CN115700146A - Preparation method and application of photocatalyst - Google Patents
Preparation method and application of photocatalyst Download PDFInfo
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- CN115700146A CN115700146A CN202211484447.1A CN202211484447A CN115700146A CN 115700146 A CN115700146 A CN 115700146A CN 202211484447 A CN202211484447 A CN 202211484447A CN 115700146 A CN115700146 A CN 115700146A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 81
- WEEGYLXZBRQIMU-UHFFFAOYSA-N Eucalyptol Chemical compound C1CC2CCC1(C)OC2(C)C WEEGYLXZBRQIMU-UHFFFAOYSA-N 0.000 claims abstract description 57
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000001035 drying Methods 0.000 claims abstract description 29
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical group CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims abstract description 28
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims abstract description 28
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229940116411 terpineol Drugs 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 15
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010949 copper Substances 0.000 claims abstract description 11
- 238000011068 loading method Methods 0.000 claims abstract description 11
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 9
- 238000002791 soaking Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims description 28
- 235000019441 ethanol Nutrition 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 230000001699 photocatalysis Effects 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims 1
- 229960005233 cineole Drugs 0.000 abstract description 15
- RFFOTVCVTJUTAD-UHFFFAOYSA-N cineole Natural products C1CC2(C)CCC1(C(C)C)O2 RFFOTVCVTJUTAD-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 9
- 230000035484 reaction time Effects 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 5
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 238000006317 isomerization reaction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 15
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 8
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 8
- 229940088601 alpha-terpineol Drugs 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 239000002535 acidifier Substances 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 7
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 230000010355 oscillation Effects 0.000 description 6
- WEEGYLXZBRQIMU-WAAGHKOSSA-N Eucalyptol Chemical compound C1C[C@H]2CC[C@]1(C)OC2(C)C WEEGYLXZBRQIMU-WAAGHKOSSA-N 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 244000166124 Eucalyptus globulus Species 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- -1 bicyclic monoterpene compound Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 241000218195 Lauraceae Species 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229930003642 bicyclic monoterpene Natural products 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
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- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 244000045947 parasite Species 0.000 description 1
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- 239000011973 solid acid Substances 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
The invention discloses a preparation method of a photocatalyst, which comprises the following operation steps: (1) Dropwise adding butyl titanate into ethanol, and stirring and adding concentrated hydrochloric acid; (2) Adding copper chloride for reaction, wherein the mass ratio of Cu to Ti is 1; (3) Drying, roasting at 180-300 deg.c and re-drying to obtain the carrier Cu-TiO for the catalyst 2 (ii) a (4) Adding ethanol, ultrasonically vibrating, adding phosphotungstic acid ethanol solution to ensure that the loading amount of phosphotungstic acid is 10-30%, soaking for 6-24 h, and drying a soaked sample to obtain PW/Cu-TiO 2 A catalyst. The catalyst prepared by the invention has good activity, the raw material for preparing and synthesizing cineole by applying the catalyst is terpineol isomerization reaction, no solvent is used, the requirement on the raw material is not strict, and the cost is saved; the reaction time is 1 hour, so that the reaction time is greatly shortened.
Description
Technical Field
The invention relates to the technical field of synthesizing cineole by using a photocatalyst, and particularly relates to a preparation method and application of the photocatalyst.
Background
The cineole belongs to a bicyclic monoterpene compound, is mainly contained in eucalyptus, eucalyptus leaves or lauraceae plants and the like, has good physiological activities of expelling parasites, diminishing inflammation, sterilizing and the like, is widely applied to the fields of medicines, spice essences, foods, cosmetics and the like, and has wide market application prospect. The current methods for obtaining cineole mainly comprise plant extraction methods and chemical synthesis methods. The plant extraction method has the advantages of low oil yield, impure product and high production cost, and the chemical synthesis method can be obtained by carrying out catalytic isomerization on terpineol.
The existing synthesis method of eucalyptol is as follows: (1) Catalyzing alpha-terpineol to synthesize 1, 8-cineole (Chinese application No. 202111481751.6) in a solvent-free system by using a solid catalyst prepared from a quaternary ammonium salt compound and phosphotungstic acid; adopts hierarchical pore HZSM-5 as catalyst to catalyze alpha-terpineol to isomerize and synthesize 1, 8-cineole (Chinese application 202110908116.5) under the condition of normal pressure heating; titanium dioxide supported phosphotungstic acid catalyst is adopted to catalyze alpha-terpineol to isomerize and synthesize 1, 8-cineole under normal pressure heating condition. (Chinese application 202010033288.8); adding alpha-terpineol and a solid acid catalyst into a high-pressure reaction kettle, then adding carbon dioxide and an additive, and catalyzing the alpha-terpineol to isomerize and synthesize 1, 8-cineole (Chinese application 201910011590.0); the preparation method comprises the steps of preparing a supported heteropolyacid catalyst by taking polyion liquid as a carrier, catalyzing alpha-terpineol to isomerize and synthesize 1, 8-cineole (Chinese application 201710026268.6), wherein raw materials are all alpha-terpineol in the existing synthesis methods (1), (2), (4) and (5), the raw materials are harsh, the price is high, and the reaction time is long; in addition, n-hexane, cyclohexane and isopropanol are used as solvents in the methods (2) and (4), the solvent ratio is high, the product separation difficulty is increased, the production cost is increased, and the industrialization is not facilitated; in the synthesis method (3), the reaction time is long, and an organic solvent is required for the reaction, so that the separation difficulty of the product is increased, the production cost is increased, and the method is not beneficial to industrialization; the method (5) also needs a large amount of organic solvent, the mass ratio of the organic solvent to the alpha-terpineol is 33.7.
In summary, the existing eucalyptol synthesis method generally needs to use a large amount of solvents, and adverse factors such as high raw material requirement and long reaction time influence the industrial application of the eucalyptol.
Disclosure of Invention
Aiming at the technical problems, the invention provides a preparation method and application of a photocatalyst, the photocatalyst is used for synthesizing eucalyptol, the used raw materials are terpineol isomer mixtures, the price is lower, a reaction system does not need an organic solvent, the reaction time is short, the reaction is normal temperature, and the production cost is reduced.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a preparation method of a photocatalyst comprises the following operation steps:
(1) Dropwise adding butyl titanate into absolute ethyl alcohol, stirring at 200-250r/min for 60min, and adding concentrated hydrochloric acid;
(2) Adding copper chloride into the substance obtained after adding concentrated hydrochloric acid in the step (1) for reaction, wherein the mass ratio of Cu to Ti is (1) - (10-1);
(3) Drying the substance obtained after the reaction in the step (2), roasting in a muffle furnace at 180-300 ℃ for 2h, drying and grinding into powder to obtain the carrier Cu-TiO of the catalyst 2 ；
(4) Taking the carrier Cu-TiO obtained in the step (3) 2 Adding absolute ethyl alcohol, ultrasonically vibrating for 20min to disperse the catalyst in the absolute ethyl alcohol, adding phosphotungstic acid ethanol solution to ensure that the loading amount of phosphotungstic acid is 10-30%, soaking for 6-24 h, and drying a soaked sample at 60-70 ℃ to obtain PW/Cu-TiO 2 A catalyst.
Preferably, 24ml of butyl titanate taken in the step (1) is dripped into 96ml of absolute ethyl alcohol within 5-10 min; 2ml of concentrated hydrochloric acid with the mass concentration of 36 percent is added as an acidifier in the step (1).
Preferably, the mass ratio of Cu to Ti in the step (2) is 1.
Preferably, the drying in the step (3) is carried out in a water bath kettle at the temperature of 60-70 ℃.
Preferably, in step (4), the carrier Cu-TiO is taken 2 2.0g of carrier, 10ml of absolute ethyl alcohol is added.
Preferably, the loading of the phosphotungstic acid in step (4) is 25%.
Preferably, the step (4) is carried out at 60 ℃ and 400r/min for 6-24 h.
The application of the photocatalyst prepared in the above way in preparing 1, 8-cineole by catalyzing terpineol is as follows: adding a certain amount of photocatalyst and terpineol (isomer mixture) into a photocatalytic reactor, reacting for 1h to obtain 1, 8-cineole, and performing GC and GC-MS analysis on the obtained catalytic product.
Preferably, 2g of photocatalyst and 20mL of terpineol are taken and added into the photocatalytic reactor.
Compared with the prior art, the invention has the following beneficial effects:
the catalyst prepared by the invention has good activity, the raw material for preparing and synthesizing the cineole by applying the catalyst is terpineol isomerization reaction, a solvent is not needed, the requirement on the raw material is not strict, and the cost is saved; the reaction time is 1 hour, so that the reaction time is greatly shortened; (3) The reaction temperature is normal temperature, and the process conditions are simple and easy to realize.
Detailed Description
The following detailed description is to be read in connection with specific embodiments, but it should be understood that the scope of the invention is not limited to the specific embodiments. The raw materials and reagents used in the examples were all commercially available unless otherwise specified.
Example 1
A preparation method of a photocatalyst comprises the following operation steps:
(1) Dripping 24ml of butyl titanate into 96ml of absolute ethyl alcohol within 5-10min, stirring for 60min at 200-250r/min, and adding 2ml of concentrated hydrochloric acid with the mass concentration of 36% as an acidifying agent;
(2) Adding a certain amount of copper chloride into the substance obtained after adding the concentrated hydrochloric acid in the step (1) for reaction, wherein the mass ratio of Cu to Ti is 1;
(3) Drying the substance obtained after the reaction in the step (2) in a water bath kettle at 60-70 ℃, roasting the dried substance in a muffle furnace at 240 ℃ for 2h, drying and grinding the substance into powder to obtain the carrier Cu-TiO of the catalyst 2 ；
(4) Taking the carrier Cu-TiO obtained in the step (3) 2 2.0g, adding 10ml of absolute ethyl alcohol, carrying out ultrasonic oscillation for 20min to disperse the catalyst in the absolute ethyl alcohol, adding a phosphotungstic acid ethanol solution (0.2 g of phosphotungstic acid is weighed and dissolved in 15ml of ethanol solution), enabling the loading of the phosphotungstic acid to be 10%, soaking for 12h at the temperature of 60 ℃ and the rotating speed of 400r/min, drying a soaked sample at the temperature of 60-70 ℃, and obtaining PW/Cu-TiO 2 A photocatalyst.
The application of the photocatalyst prepared in the preparation of 1, 8-cineole by catalyzing terpineol is as follows: taking 2.0gPW/Cu-TiO 2 Adding a photocatalyst and 20mL of terpineol (isomer mixture) into a photocatalytic reactor, reacting at normal temperature for 1h to obtain 1, 8-cineole, and carrying out GC and GC-MS analysis on a reaction product to obtain the terpineol conversion rate of 55.18%; the selectivity of cineole at this point was 72.65%.
Example 2
A preparation method of a photocatalyst comprises the following operation steps:
(1) Dripping 24ml of butyl titanate into 96ml of absolute ethyl alcohol within 5-10min, stirring for 60min at 200-250r/min, and adding 2ml of concentrated hydrochloric acid with the mass concentration of 36% as an acidifying agent;
(2) Adding a certain amount of copper chloride into the substance obtained after adding the concentrated hydrochloric acid in the step (1) to ensure that the mass ratio of Cu to Ti is 1;
(3) Drying the substance obtained after the reaction in the step (2) in a water bath kettle at the temperature of 60-70 ℃, roasting the dried substance in a muffle furnace at the temperature of 240 ℃ for 2h, and drying and grinding the substance into powder to obtain the carrier Cu-TiO of the catalyst 2 ；
(4) Taking the carrier Cu-TiO obtained in the step (3) 2 5.0g, adding 10ml of absolute ethyl alcohol, carrying out ultrasonic oscillation for 20min to disperse the catalyst in the absolute ethyl alcohol, adding a phosphotungstic acid ethanol solution (weighing 1.50g of phosphotungstic acid to be dissolved in 15ml of the ethanol solution), enabling the loading amount of the phosphotungstic acid to be 30%, soaking for 12h at the temperature of 60 ℃ and the rotating speed of 400r/min, drying a soaked sample at the temperature of 60-70 ℃, and obtaining PW/Cu-TiO 2 A photocatalyst.
The application of the photocatalyst prepared in the preparation of 1, 8-cineole by catalyzing terpineol is as follows: taking 2.0g of PW/Cu-TiO 2 Adding a photocatalyst and 20mL of terpineol (isomer mixture) into a photocatalytic reactor, reacting at normal temperature for 1h to obtain 1, 8-cineole, and carrying out GC and GC-MS analysis on a reaction product to obtain the terpineol conversion rate of 95.52%; the eucalyptol selectivity at this point was 56.12%.
Example 3
A preparation method of a photocatalyst comprises the following operation steps:
(1) Dripping 24ml of butyl titanate into 96ml of absolute ethyl alcohol within 5-10min, stirring for 60min at 200-250r/min, and adding 2ml of concentrated hydrochloric acid with the mass concentration of 36% as an acidifying agent;
(2) Adding a certain amount of copper chloride into the substance obtained after the concentrated hydrochloric acid is added in the step (1) to ensure that the mass ratio of Cu to Ti is 1;
(3) Drying the substance obtained after the reaction in the step (2) in a water bath kettle at the temperature of 60-70 ℃, roasting the dried substance in a muffle furnace at the temperature of 240 ℃ for 2h, and drying and grinding the substance into powder to obtain the carrier Cu-TiO of the catalyst 2 ；
(4) Taking the carrier Cu-TiO obtained in the step (3) 2 2.0g, adding 10ml of absolute ethyl alcohol, carrying out ultrasonic oscillation for 20min to disperse the catalyst in the absolute ethyl alcohol, adding a phosphotungstic acid ethanol solution (0.5 g of phosphotungstic acid is weighed and dissolved in 15ml of the ethanol solution), enabling the loading amount of the phosphotungstic acid to be 25%, soaking for 12h at the temperature of 60 ℃ and the rotating speed of 400r/min, drying a soaked sample at the temperature of 60-70 ℃, and obtaining PW/Cu-TiO 2 A photocatalyst.
The application of the photocatalyst prepared in the preparation of 1, 8-cineole by catalyzing terpineol is as follows: taking 2.0gPW/Cu-TiO 2 Adding a photocatalyst and 20mL of terpineol (isomer mixture) into a photocatalytic reactor, reacting at normal temperature for 1h to obtain 1, 8-cineole, and carrying out GC and GC-MS analysis on a reaction product to obtain the terpineol conversion rate of 89.49%; the selectivity of cineole at this point was 73.94%.
Comparative example 1
A preparation method of a photocatalyst comprises the following operation steps:
(1) Dripping 24ml of butyl titanate into 96ml of absolute ethyl alcohol within 5-10min, stirring for 60min at 200-250r/min, and adding 2ml of concentrated hydrochloric acid with the mass concentration of 36% as an acidifying agent;
(2) Adding a certain amount of copper chloride into the substance obtained after the concentrated hydrochloric acid is added in the step (1) to ensure that the mass ratio of Cu to Ti is 1;
(3) Drying the substance obtained after the reaction in the step (2) in a water bath kettle at the temperature of 60-70 ℃, roasting the dried substance in a muffle furnace at the temperature of 240 ℃ for 2h, and drying and grinding the substance into powder to obtain the carrier Cu-TiO of the catalyst 2 ；
(4) Taking the carrier Cu-TiO obtained in the step (3) 2 2.0g, adding 10mL of absolute ethyl alcohol, carrying out ultrasonic oscillation for 20min to disperse the catalyst in the absolute ethyl alcohol, adding a phosphotungstic acid ethanol solution (0.5 g of phosphotungstic acid is weighed and dissolved in 15mL of ethanol solution), enabling the loading amount of the phosphotungstic acid to be 25%, soaking for 26h at the temperature of 60 ℃ and the rotating speed of 400r/min, drying a soaked sample at the temperature of 60-70 ℃, and obtaining PW/Cu-TiO 2 A photocatalyst.
The application of the photocatalyst prepared in the preparation of 1, 8-cineole by catalyzing terpineol is as follows: taking 2.0g of PW/Cu-TiO 2 Adding a photocatalyst and 20mL of terpineol (isomer mixture) into a photocatalytic reactor, reacting at normal temperature for 1h to obtain 1, 8-cineole, and carrying out GC and GC-MS analysis on a reaction product to obtain the terpineol conversion rate of 72.95%; the selectivity of cineole at this point was 48.40%.
Comparative example 2
A preparation method of a photocatalyst comprises the following operation steps:
(1) Dropwise adding 24ml of butyl titanate into 96ml of absolute ethyl alcohol within 5-10min, stirring for 60min at 200-250r/min, and adding 2ml of concentrated hydrochloric acid with the mass concentration of 36% as an acidifying agent;
(2) Adding a certain amount of copper chloride into the substance obtained after adding the concentrated hydrochloric acid in the step (1) to ensure that the mass ratio of Cu to Ti is 1:20;
(3) Drying the substance obtained after the reaction in the step (2) in a water bath kettle at 60-70 ℃, roasting the dried substance in a muffle furnace at 240 ℃ for 2h, and drying and grinding the substance into powder to obtain the carrier Cu-TiO of the catalyst 2 ；
(4) Taking the carrier Cu-TiO obtained in the step (3) 2 2.0g, adding 10mL of absolute ethyl alcohol, carrying out ultrasonic oscillation for 20min to disperse the catalyst in the absolute ethyl alcohol, adding a phosphotungstic acid ethanol solution (0.5 g of phosphotungstic acid is weighed and dissolved in 15mL of ethanol solution), enabling the loading amount of the phosphotungstic acid to be 25%, soaking for 12h at the temperature of 60 ℃ and the rotating speed of 400r/min, drying a soaked sample at the temperature of 60-70 ℃, and obtaining PW/Cu-TiO 2 A photocatalyst.
The application of the photocatalyst prepared in the preparation of 1, 8-cineole by catalyzing terpineol is as follows: taking 2.0g of PW/Cu-TiO 2 Photocatalyst andadding 20mL of terpineol (isomer mixture) into a photocatalytic reactor, reacting at normal temperature for 1.5h to obtain 1, 8-cineole, filtering 3mL of reaction solution by using a disposable injector, and carrying out GC and GC-MS analysis on the catalytic product, wherein the conversion rate of the terpineol is 92.63%; the selectivity of cineole at this point was 65.14%.
Comparative example 3
A preparation method of a photocatalyst comprises the following operation steps:
(1) Dropwise adding 24ml of butyl titanate into 96ml of absolute ethyl alcohol within 5-10min, stirring for 60min at 200-250r/min, and adding 2ml of concentrated hydrochloric acid with the concentration of 36% as an acidifying agent;
(2) Adding a certain amount of copper chloride into the substance obtained after adding the concentrated hydrochloric acid in the step (1) to ensure that the mass ratio of Cu to Ti is 1:20;
(3) Drying the substance obtained after the reaction in the step (2) in a water bath kettle at the temperature of 60-70 ℃, roasting the dried substance in a muffle furnace at the temperature of 240 ℃ for 2h, and drying and grinding the substance into powder to obtain the carrier Cu-TiO of the catalyst 2 ；
(4) Taking the carrier Cu-TiO obtained in the step (3) 2 2.0g, adding 10mL of absolute ethyl alcohol, carrying out ultrasonic oscillation for 20min to disperse the catalyst in the absolute ethyl alcohol, adding a phosphotungstic acid ethanol solution (0.5 g of phosphotungstic acid is weighed and dissolved in 15mL of ethanol solution), enabling the loading amount of the phosphotungstic acid to be 25%, soaking for 12h at the temperature of 60 ℃ and the rotating speed of 400r/min, drying a soaked sample at the temperature of 60-70 ℃, and obtaining PW/Cu-TiO 2 A photocatalyst.
The application of the photocatalyst prepared in the preparation of 1, 8-cineole by catalyzing terpineol is as follows: taking 2.5gPW/Cu-TiO 2 Adding a photocatalyst and 20mL of terpineol (isomer mixture) into a photocatalytic reactor, reacting at normal temperature for 1h to obtain 1, 8-cineole, and carrying out GC and GC-MS analysis on a reaction product to obtain the terpineol conversion rate of 90.98%; the selectivity to cineole was then 68.21%.
The foregoing description of specific exemplary embodiments of the invention has been presented for the purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (9)
1. The preparation method of the photocatalyst is characterized by comprising the following operation steps:
(1) Dropwise adding butyl titanate into ethanol, and stirring and adding concentrated hydrochloric acid;
(2) Adding copper chloride into the substance obtained after adding concentrated hydrochloric acid in the step (1) for reaction, wherein the mass ratio of Cu to Ti is 1;
(3) Drying the substance obtained after the reaction in the step (2), roasting at 180-300 ℃, and drying again to obtain the carrier Cu-TiO of the catalyst 2 ；
(4) Taking the carrier Cu-TiO obtained in the step (3) 2 Adding ethanol, ultrasonically vibrating, adding phosphotungstic acid ethanol solution to ensure that the loading capacity of phosphotungstic acid is 10-30%, soaking for 6-24 h, and drying a soaked sample to obtain PW/Cu-TiO 2 A catalyst.
2. The method for preparing a photocatalyst according to claim 1, characterized in that: step (1), 24ml of butyl titanate is taken and dripped into 96ml of absolute ethyl alcohol within 5-10 min; 2ml of concentrated hydrochloric acid with the mass concentration of 36% is added in the step (1).
3. The method for preparing a photocatalyst according to claim 1, characterized in that: in the step (2), the mass ratio of Cu to Ti is 1.
4. The method for preparing a photocatalyst according to claim 1, characterized in that: and (3) drying in a water bath kettle at the temperature of 60-70 ℃.
5. The method for preparing a photocatalyst according to claim 1, wherein: taking the carrier Cu-TiO in the step (4) 2 2.0g of carrier, 10ml ofAnd (5) water and ethanol.
6. The method for preparing a photocatalyst according to claim 1, characterized in that: the loading amount of the phosphotungstic acid in the step (4) is 25%.
7. The method for preparing a photocatalyst according to claim 1, characterized in that: in the step (4), the dipping is carried out for 6 to 24 hours at the temperature of 60 ℃ and the rotating speed of 400 r/min.
8. The use of the photocatalyst prepared by the method of any one of claims 1 to 7 for the preparation of 1, 8-cineole from terpineol, wherein the photocatalyst comprises: adding the photocatalyst and terpineol into a photocatalytic reactor, and reacting for 1h to obtain the 1, 8-cineole.
9. Use according to claim 8, characterized in that: 2g of photocatalyst and 20mL of terpineol were added to the photocatalytic reactor.
Priority Applications (1)
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| WO2012028566A1 (en) * | 2010-09-03 | 2012-03-08 | Danmarks Tekniske Universitet | HETEROPOLY ACID PROMOTED CATALYST FOR SCR OF NOx WITH AMMONIA |
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