclopentane-1,2-dione Chemical compound CC1CC(C)C(=O)C1=O MIDXCONKKJTLDX-UHFFFAOYSA-N 0.000 description 1
- CVQUWLDCFXOXEN-UHFFFAOYSA-N Pyran-4-one Chemical class O=C1C=COC=C1 CVQUWLDCFXOXEN-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013736 caramel Nutrition 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 239000008369 fruit flavor Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005858 glycosidation reaction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- BEJNERDRQOWKJM-UHFFFAOYSA-N kojic acid Chemical compound OCC1=CC(=O)C(O)=CO1 BEJNERDRQOWKJM-UHFFFAOYSA-N 0.000 description 1
- 229960004705 kojic acid Drugs 0.000 description 1
- WZNJWVWKTVETCG-UHFFFAOYSA-N kojic acid Natural products OC(=O)C(N)CN1C=CC(=O)C(O)=C1 WZNJWVWKTVETCG-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011388 polymer cement concrete Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/34—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D309/36—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms
- C07D309/40—Oxygen atoms attached in positions 3 and 4, e.g. maltol
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the technical field of maltol, and particularly relates to a synthesis process of ethyl maltol. The process comprises mixing nano TiO2Loading carbon nano tubes on stainless steel wire mesh filler of an ultrasonic rotating packed bed, adding acetonitrile solution into the rotating packed bed, starting an ultrasonic generator, controlling the temperature in the packed bed to be 30-70 ℃, respectively introducing α -furylalcohol and 10-30% hydrogen peroxide from two liquid inlets of the ultrasonic rotating packed bed, simultaneously controlling the rotating speed of the ultrasonic rotating packed bed to be 400-fold-over-1000 r/min, and reacting for 1-3H to generate 6-hydroxy-2-ethyl-2H-pyrone- [3]]The intermediate product is mixed with solution, and then acetalization, oxidation and hydrolysis are carried out to prepare the ethyl maltol. The process of the invention is environment-friendlyAnd the process is easy to control, the catalytic efficiency is high, the reaction time is short, and the yield of the intermediate product reaches 93 percent.
Description
Technical Field
The invention belongs to the technical field of maltol, and particularly relates to a synthesis process of ethyl maltol.
Background
Ethyl maltol, English name:ethylmaltol, chemical name2-ethyl-3-hydroxy-4H-pyrone (2-ethyl-3-hydroxy-4H-pyrone) with the molecular formula of C7H803The powder is white needle-shaped or white crystal powder with aromatic fragrance, and is widely applied as a fragrance modifier and a flavoring agent. Is a food additive which is well recognized by people and has the advantages of safety, reliability, small dosage and obvious effect. Ethyl maltol is a derivative of gamma-pyrone, is white or yellowish crystal, and is yellow when being subjected to alkali. Has a melting point of 89-92 deg.C, is easily soluble in hot water, ethanol, chloroform and glycerol, and has caramel and fruit flavor.
The preparation method of ethyl maltol mainly comprises a fermentation method/kojic acid method, a pyromellitic acid method, a closed-loop method, a furfuryl alcohol method, a condensation method, a furfural method and the like, wherein the furfuryl alcohol method and the furfural method are widely applied because of the advantages of easily available raw materials, simple production process, low production cost, less three wastes, easily-achieved conditions and the like. For the furfuryl alcohol method and the furfural method, the process commonly adopted in the industry at present adopts a halogen elementary substance such as chlorine as an oxidant, however, the chlorine is toxic and harmful gas, can seriously corrode equipment, is relatively difficult to control in safety, is a great risk source in the production process, and can cause environmental pollution and great potential safety hazard if leakage or incomplete production occurs.
Related enterprises and scholars at home and abroad have developed various oxidation modes, such as electrochemical oxidation and catalytic oxidation, and used different catalysts, such as hydrogen peroxide, pyridinium chlorochromate PCC, N-bromosuccinimide, tert-butyl hydroperoxide, and particularly, JoosWahlen et al (Wahlenjet, titanium silicate1(TS-1) catalyzed synthesis and synthesis of modified hydrogen peroxide at home and abroad&Catalysis, 2004, 346 (23): 336-338) adopts titanium silicon-1 (TS-1) as a catalyst, adopts hydrogen peroxide to oxidize furan alcohol to obtain 6-hydroxy-2-methyl-2H-pyrone- [3]The conversion rate is 93%, the selectivity is 80%, although the hydrogen peroxide used in the synthesis process is an oxidant with small environmental pollution, low cost and easy obtaining, the preparation condition of the catalyst TS-1 is harsh, the cost is high, and the content of Ti in the catalyst is difficult to regulate and control because the Ti exists in a molecular sieve skeleton structure, and correspondingly, the catalytic performance of the catalyst cannot be regulated and controlled by regulating the content of TiAnd (5) controlling. In China, the process research of synthesizing ethyl maltol by using a titanium silicalite TS-1 as a catalyst and the research of the university of Beijing chemical industry, Master research academic thesis of Jiangyongqiang (Jiangyongqiang, titanium silicalite TS-1) also take the titanium silicalite TS-1 as a catalyst, and H2O2The product is used as oxidant to synthesize precursor of ethyl maltol through catalytic oxidation, and its yield can be up to 95.1%, and then it is undergone the processes of glycosidation, oxidation and hydrolysis to synthesize ethyl maltol, and its maximum yield can be up to 57.4%. However, since the catalyst TS-1 has a small particle size and is expensive to prepare, it is recovered and recycled by means of filtration, chloroform washing and drying, the process is cumbersome, and there is an inevitable loss of the catalyst.
In summary, there is a need to develop a synthesis process of ethyl maltol, which can ensure catalytic oxidation efficiency, realize process controllability, reduce environmental pollution, facilitate recovery of the catalyst after reaction, and avoid excessive loss of the catalyst.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a synthesis process of ethyl maltol, which improves the catalytic reaction efficiency, is convenient to recover the catalyst existing after the reaction, avoids the loss of the catalyst, has low cost and environmental protection, is easy to control the process and can be used for industrial production.
In order to realize the purpose, the synthesis process adopted by the invention comprises the following specific steps:
a preparation method of ethyl maltol is characterized by comprising the following steps:
(1) mixing nanometer TiO2Loading carbon nano tubes on stainless steel wire mesh filler of an ultrasonic rotating packed bed, adding acetonitrile solution into the rotating packed bed, starting an ultrasonic generator, controlling the temperature in the packed bed to be 30-70 ℃, respectively introducing α -furylalcohol and 10-30% hydrogen peroxide from two liquid inlets of the ultrasonic rotating packed bed, simultaneously controlling the rotating speed of the ultrasonic rotating packed bed to be 400-fold-over-1000 r/min, and reacting for 1-3H to generate 6-hydroxy-2-ethyl-2H-pyrone- [3]]Intermediate product mixed solution;
(2) and (2) adding a hydrochloric acid solution and an ethanol solution into the intermediate product mixed solution prepared in the step (1), controlling the reaction temperature to be 40-80 ℃ under stirring, reacting 6-hydroxy-2-ethyl-2H-pyrone- [3] in the mixed solution with ethanol to obtain a 2-ethyl-6-ethoxy-2H-pyrone- [3] mixed solution, then adding hydrogen peroxide for further oxidation, and performing hydrolysis rearrangement to prepare the ethyl maltol.
Preferably, the TiO is2The preparation method of the carbon nano tube comprises the following steps: dispersing the carbon nano tube modified by the oxygen plasma in an ethanol solution under the ultrasonic condition, adjusting the pH value of the mixed solution to 8-10, then adding a titanium-containing compound, heating to 100-200 ℃ for hydrothermal reaction, filtering, washing and drying to obtain the anatase type nano TiO loaded by the carbon nano tube2。
Preferably, TiO in step (1)2The loading mode of the carbon nano tube is that TiO is added2The carbon nano tube and the polyethylene glycol solution are uniformly mixed, then the stainless steel wire mesh filler is soaked in the mixture, and the mixture is taken out and sintered at the temperature of 250-450 ℃ to obtain the composite material.
Preferably, the step (2) further oxidizing specifically comprises adjusting the pH of the 2-ethyl-6-ethoxy-2H-pyrone mixed solution to be neutral by using ammonia water, and then adding hydrogen peroxide to react at 0-5 ℃.
Preferably, the hydrolysis rearrangement in the step (2) is to add the product after further oxidation into hydrochloric acid solution for mixing, and the hydrolysis rearrangement is carried out at 80-100 ℃ to obtain the ethyl maltol.
Preferably, the carbon nanotubes in step (1) are single-walled or multi-walled carbon nanotubes, and the ultrasonic frequency is 25KHz to 130 KHz.
Preferably, the concentration of the hydrochloric acid solution in the step (2) is 5-15%.
Preferably, the molar ratio of the hydrogen peroxide to the alpha-furylpropanol in the step (1) is 1-5: 1.
Preferably, TiO in step (1)2The dosage of the carbon nano tube is 0.1-5% of the mass of α -furan ethanol.
Preferably, TiO in step (1)2TiO in carbon nano tube2The content of (A) is 1% -10%.
In the technical scheme of the invention, nano TiO is adopted2Carbon nanotubes as catalystsIn contrast to the existing TS-1 catalysts, in which TiO is present2The content in the carbon nano tube is easy to adjust, the catalytic performance of the catalyst is easy to adjust, and the nano TiO is2The carbon nano tube has high catalytic activity, is nontoxic and is stable in air and humid environment; preparation of anatase type nano TiO loaded by carbon nano tube by using oxygen plasma modified carbon nano tube as raw material2The carbon nano tube is modified by oxygen plasma, the surface of the carbon nano tube is rich in hydroxyl, the dispersibility of the carbon nano tube in ethanol solution is improved, the carbon nano tube is favorably combined with a titanium-containing compound in the solution, and nano anatase TiO with high catalytic activity is obtained by one-step hydrothermal method2Loading catalyst on stainless steel wire gauze filler of ultrasonic rotating filler bed, under the double action of ultrasonic cavitation and rotating centrifugal force improving mass transfer process of reaction material, and cutting liquid reaction material into very small liquid by strong shearing action of stainless steel wire gauze filler when it passes through stainless steel wire gauze filler, further oxidizing α -furylpropanol into intermediate product 6-hydroxy-2-ethyl-2H-pyrone- [3] by catalytic action of catalyst on stainless steel wire gauze]The efficiency of catalytic oxidation reaction is improved, and the nano TiO2The carbon nano tube is loaded on the stainless steel wire mesh, and is easy to separate from reaction liquid after reaction, so that the loss of the catalyst is avoided.
Compared with the prior art, the invention has the beneficial effects that:
1. in the invention, nano TiO is adopted2Carbon nanotube as catalyst, TiO in the catalyst2The content of (A) is easy to adjust, nontoxic and has high catalytic activity, the process is environment-friendly, and the process is easy to control.
2. The invention carries out reaction in the ultrasonic wave rotating packed bed, improves the catalytic oxidation efficiency, has the intermediate product yield up to 93 percent, has less reaction time consumption, and can complete the catalytic reaction within 3 hours.
3. The catalyst is loaded on the stainless steel wire mesh, the catalyst and the stainless steel wire mesh are firmly combined, and the catalyst is easy to separate from a reaction solution after reaction, so that the loss of the catalyst is avoided.
Detailed Description
The present invention will be described in detail with reference to specific embodiments, which are illustrative of the invention and are not to be construed as limiting the invention.
Example 1
(1) Dispersing 50g of carbon nano tube modified by oxygen plasma in 500ml of ethanol solution under the ultrasonic condition, adjusting the pH value of the mixed solution to be 8, then adding 20ml of n-butyl titanate solution, heating to 120 ℃ for hydrothermal reaction for 4h, filtering, washing and drying to obtain TiO2Carbon nanotube-loaded anatase nano TiO with mass content of 4%2。
(2) Taking anatase type nano TiO prepared in the step (1)2Uniformly mixing 10g of carbon nano tube with 0.2g of polyethylene glycol aqueous solution, then dipping a stainless steel wire mesh in an ultrasonic rotary packed bed into the mixed solution, taking out the stainless steel wire mesh, and sintering the stainless steel wire mesh at 300 ℃ for 0.5h to obtain nano TiO loaded on the stainless steel wire mesh2A carbon nanotube catalyst.
(3) Nano TiO prepared in the step (2)2Loading a carbon nano tube loaded stainless steel wire mesh into an ultrasonic rotating packed bed as a filler, adding 200mL of acetonitrile solution into the rotating packed bed, starting an ultrasonic generator, controlling the ultrasonic frequency to be 125KHz, controlling the temperature in the packed bed to be 60 ℃, respectively introducing α -furylpropanol and 10-30% hydrogen peroxide from two liquid inlets of the ultrasonic rotating packed bed, controlling the molar ratio of the hydrogen peroxide to α -furylpropanol to be 5:1, controlling the rotating speed of the ultrasonic rotating packed bed to be 1000r/min, and reacting for 1H to generate 6-hydroxy-2-ethyl-2H-pyrone- [3] 3]The yield of the intermediate product mixed solution reaches 92.7 percent; discharging the mixed solution generated by the reaction, taking out the stainless steel wire mesh, washing with ethanol, drying for later use, and loading anatase type nano TiO after 5 times of repeated use2The quality of the stainless steel wire mesh filler/carbon nanotubes was not changed.
(4) Adding a hydrochloric acid solution with the mass concentration of 10% and an ethanol solution into the intermediate product mixed solution prepared in the step (3), controlling the reaction temperature to be 40 ℃ under stirring, enabling 6-hydroxy-2-ethyl-2H-pyrone- [3] in the mixed solution to react with ethanol to obtain a 2-ethyl-6-ethoxy-2H-pyrone- [3] mixed solution, adjusting the pH of the 2-ethyl-6-ethoxy-2H-pyrone mixed solution to be neutral by adopting ammonia water, then adding hydrogen peroxide into the mixed solution at 5 ℃ for reaction, adding a reacted product into the hydrochloric acid solution for mixing, and performing hydrolysis rearrangement at 100 ℃ to obtain ethyl maltol, wherein the yield is 61.9%.
Example 2
(1) Preparation of TiO according to step (1) of example 12Anatase type nano TiO loaded by carbon nano tube with mass content of 10%2；
(2) Anatase type nano TiO supported on stainless steel wire mesh was prepared according to the step (2) of example 12Carbon nanotube catalyst
(3) Nano TiO prepared in the step (2)2Loading a carbon nano tube loaded stainless steel wire mesh into an ultrasonic rotating packed bed as a filler, adding 200mL of acetonitrile solution into the rotating packed bed, starting an ultrasonic generator, controlling the ultrasonic frequency to be 50KHz, controlling the temperature in the packed bed to be 40 ℃, respectively introducing α -furylalcohol and 10-30% hydrogen peroxide from two liquid inlets of the ultrasonic rotating packed bed, controlling the molar ratio of the hydrogen peroxide to α -furylalcohol to be 2: 1, simultaneously controlling the rotating speed of the ultrasonic rotating packed bed to be 400r/min, and reacting for 3 hours to generate 6-hydroxy-2-ethyl-2H-pyrone- [3] 3]The yield of the intermediate product mixed solution reaches 91.6 percent; discharging the mixed solution generated by the reaction, taking out the stainless steel wire mesh, washing with ethanol, drying for later use, and loading anatase type nano TiO after 5 times of repeated use2The quality of the stainless steel wire mesh filler/carbon nanotubes was not changed.
(4) Adding a hydrochloric acid solution with the mass concentration of 15% and an ethanol solution into the intermediate product mixed solution prepared in the step (3), controlling the reaction temperature to be 70 ℃ under stirring, enabling 6-hydroxy-2-ethyl-2H-pyrone- [3] in the mixed solution to react with ethanol to obtain a 2-ethyl-6-ethoxy-2H-pyrone- [3] mixed solution, adjusting the pH of the 2-ethyl-6-ethoxy-2H-pyrone mixed solution to be neutral by adopting ammonia water, then adding hydrogen peroxide into the mixed solution at 0 ℃ for reaction, adding a reacted product into the hydrochloric acid solution for mixing, and performing hydrolysis rearrangement at 90 ℃ to obtain ethyl maltol, wherein the yield is 59.4%.
Comparative example 1
The ethyl maltol preparation method as in example 1 was used, except that anatase type nano TiO was used2The carbon nano tube is directly sent into an ultrasonic rotating packed bed, and the nano TiO is reacted2The carbon nano tube enters the intermediate product mixed solution, the intermediate product mixed solution is filtered, washed and dried, the weight of the catalyst is reduced by 36.8 percent, and the catalyst loss is obvious.
Comparative example 2
The ethyl maltol preparation method as in example 1 was used, except that the ultrasonic generator was not turned on during the catalytic oxidation reaction, and the yield of the intermediate product reached 89.4%.
Comparative example 3
The ethyl maltol preparation method as in example 1 was used except that rotation was not performed during the catalytic oxidation reaction, and the yield of the intermediate product reached 88.1%.
Comparative example 4
The preparation method of ethyl maltol as in example 1 was used, except that rutile type nano TiO supported by carbon nanotubes was used2As a catalyst, the yield of the intermediate product reaches 89.8 percent.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (10)
1. A preparation method of ethyl maltol is characterized by comprising the following steps:
(1) mixing nanometer TiO2Loading carbon nanotube on stainless steel wire mesh filler of ultrasonic rotating packed bed, adding acetonitrile solution into the rotating packed bed, and starting ultrasonic waveA generator, controlling the temperature in the packed bed to be 30-70 ℃, respectively introducing α -furylpropanol and 10-30% hydrogen peroxide from two liquid inlets of the ultrasonic rotating packed bed, simultaneously controlling the rotating speed of the ultrasonic rotating packed bed to be 400-one-step at 1000r/min, and reacting for 1-3H to generate 6-hydroxy-2-ethyl-2H-pyrone- [3]]Intermediate product mixed solution;
(2) and (2) adding a hydrochloric acid solution and an ethanol solution into the intermediate product mixed solution prepared in the step (1), controlling the reaction temperature to be 40-80 ℃ under stirring, reacting 6-hydroxy-2-ethyl-2H-pyrone- [3] in the mixed solution with ethanol to obtain a 2-ethyl-6-ethoxy-2H-pyrone- [3] mixed solution, then adding hydrogen peroxide for further oxidation, and performing hydrolysis rearrangement to prepare the ethyl maltol.
2. The method of claim 1, wherein the TiO is selected from the group consisting of2The preparation method of the carbon nano tube comprises the following steps: dispersing the carbon nano tube modified by the oxygen plasma in an ethanol solution under the ultrasonic condition, adjusting the pH value of the mixed solution to 8-10, then adding a titanium-containing compound, heating to 100-200 ℃ for hydrothermal reaction, filtering, washing and drying to obtain the anatase type nano TiO loaded by the carbon nano tube2。
3. The method according to claim 1, wherein TiO in the step (1)2The loading mode of the carbon nano tube is that TiO is added2The carbon nano tube and the polyethylene glycol solution are uniformly mixed, then the stainless steel wire mesh filler is soaked in the mixture, and the mixture is taken out and sintered at the temperature of 250-450 ℃ to obtain the composite material.
4. The preparation method of claim 1, wherein the further oxidation in the step (2) is specifically that ammonia water is used for adjusting the pH value of the 2-ethyl-6-ethoxy-2H-pyrone mixed solution to be neutral, and then hydrogen peroxide is added for reaction at 0-5 ℃.
5. The process according to claim 1, wherein the hydrolysis rearrangement in the step (2) comprises adding the further oxidized product to a hydrochloric acid solution, mixing, and hydrolyzing rearrangement at 80-100 ℃ to obtain ethyl maltol.
6. The method of claim 1, wherein the carbon nanotubes of step (1) are single-walled or multi-walled carbon nanotubes.
7. The method according to claim 1, wherein the ultrasonic frequency in the step (1) is 25KHz to 130 KHz.
8. The method according to claim 1, wherein the concentration of the hydrochloric acid solution in the step (2) is 5 to 15%.
9. The preparation method according to claim 1, wherein the molar ratio of hydrogen peroxide to alpha-furylpropanol in step (1) is 1-5: 1.
10. The method according to claim 1, wherein TiO in the step (1)2TiO in carbon nano tube2The content of (A) is 1% -10%.
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