CN113980030A - Method for high-selectivity catalytic synthesis of1,8-cineole - Google Patents
Method for high-selectivity catalytic synthesis of1,8-cineole Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000007036 catalytic synthesis reaction Methods 0.000 title claims abstract description 39
- 229960005233 cineole Drugs 0.000 title claims abstract description 33
- WEEGYLXZBRQIMU-UHFFFAOYSA-N Eucalyptol Chemical compound C1CC2CCC1(C)OC2(C)C WEEGYLXZBRQIMU-UHFFFAOYSA-N 0.000 claims abstract description 93
- 238000006243 chemical reaction Methods 0.000 claims abstract description 83
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 claims abstract description 50
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 claims abstract description 47
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- 239000003054 catalyst Substances 0.000 claims abstract description 39
- 239000002808 molecular sieve Substances 0.000 claims abstract description 34
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 34
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002149 hierarchical pore Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000005342 ion exchange Methods 0.000 claims abstract description 4
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- 238000003756 stirring Methods 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 30
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- 239000007864 aqueous solution Substances 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 2
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- 239000007810 chemical reaction solvent Substances 0.000 claims 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims 1
- 238000005530 etching Methods 0.000 claims 1
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- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
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- 238000001514 detection method Methods 0.000 description 24
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- 238000000967 suction filtration Methods 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000006317 isomerization reaction Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 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 description 4
- 241000723346 Cinnamomum camphora Species 0.000 description 3
- 244000166124 Eucalyptus globulus Species 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 2
- IBVJWOMJGCHRRW-UHFFFAOYSA-N 3,7,7-Trimethylbicyclo[4.1.0]hept-2-ene Chemical compound C1CC(C)=CC2C(C)(C)C12 IBVJWOMJGCHRRW-UHFFFAOYSA-N 0.000 description 2
- 235000004692 Eucalyptus globulus Nutrition 0.000 description 2
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 229920000831 ionic polymer Polymers 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
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- PXRCIOIWVGAZEP-UHFFFAOYSA-N Camphene hydrate Chemical compound C1CC2C(O)(C)C(C)(C)C1C2 PXRCIOIWVGAZEP-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- WEEGYLXZBRQIMU-WAAGHKOSSA-N Eucalyptol Chemical compound C1C[C@H]2CC[C@]1(C)OC2(C)C WEEGYLXZBRQIMU-WAAGHKOSSA-N 0.000 description 1
- 241000218195 Lauraceae Species 0.000 description 1
- 241000219926 Myrtaceae Species 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- RFFOTVCVTJUTAD-UHFFFAOYSA-N cineole Natural products C1CC2(C)CCC1(C(C)C)O2 RFFOTVCVTJUTAD-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
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- 239000000446 fuel Substances 0.000 description 1
- 150000002268 gamma-terpinene derivatives Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000346 nonvolatile oil Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
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- 229940035637 spectrum-4 Drugs 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/08—Bridged systems
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
Abstract
The invention is suitable for the field of synthesizing hierarchical pore HZSM-5 catalysts, and provides a method for high-selectivity catalytic synthesis of1,8-cineole, wherein the method for high-selectivity catalytic synthesis of1,8-cineole comprises the following steps: 1) and (3) carrying out desiliconization treatment on the ZSM-5 molecular sieve, and introducing NH4NO3 solution to realize ion exchange to obtain hierarchical pore HZSM-5. 2) The alpha-terpineol is used as a raw material, the prepared hierarchical pore HZSM-5 is used as a catalyst, and the alpha-terpineol is catalyzed to isomerize under the heating condition of normal pressure to synthesize the 1, 8-cineole. Breaks through the technical barrier of low yield of the prior alpha-terpineol synthesized 1, 8-cineole. The molecular sieve ZSM-5 with different silica-alumina ratios is adopted for modification, so that the catalytic effect on catalytic reaction is different, the optimal reaction conditions are different, and the total yield is higher, so that the method has the potential of larger adjustability and exploration conditions.
Description
Technical Field
The invention belongs to the field of synthesizing hierarchical pore HZSM-5 catalysts, and particularly relates to a method for high-selectivity catalytic synthesis of1, 8-cineole.
Background
1,8-cineole, known under the scientific name 1,3,3 trimethyl-2-oxabicyclo [2, 2, 2] octane, having the molecular formula C10H18O, is a colorless transparent oily liquid, is easily volatile, has an irritating camphor smell and a special herbal taste. Slightly soluble in water, readily soluble in organic solvents and most non-volatile oils.
The natural 1,8-cineole is mainly stored in eucalyptus globulus labdana of Myrtaceae and Cinnamomum camphora of Lauraceae, is an important fine chemical product, has good antibacterial, anti-inflammatory, antiseptic, insecticidal and mosquito-repellent effects, is widely applied to the fields of essence, perfume, health and medicine, and has wide market prospect (south well I. Eucalyptus leaf oils: use, chemistry, diagnosis and marking [ J ]. Journal of Chromatography A,1992,598(2): 316). The current methods for preparing 1,8-cineole mainly include natural extraction and chemical synthesis (Wu H W, Hendrawiana W, Yu Y, et al. Effect of hydrolysis on1, 8-cyclic extraction from maleic leaf and the fuel properties of biological [ J ]. Industrial & Engineering Chemistry Research,2011, 50(19): 11280-. Because the natural plant eucalyptus globulus labill or camphor tree has limited resources, the chemical synthesis method of1,8-cineole is continuously researched at home and abroad. Greider CE et al (Greider CE, Cleveland. Process for the production of cineole U.S. patent [ P ].1935) conducted preliminary studies on the catalytic synthesis of eucalyptol by terpineol isomerization, theoretically demonstrating the feasibility of the catalytic reaction for the synthesis of l, 8-cineole; farina L et al (Farina L, Boido E, Carrau F, et al. Terylene compounds as able to be compressed particulates of1,8-cineole in red grains and wires [ J ]. Journal of agricultural and food chemistry,2005,53 (5); 1633-) 1636.) demonstrate that limonene and a-terpineol can both be converted to 1,8-cineole under liquid acid catalysis; leao Lana E J et al (Leao Lana E J, da Silva Rocha KA, Kozhevnikov I V, et al. Synthesis of l,8-cineole and l,4-cineole by I analysis of a-terpineol catalyzed by a-heteropolyyacid [ J ]. Journal of Molecular Catalysis A: Chemical,2006,259(1):99-102) first convert a heteropoly acid having a Keggin structure: phosphotungstic acid (H3PW12O40) and solid acid prepared by loading phosphotungstic acid are used as catalysts to catalyze a-terpineol to isomerize and synthesize 1,8-cineole in homogeneous and heterogeneous catalysis systems respectively, and 70% of alpha-terpineol conversion rate and 1,8-cineole selectivity close to 35% are obtained in the heterogeneous catalysis system; in recent years, Wubanjun et al (Wubanjun, research on imidazole polyion liquid immobilized phosphotungstic acid and catalytic alpha-terpineol isomerization synthesis of1,8-cineole [ D ] Xiamen university, 2017.) in China utilize imidazole polyion liquid immobilized phosphotungstic acid and catalytic alpha-terpineol isomerization synthesis of the same, and research on1,8-cineole obtains 100% alpha-terpineol conversion rate and 51.7% 1,8-cineole selectivity; hongyanzhen and the like ((Hongyanzhen, Wangdui, Li Zhuo Yi, Xuya, Wang hongtao, Suyu fai, Pengli, Li Jun.) supercritical carbon dioxide intervened alpha-terpineol catalytic synthesis 1,8-cineole [ J/OL ]. the chemical project: 1-10[2021-06-16].) utilizes supercritical CO2 intervened alpha-terpineol isomerization synthesis 1,8-cineole to obtain 100% alpha-terpineol conversion rate and 54.6% 1,8-cineole selectivity.
Disclosure of Invention
The invention provides a low-cost high-catalytic-activity and selective catalyst synthesis process and a simple and easy catalytic reaction process flow, aiming at the problems of complex steps, complex catalyst synthesis process, high cost, poor catalytic activity and low yield of a target 1,8-cineole in the existing alpha-terpineol catalytic synthesis process.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for high-selectivity catalytic synthesis of1,8-cineole comprises the following steps:
1) and (3) carrying out desiliconization treatment on the ZSM-5 molecular sieve, and introducing NH4NO3 solution to realize ion exchange to obtain hierarchical pore HZSM-5.
2) The alpha-terpineol is used as a raw material, the prepared hierarchical pore HZSM-5 is used as a catalyst, and the alpha-terpineol is catalyzed to isomerize under the heating condition of normal pressure to synthesize the 1, 8-cineole.
The method for high-selectivity catalytic synthesis of1,8-cineole provided by the embodiment of the invention has the following beneficial effects:
1) the obtained hierarchical pore HZSM-5 catalyst is used for catalyzing alpha-terpineol to synthesize 1,8-cineole, the alpha-terpineol conversion rate and the 1,8-cineole selectivity are high, and the alpha-terpineol conversion rate of 100% and the 1,8-cineole selectivity of 59% can be obtained at most. The technical barrier of low yield of the prior alpha-terpineol synthesized 1,8-cineole is broken through, and the reaction is carried out under normal pressure and low temperature, so that the energy consumption is low, the process is simple, and the generation cost is low.
2) The hierarchical pore HZSM-5 molecular sieve with high catalytic activity and high selectivity is prepared by a simple method. The catalyst has good stability and no pollution to the environment, and simultaneously, the catalyst adopts the industrial commercial molecular sieve ZSM-5 as the raw material, has wide sources and low price, is simple in modification operation, low in energy consumption and equipment investment, and is easy to realize large-scale industrial production of the reaction for catalytically synthesizing the 1,8-cineole from the alpha-terpineol.
3) The hierarchical pore HZSM-5 catalyst prepared by the invention has various raw material ZSM-5 molecular sieve silica-alumina ratios, adopts the molecular sieves ZSM-5 with different silica-alumina ratios for modification, has different catalytic effects on catalytic reaction, has different optimal reaction conditions and higher overall yield, and therefore has greater adjustability and potential for exploring conditions.
Drawings
FIG. 1 is a GC-MS detection spectrum 1 of the reaction of the method for high-selectivity catalytic synthesis of1,8-cineole provided by the embodiment of the invention;
FIG. 2 is a GC-MS detection spectrum 2 of the reaction of the method for high-selectivity catalytic synthesis of1,8-cineole provided by the embodiment of the invention;
FIG. 3 is a GC-MS detection spectrum 3 of the reaction of the method for high-selectivity catalytic synthesis of1,8-cineole provided by the embodiment of the invention;
FIG. 4 is a GC-MS detection spectrum 4 of the reaction of the method for high-selectivity catalytic synthesis of1,8-cineole provided by the embodiment of the invention;
FIG. 5 is a GC-MS detection spectrum 5 of the reaction of the method for the high-selectivity catalytic synthesis of1,8-cineole provided by the embodiment of the invention;
FIG. 6 is a GC-MS detection spectrum 6 of the reaction of the method for high-selectivity catalytic synthesis of1,8-cineole provided by the embodiment of the invention;
FIG. 7 is a GC-MS detection spectrum 7 of the reaction of a method for the highly selective catalytic synthesis of1,8-cineole according to the embodiment of the present invention;
FIG. 8 is a GC-MS detection spectrum 8 of the reaction of a method for the highly selective catalytic synthesis of1,8-cineole according to the embodiment of the present invention;
FIG. 9 is a GC-MS detection spectrum 9 of the reaction of a method for the highly selective catalytic synthesis of1,8-cineole according to the embodiment of the present invention;
FIG. 10 is a GC-MS detection spectrum 10 of the reaction of a method for the highly selective catalytic synthesis of1,8-cineole according to the embodiment of the present invention;
FIG. 11 is a GC-MS detection spectrum 11 of the reaction of a method for the highly selective catalytic synthesis of1,8-cineole according to the embodiment of the present invention;
FIG. 12 is a GC-MS detection spectrum 12 of the reaction of the method for the high-selectivity catalytic synthesis of1,8-cineole according to the embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Specific implementations of the present invention are described in detail below with reference to specific embodiments.
Example 1
As shown in FIG. 1, for the GC-MS detection spectrum of the reaction of this example, first, a ZSM-5 molecular sieve having a silica-alumina ratio of 170 and a NaOH aqueous solution having a concentration of 0.1mol/l were mixed according to a solid-to-liquid ratio of 1: 20(g/ml), stirred at a rotation speed of 200r/min, heated at 80 ℃ for 1h, and then filtered to obtain a solid filter cake, which was dried at 80 ℃ for 24h under constant temperature air blowing to obtain Na-type ZSM-5.
Mixing the obtained Na-type ZSM-5 molecular sieve with a NH4NO3 solution with the concentration of 1mol/L according to the solid-to-liquid ratio of 1: 100, stirring at the rotating speed of 400r/min, heating at the temperature of 80 ℃, performing suction filtration after 4 hours to obtain a solid filter cake, drying the filter cake for 24 hours under constant temperature air blast at the temperature of 100 ℃, and performing roasting procedures as follows: and (4) heating for 100min to 550 ℃ (keeping the temperature constant for 4h) at normal temperature, and roasting to obtain the HZSM-5 catalyst.
The catalytic synthesis of the 1,8-cineole is carried out according to the mass ratio of the alpha-terpineol to the solvent n-hexane of 1: 39, the mass ratio of the catalyst to the reaction solution of 0.0112: 1, stirring and heating are carried out, the stirring speed is 400r/min, the reaction temperature is 65 ℃, the reaction time is 4 hours, the conversion rate of the alpha-terpineol is 59.76% and the selectivity of the 1,8-cineole is 42.46% through gas-mass chromatography analysis of reaction products.
| Peak number | Retention time | Percentage of peak area | Peak area | Peak height | Content (%) |
| 1 | 7.535 | 4.8 | 1918825.96 | 393428.25 | 1.93 |
| 2 | 8.025 | 20.75 | 8288987.4 | 1595017.4 | 8.35 |
| 3 | 8.537 | 36.55 | 14597270.67 | 3444843.7 | 14.71 |
| 4 | 8.637 | 63.06 | 25188958.3 | 6081284.1 | 25.38 |
| 5 | 9.909 | 5.24 | 2092382.53 | 285635.27 | 2.11 |
| 6 | 11.345 | 15.4 | 6150385.04 | 625594.79 | 6.2 |
| 7 | 14.743 | 1.45 | 580154.37 | 67086.8 | 0.58 |
| 8 | 16.456 | 1.24 | 496758.08 | 69552.01 | 0.5 |
| 9 | 17.48 | 100 | 39942010.11 | 4400976.2 | 40.24 |
| In total | 99255732.46 | 16963418 | 100 |
TABLE 1 GC-MS analysis of the reaction of example 1
Example 2
As shown in FIG. 2, for the GC-MS detection spectrum of the reaction of this example, first, a ZSM-5 molecular sieve having a silica-alumina ratio of 170 and a NaOH aqueous solution having a concentration of 0.3mol/l were mixed according to a solid-to-liquid ratio of 1: 20(g/ml), stirred at a rotation speed of 200r/min, heated at 80 ℃ for 1h, and then filtered to obtain a solid filter cake, which was dried at 80 ℃ for 24h under constant temperature air blowing to obtain Na type ZSM-5.
Mixing the obtained Na-type ZSM-5 molecular sieve with a NH4NO3 solution with the concentration of 1mol/L according to the solid-to-liquid ratio of 1: 100, stirring at the rotating speed of 400r/min, heating at the temperature of 80 ℃, performing suction filtration after 4 hours to obtain a solid filter cake, drying the filter cake for 24 hours under constant temperature air blast at the temperature of 100 ℃, and performing roasting procedures as follows: and (4) heating for 100min to 550 ℃ (keeping the temperature constant for 4h) at normal temperature, and roasting to obtain the HZSM-5 catalyst.
The catalytic synthesis of the 1,8-cineole is carried out according to the mass ratio of the alpha-terpineol to the solvent n-hexane of 1: 39, the mass ratio of the catalyst to the reaction solution of 0.0112: 1, stirring and heating are carried out, the stirring speed is 400r/min, the reaction temperature is 65 ℃, the reaction time is 4 hours, the conversion rate of the alpha-terpineol is 85.66% and the selectivity of the 1,8-cineole is 54.80% through gas-mass chromatography analysis of reaction products.
| Peak number | Retention time | Percentage of peak area | Peak area | Peak height | Content (%) |
| 1 | 7.578 | 4.74 | 1208547.28 | 221252.98 | 2.22 |
| 2 | 8.068 | 23.28 | 5936994.85 | 917876.84 | 10.93 |
| 3 | 8.573 | 32.05 | 8172694.64 | 2144664.33 | 15.04 |
| 4 | 8.658 | 100 | 25502599.37 | 5182758.63 | 46.94 |
| 5 | 9.98 | 5.3 | 1351279.51 | 131292.6 | 2.49 |
| 6 | 11.438 | 16.05 | 4093703.19 | 270362.32 | 7.53 |
| 7 | 16.684 | 1.09 | 277925.73 | 17502.1 | 0.51 |
| 8 | 17.7 | 30.54 | 7789132.23 | 379681.34 | 14.34 |
| In total | 54332876.8 | 9265391.14 | 100 |
TABLE 2 GC-MS analysis of the reaction of example 2
Example 3
As shown in FIG. 3, for the GC-MS detection spectrum of the reaction of this example, first, a ZSM-5 molecular sieve having a silica-alumina ratio of 170 and a NaOH aqueous solution having a concentration of 0.5mol/l were mixed according to a solid-to-liquid ratio of 1: 20(g/ml), stirred at a rotation speed of 200r/min, heated at 80 ℃ for 1h, and then filtered to obtain a solid filter cake, which was dried at 80 ℃ for 24h under constant temperature air blowing to obtain Na type ZSM-5.
Mixing the obtained Na-type ZSM-5 molecular sieve with a NH4NO3 solution with the concentration of 1mol/L according to the solid-to-liquid ratio of 1: 100, stirring at the rotating speed of 400r/min, heating at the temperature of 80 ℃, performing suction filtration after 4 hours to obtain a solid filter cake, drying the filter cake for 24 hours under constant temperature air blast at the temperature of 100 ℃, and performing roasting procedures as follows: and (4) heating for 100min to 550 ℃ (keeping the temperature constant for 4h) at normal temperature, and roasting to obtain the HZSM-5 catalyst.
The catalytic synthesis of the 1,8-cineole is carried out according to the mass ratio of the alpha-terpineol to the solvent n-hexane of 1: 39, the mass ratio of the catalyst to the reaction solution of 0.0112: 1, stirring and heating are carried out, the stirring speed is 400r/min, the reaction temperature is 65 ℃, the reaction time is 4 hours, the conversion rate of the alpha-terpineol is 100 percent and the selectivity of the 1,8-cineole is 44.35 percent through gas-mass chromatography analysis of reaction products.
| Peak number | Retention time | Percentage of peak area | Peak area | Peak height | Content (%) |
| 1 | 7.535 | 4.72 | 1988091.15 | 321316.48 | 2.09 |
| 2 | 8.025 | 42.31 | 17811846.1 | 2853702.93 | 18.76 |
| 3 | 8.537 | 35.79 | 15065937.5 | 4117582.5 | 15.87 |
| 4 | 8.615 | 100 | 42096952.61 | 8835974.05 | 44.35 |
| 5 | 9.923 | 11.67 | 4914300.18 | 382166.42 | 5.18 |
| 6 | 11.366 | 31 | 13049258.16 | 656606.27 | 13.75 |
| In total | 94926385.7 | 17167348.65 | 100 |
TABLE 3 GC-MS analysis of the reaction of example 3
Example 4
As shown in FIG. 4, for the GC-MS detection spectrum of the reaction of this example, first, a ZSM-5 molecular sieve having a silica-alumina ratio of 170 and a NaOH aqueous solution having a concentration of 0.5mol/l were mixed according to a solid-to-liquid ratio of 1: 20(g/ml), stirred at a rotation speed of 200r/min, heated at 80 ℃ for 1h, and then filtered to obtain a solid filter cake, which was dried at 80 ℃ for 24h under constant temperature air blowing to obtain Na type ZSM-5.
Mixing the obtained Na-type ZSM-5 molecular sieve with a NH4NO3 solution with the concentration of 1mol/L according to the solid-to-liquid ratio of 1: 100, stirring at the rotating speed of 400r/min, heating at the temperature of 80 ℃, performing suction filtration after 4 hours to obtain a solid filter cake, drying the filter cake for 24 hours under constant temperature air blast at the temperature of 100 ℃, and performing roasting procedures as follows: and (4) heating for 100min to 550 ℃ (keeping the temperature constant for 4h) at normal temperature, and roasting to obtain the HZSM-5 catalyst.
The catalytic synthesis of the 1,8-cineole is carried out according to the mass ratio of the alpha-terpineol to the solvent n-hexane of 1: 39, the mass ratio of the catalyst to the reaction solution of 0.0112: 1, stirring and heating are carried out, the stirring speed is 400r/min, the reaction temperature is 65 ℃, the reaction time is 8 hours, the conversion rate of the alpha-terpineol is 100 percent and the selectivity of the 1,8-cineole is 31.76 percent through gas-mass chromatography analysis of reaction products.
TABLE 4 GC-MS analysis of the reaction of example 4
Example 5
As shown in FIG. 5, for the GC-MS detection spectrum of the reaction of this example, first, a ZSM-5 molecular sieve having a silica-alumina ratio of 170 and a NaOH aqueous solution having a concentration of 0.3mol/l were mixed according to a solid-to-liquid ratio of 1: 20(g/ml), stirred at a rotation speed of 200r/min, heated at 80 ℃ for 1h, and then filtered to obtain a solid filter cake, which was dried at 80 ℃ for 24h under constant temperature air blowing to obtain Na type ZSM-5.
Mixing the obtained Na-type ZSM-5 molecular sieve with a NH4NO3 solution with the concentration of 1mol/L according to the solid-to-liquid ratio of 1: 100, stirring at the rotating speed of 400r/min, heating at the temperature of 80 ℃, performing suction filtration after 4 hours to obtain a solid filter cake, drying the filter cake for 24 hours under constant temperature air blast at the temperature of 100 ℃, and performing roasting procedures as follows: and (4) heating for 100min to 550 ℃ (keeping the temperature constant for 4h) at normal temperature, and roasting to obtain the HZSM-5 catalyst.
The catalytic synthesis of the 1,8-cineole is carried out according to the mass ratio of the alpha-terpineol to the solvent n-hexane of 1: 39, the mass ratio of the catalyst to the reaction solution of 0.0112: 1, stirring and heating are carried out, the stirring speed is 400r/min, the reaction temperature is 69 ℃, the reaction time is 4 hours, the conversion rate of the alpha-terpineol is 90.02 percent and the selectivity of the 1,8-cineole is 51.79 percent through gas-mass chromatography analysis of reaction products.
TABLE 5 GC-MS analysis of the reaction of example 5
Example 6
As shown in FIG. 6, for the GC-MS detection spectrum of the reaction of this example, first, a ZSM-5 molecular sieve having a silica-alumina ratio of 170 and a NaOH aqueous solution having a concentration of 0.3mol/l were mixed according to a solid-to-liquid ratio of 1: 20(g/ml), stirred at a rotation speed of 200r/min, heated at 80 ℃ for 1h, and then filtered to obtain a solid filter cake, which was dried at 80 ℃ for 24h under constant temperature air blowing to obtain Na type ZSM-5.
Mixing the obtained Na-type ZSM-5 molecular sieve with a NH4NO3 solution with the concentration of 1mol/L according to the solid-to-liquid ratio of 1: 100, stirring at the rotating speed of 400r/min, heating at the temperature of 80 ℃, performing suction filtration after 4 hours to obtain a solid filter cake, drying the filter cake for 24 hours under constant temperature air blast at the temperature of 100 ℃, and performing roasting procedures as follows: and (4) heating for 100min to 550 ℃ (keeping the temperature constant for 4h) at normal temperature, and roasting to obtain the HZSM-5 catalyst.
The catalytic synthesis of the 1,8-cineole is carried out according to the mass ratio of the alpha-terpineol to the solvent n-hexane of 1: 39, the mass ratio of the catalyst to the reaction solution of 0.0112: 1, stirring and heating are carried out, the stirring speed is 400r/min, the reaction temperature is 75 ℃, the reaction time is 4 hours, the conversion rate of the alpha-terpineol is 100 percent and the selectivity of the 1,8-cineole is 36 percent through gas-mass chromatography analysis of reaction products.
TABLE 6 GC-MS analysis of the reaction of example 6
Example 7
As shown in FIG. 7, for the GC-MS detection spectrum of the reaction of this example, first, a ZSM-5 molecular sieve having a silica-alumina ratio of 170 and a NaOH aqueous solution having a concentration of 0.3mol/l were mixed according to a solid-to-liquid ratio of 1: 20(g/ml), stirred at a rotation speed of 200r/min, heated at 80 ℃ for 1h, and then filtered to obtain a solid filter cake, which was dried at 80 ℃ for 24h under constant temperature air blowing to obtain Na type ZSM-5.
Mixing the obtained Na-type ZSM-5 molecular sieve with a NH4NO3 solution with the concentration of 1mol/L according to the solid-to-liquid ratio of 1: 100, stirring at the rotating speed of 400r/min, heating at the temperature of 80 ℃, performing suction filtration after 4 hours to obtain a solid filter cake, drying the filter cake for 24 hours under constant temperature air blast at the temperature of 100 ℃, and performing roasting procedures as follows: and (4) heating for 100min to 550 ℃ (keeping the temperature constant for 4h) at normal temperature, and roasting to obtain the HZSM-5 catalyst.
The catalytic synthesis of the 1,8-cineole is carried out according to the mass ratio of the alpha-terpineol to the solvent n-hexane of 1: 39, the mass ratio of the catalyst to the reaction solution of 0.0112: 1, stirring and heating are carried out, the stirring speed is 400r/min, the reaction temperature is 69 ℃, the reaction time is 8 hours, the conversion rate of the alpha-terpineol is 100 percent and the selectivity of the 1,8-cineole is 59.98 percent through gas-mass chromatography analysis of reaction products.
TABLE 7 GC-MS analysis of the reaction of example 7
Example 8
As shown in FIG. 8, for the GC-MS detection spectrum of the reaction of this example, first, a ZSM-5 molecular sieve having a silica-alumina ratio of 170 and a NaOH aqueous solution having a concentration of 0.3mol/l were mixed according to a solid-to-liquid ratio of 1: 20(g/ml), stirred at a rotation speed of 200r/min, heated at 80 ℃ for 1h, and then filtered to obtain a solid filter cake, which was dried at 80 ℃ for 24h under constant temperature air blowing to obtain Na type ZSM-5.
Mixing the obtained Na-type ZSM-5 molecular sieve with a NH4NO3 solution with the concentration of 1mol/L according to the solid-to-liquid ratio of 1: 100, stirring at the rotating speed of 400r/min, heating at the temperature of 80 ℃, performing suction filtration after 4 hours to obtain a solid filter cake, drying the filter cake for 24 hours under constant temperature air blast at the temperature of 100 ℃, and performing roasting procedures as follows: and (4) heating for 100min to 550 ℃ (keeping the temperature constant for 4h) at normal temperature, and roasting to obtain the HZSM-5 catalyst.
The catalytic synthesis of the 1,8-cineole is carried out according to the mass ratio of the alpha-terpineol to the solvent n-hexane of 1: 39, the mass ratio of the catalyst to the reaction solution of 0.0112: 1, stirring and heating are carried out, the stirring speed is 400r/min, the reaction temperature is 69 ℃, the reaction time is 10 hours, the conversion rate of the alpha-terpineol is 100 percent and the selectivity of the 1,8-cineole is 35.10 percent through gas-mass chromatography analysis of reaction products.
TABLE 8 GC-MS analysis of the reaction of example 8
Example 9
As shown in FIG. 9, for the GC-MS detection spectrum of the reaction of this example, first, a ZSM-5 molecular sieve having a silica-alumina ratio of 38 and a NaOH aqueous solution having a concentration of 0.3mol/l were mixed according to a solid-to-liquid ratio of 1: 20(g/ml), stirred at a rotation speed of 200r/min, heated at 80 ℃ for 1h, and then filtered to obtain a solid filter cake, which was dried at 80 ℃ for 24h under constant temperature air blowing to obtain Na-type ZSM-5.
Mixing the obtained Na-type ZSM-5 molecular sieve with a NH4NO3 solution with the concentration of 1mol/L according to the solid-to-liquid ratio of 1: 100, stirring at the rotating speed of 400r/min, heating at the temperature of 80 ℃, performing suction filtration after 4 hours to obtain a solid filter cake, drying the filter cake for 24 hours under constant temperature air blast at the temperature of 100 ℃, and performing roasting procedures as follows: and (4) heating for 100min to 550 ℃ (keeping the temperature constant for 4h) at normal temperature, and roasting to obtain the HZSM-5 catalyst.
The catalytic synthesis of the 1,8-cineole is carried out according to the mass ratio of the alpha-terpineol to the solvent n-hexane of 1: 39, the mass ratio of the catalyst to the reaction solution of 0.0112: 1, stirring and heating are carried out, the stirring speed is 400r/min, the reaction temperature is 69 ℃, the reaction time is 8 hours, the conversion rate of the alpha-terpineol is 100 percent and the selectivity of the 1,8-cineole is 45.17 percent through gas-mass chromatography analysis of reaction products.
TABLE 9 GC-MS analysis of the reaction of example 9
Example 10
As shown in FIG. 10, for the GC-MS detection spectrum of the reaction of this example, first, a ZSM-5 molecular sieve having a silica-alumina ratio of 70 and a NaOH aqueous solution having a concentration of 0.3mol/l were mixed according to a solid-to-liquid ratio of 1: 20(g/ml), stirred at a rotation speed of 200r/min, heated at 80 ℃ for 1h, and then filtered to obtain a solid filter cake, which was dried at 80 ℃ for 24h under constant temperature air blowing to obtain Na-type ZSM-5.
Mixing the obtained Na-type ZSM-5 molecular sieve with a NH4NO3 solution with the concentration of 1mol/L according to the solid-to-liquid ratio of 1: 100, stirring at the rotating speed of 400r/min, heating at the temperature of 80 ℃, performing suction filtration after 4 hours to obtain a solid filter cake, drying the filter cake for 24 hours under constant temperature air blast at the temperature of 100 ℃, and performing roasting procedures as follows: and (4) heating for 100min to 550 ℃ (keeping the temperature constant for 4h) at normal temperature, and roasting to obtain the HZSM-5 catalyst.
The catalytic synthesis of the 1,8-cineole is carried out according to the mass ratio of the alpha-terpineol to the solvent n-hexane of 1: 39, the mass ratio of the catalyst to the reaction solution of 0.0112: 1, stirring and heating are carried out, the stirring speed is 400r/min, the reaction temperature is 69 ℃, the reaction time is 8 hours, the conversion rate of the alpha-terpineol is 100 percent and the selectivity of the 1,8-cineole is 55.17 percent through gas-mass chromatography analysis of reaction products.
TABLE 10 GC-MS analysis of the example 10 reaction
Example 11
As shown in FIG. 11, for the GC-MS detection spectrum of the reaction of this example, first, a ZSM-5 molecular sieve having a silica-alumina ratio of 380 and a NaOH aqueous solution having a concentration of 0.3mol/l were mixed according to a solid-to-liquid ratio of 1: 20(g/ml), stirred at a rotation speed of 200r/min, heated at 80 ℃ for 1h, and then filtered to obtain a solid filter cake, which was dried at 80 ℃ for 24h under constant temperature air blowing to obtain Na-type ZSM-5.
Mixing the obtained Na-type ZSM-5 molecular sieve with a NH4NO3 solution with the concentration of 1mol/L according to the solid-to-liquid ratio of 1: 100, stirring at the rotating speed of 400r/min, heating at the temperature of 80 ℃, performing suction filtration after 4 hours to obtain a solid filter cake, drying the filter cake for 24 hours under constant temperature air blast at the temperature of 100 ℃, and performing roasting procedures as follows: and (4) heating for 100min to 550 ℃ (keeping the temperature constant for 4h) at normal temperature, and roasting to obtain the HZSM-5 catalyst.
The catalytic synthesis of the 1,8-cineole is carried out according to the mass ratio of the alpha-terpineol to the solvent n-hexane of 1: 39, the mass ratio of the catalyst to the reaction solution of 0.0112: 1, stirring and heating are carried out, the stirring speed is 400r/min, the reaction temperature is 69 ℃, the reaction time is 8 hours, the conversion rate of the alpha-terpineol is 97.97% and the selectivity of the 1,8-cineole is 45.69% through gas-mass chromatography analysis of reaction products.
TABLE 11 GC-MS analysis of the reaction of example 11
Example 12
As shown in FIG. 12, for the GC-MS detection spectrum of the reaction of this example, first, a ZSM-5 molecular sieve having a silica-alumina ratio of 500 and a NaOH aqueous solution having a concentration of 0.3mol/l were mixed according to a solid-to-liquid ratio of 1: 20(g/ml), stirred at a rotation speed of 200r/min, heated at 80 ℃ for 1h, and then filtered to obtain a solid filter cake, which was dried at 80 ℃ for 24h under constant temperature air blowing to obtain Na-type ZSM-5.
Mixing the obtained Na-type ZSM-5 molecular sieve with a NH4NO3 solution with the concentration of 1mol/L according to the solid-to-liquid ratio of 1: 100, stirring at the rotating speed of 400r/min, heating at the temperature of 80 ℃, performing suction filtration after 4 hours to obtain a solid filter cake, drying the filter cake for 24 hours under constant temperature air blast at the temperature of 100 ℃, and performing roasting procedures as follows: and (4) heating for 100min to 550 ℃ (keeping the temperature constant for 4h) at normal temperature, and roasting to obtain the HZSM-5 catalyst.
The catalytic synthesis of the 1,8-cineole is carried out according to the mass ratio of the alpha-terpineol to the solvent n-hexane of 1: 39, the mass ratio of the catalyst to the reaction solution of 0.0112: 1, stirring and heating are carried out, the stirring speed is 400r/min, the reaction temperature is 69 ℃, the reaction time is 8 hours, the conversion rate of the alpha-terpineol is 77.91% and the selectivity of the 1,8-cineole is 42.96% through gas-mass chromatography analysis of reaction products.
| Peak number | Retention time | Percentage of peak area | Peak area | Peak height | Content (%) |
| 1 | 7.542 | 7.21 | 4025444.7 | 747733.61 | 2.41 |
| 2 | 8.025 | 30.59 | 17078223.66 | 3093780.08 | 10.23 |
| 3 | 8.566 | 61.77 | 34487903.51 | 7856772.21 | 20.67 |
| 4 | 8.644 | 100 | 55836047.81 | 12719239.74 | 33.47 |
| 5 | 9.916 | 8.56 | 4779497.77 | 548793.61 | 2.86 |
| 6 | 11.362 | 24.73 | 13807039.07 | 1317810.54 | 8.27 |
| 7 | 17.423 | 66.02 | 36864806.43 | 1943786.19 | 22.09 |
| In total | 166878963 | 28227915.98 | 100 |
TABLE 12 GC-MS analysis of the reaction of example 12
Analysis conditions of gas chromatography-mass spectrometry: chromatographic column Rtx-5 capillary column 30m × 250um × 0.25 um; temperature programming is carried out at 60 ℃ (2min) to 90 ℃ and 2/min; at 90-240 deg.c and 50 deg.c/min; the sample introduction temperature is 210 ℃; carrier gas He,3 ml/min; the sample injection amount is 1 mu L, and the split ratio (the volume ratio) is 60: 1; the interface temperature is 210 ℃; by retrieving the energy of 70 ev; the ion source temperature is 230 ℃; multiplier voltage 0.77 kV; the scanning range is 20-650 m/z, and a full-scanning working mode is adopted.
The main reaction product composition was determined by searching the NIST98 library and combining the standard mass library and the literature, and the specific composition is shown in figure 11 and the table below.
| Peak number | Time of | Component name | |
| 1 | 7.535 | Alpha- |
|
| 2 | 8.025 | 2-carene | |
| 3 | 8.530 | |
|
| 4 | 8.615 | 1,8- |
|
| 5 | 9.909 | |
|
| 6 | 11.359 | Terpinolene | |
| 7 | 17.686 | Alpha-terpineol |
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (5)
1. A method for high-selectivity catalytic synthesis of1,8-cineole is characterized by comprising the following steps:
1) desiliconizing a ZSM-5 molecular sieve, introducing NH4NO3 solution to realize ion exchange, and obtaining hierarchical pore HZSM-5;
2) the method comprises the steps of taking alpha-terpineol as a raw material, taking the prepared hierarchical pore HZSM-5 as a catalyst, and catalyzing the alpha-terpineol and a reaction solvent to isomerize under a normal-pressure heating condition to synthesize the 1, 8-cineole.
2. The method for the high-selectivity catalytic synthesis of1,8-cineole as claimed in claim 1, wherein in step 1), the ZSM-5 molecular sieve is one of industrial catalyst ZSM-5 molecular sieves with silica/alumina ratio of 38, 70, 380 and 500.
3. The method for high-selectivity catalytic synthesis of1,8-cineole as claimed in claim 2, wherein in step 1), the desiliconization treatment is carried out by alkaline hot solution etching, and the concentration is 0.1-0.5 mol/L; the solid-liquid ratio of ZSM-5 to NaOH is 1: 15-25; the reaction temperature is 70-90 ℃.
4. The method for high-selectivity catalytic synthesis of1,8-cineole as claimed in claim 1, wherein in step 1), the concentration of NH4NO3 aqueous solution in the ion exchange process is 0.5-2 mol/L; the solid-to-liquid ratio of the catalyst to the NH4NO3 aqueous solution is 1: 80-120; the stirring speed is 300 r/min-400 r/min; the heating temperature is 70-90 ℃.
5. The method for the highly selective catalytic synthesis of1,8-cineole as claimed in claim 1, wherein in step 2), the reaction solvent is one of n-hexane, cyclohexane and isopropanol; the mass ratio of the alpha-terpineol to the solvent is 1: 39, the reaction temperature is 65-75 ℃, the mass ratio of the hierarchical pore HZSM-5 catalyst to the alpha-terpineol is 0.008: 1-0.0112: 1, and the reaction time is 4-10 hours.
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