CN107008499B - Combined catalyst and method capable of converting terpenoids into aromatic hydrocarbons - Google Patents
Combined catalyst and method capable of converting terpenoids into aromatic hydrocarbons Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/36—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of vanadium, niobium or tantalum
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
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- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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- C—CHEMISTRY; METALLURGY
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- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/247—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by splitting of cyclic ethers
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- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/367—Formation of an aromatic six-membered ring from an existing six-membered ring, e.g. dehydrogenation of ethylcyclohexane to ethylbenzene
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Abstract
The invention provides a combined catalyst and a method for converting terpenoids into aromatic hydrocarbons. The combined catalyst capable of converting terpenoids into aromatic hydrocarbons is characterized by comprising at least one of super acid and heteropoly acid. The combined catalyst is easier to prepare and lower in cost, when the catalyst is used, the reaction condition is milder, the conversion rate and the selectivity are higher, and the defects that the existing reaction efficiency for converting terpenoids into aromatic hydrocarbons is low, the catalyst is expensive, the reaction condition is harsh and the like can be overcome, so that a green, cheap and efficient way is provided for converting terpenoids into aromatic hydrocarbons.
Description
Technical Field
The invention relates to a combined catalyst and a method for converting terpenoids into aromatic hydrocarbons.
Background
Aromatic hydrocarbons are important raw materials of organic chemical industry and mainly come from non-renewable resources such as coal, tar and petroleum. The search for producing aromatic hydrocarbons from renewable resources is very necessary for energy conservation, emission reduction and reduction of dependence of industries on petroleum resources. The terpenoid is an important renewable biomass resource, and is widely distributed in nature, and has various structures and abundant reserves. The renewable terpenoid is converted into aromatic hydrocarbon through reactions such as catalytic reforming, oxidation and the like, and the method is a new way for biomass conversion.
As early as 1938, Palmer et al used Cu-Ni alloy as a reforming catalyst to disproportionate monocyclic terpenes into p-cymene and p-menthane at 190 ℃ at 170 ℃ and separated by distillation (U.S. Pat. No. 2211432). Since then, most of the related researches use transition or its compounds as catalysts, and the reaction conditions are all relatively harsh. For example, Leita et Al used a support for γ -Al in 20102O3Pd catalyst of (2) in O2Ar mixed gas is used for converting the eucalyptol into p-cymene at the temperature of 250-350 ℃ (WO2011/006183), but the raw materials for preparing the catalyst are expensive, and the catalytic reaction conditions are harsh.
Therefore, the existing terpenoid substance has limited ways of converting into aromatic hydrocarbon, the needed catalyst is expensive, the reaction conditions are harsh, and the improvement space is large.
Disclosure of Invention
The present invention has an object to provide a catalyst capable of converting terpenoids into aromatic hydrocarbons under mild conditions and to provide a method for converting terpenoids into aromatic hydrocarbons using the catalyst.
In order to achieve the above object, the present invention provides a composite catalyst capable of converting terpenoids into aromatic hydrocarbons, characterized by comprising at least one of a super acid and a heteropoly acid.
Preferably, the super acid is trifluoromethanesulfonic acid (CF)3SO3H, or HOTf) or bis (trifluoromethanesulfonyl) imide [ (CF)3SO2)2NH, or Tf2NH]。
Preferably, the heteropoly acid contains at least two of phosphorus, vanadium, molybdenum and tungsten.
Preferably, the heteropoly acid is H4[PMo11VO40]、H5[PMo10V2O40]Or H6[PMo9V3O40]。
More preferably, the heteropoly acid is H4[PMo11VO40]。
Preferably, the molar ratio of the super acid to the multi-element heteropoly acid is 0-25: 1.
The invention also provides a method for converting terpenoids into aromatic hydrocarbons, which is characterized by comprising the following steps: adding reaction substrate terpenoid, the catalyst and the solvent into a reaction vessel, introducing oxygen as an oxidant, and converting the terpenoid into aromatic hydrocarbon at the temperature of 50-80 ℃.
Preferably, the molar ratio of the terpenoid to the super acid is 100: 0-15.
Preferably, the reaction vessel is also added with additives.
Preferably, an additive which is tetraethylene glycol dimethyl ether is further added into the reaction vessel, and the molar ratio of the terpenoid to the tetraethylene glycol dimethyl ether is 100: 0-15.
Preferably, the terpenoid is eucalyptol, 1, 4-cineole, terpineol, terpene-4-ol, gamma-terpinene, terpinolene or limonene.
Preferably, the aromatic hydrocarbon is p-cymene.
Preferably, the solvent is 1, 2-dichloroethane or diethyl carbonate.
Compared with the prior art, the invention has the beneficial effects that:
the combined catalyst is easier to prepare and lower in cost, when the catalyst is used, the reaction condition is milder, the conversion rate and the selectivity are higher, and the defects that the existing reaction efficiency for converting terpenoids into aromatic hydrocarbons is low, the catalyst is expensive, the reaction condition is harsh and the like can be overcome, so that a green, cheap and efficient way is provided for converting terpenoids into aromatic hydrocarbons.
Drawings
FIG. 1 is a nuclear magnetic spectrum of the initial mixture liquid for the reaction in example 1;
FIG. 2 is a nuclear magnetic spectrum of a reaction mixture in example 1 after 6 hours of reaction;
FIG. 3 is a diagram showing the structure of the substrate in examples 1 to 38.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes and modifications of the present invention may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are also within the scope of the present invention as defined in the appended claims.
Examples 1-30 the optimal reaction conditions were screened using eucalyptol as the substrate for the template reaction. Examples 31-37 were subjected to substrate development. In all reactions of examples 1 to 30, the nuclear magnetic yields were determined by measuring with an oxygen balloon as an oxygen source and 1, 1, 2, 2-tetrachloroethane as an internal standard, the amounts of the reaction substrates were 2.5mmol, and the reaction times were 6 hours. The mole percentages of each example are based on the reaction substrate.
Examples 1 to 3
A method for converting terpenoids into aromatic hydrocarbons comprises the following specific steps: a mixture (as an oxidative dehydrogenation reaction catalyst) of reaction substrates eucalyptol, a super acid HOTf and a heteropoly acid shown in the table 1, an additive and a solvent are added into a flask, oxygen is introduced as an oxidant, the oxygen flow is 1.0mL/min, and the reaction substrates eucalyptol is converted into aromatic hydrocarbon p-cymene under the condition that the temperature is constantly 70 ℃. Wherein, the usage amount of HOTf is 5 mol%, the usage amount of the heteropoly acid is 1 mol%, the additive is tetraethylene glycol dimethyl ether, the usage amount is 3 mol%, the solvent is 5mL of 1, 2-dichloroethane, and the reaction time is 6 hours.
The product was analyzed by a 500MHz liquid nmr spectrometer.
Nuclear magnetic spectrum of raw material eucalyptol:1H NMR(500MHz，CDCl3) δ 2.06-1.98(m, 2H), 1.69-1.63(m, 2H), 1.54-1.45(m, 4H), 1.41(d, J ═ 1.1Hz, 1H), 1.24(s, 6H), 1.05(s, 3H). Nuclear magnetic spectrum of product p-cymene:1H NMR(500MHz，CDCl3)δ7.14-7.09(m，4H)，2.87(dt，J＝13.8，6.9Hz，1H)，2.32(s，3H)，1.23(d, J ═ 6.9Hz, 6H). Nuclear magnetic spectrum of internal standard 1, 1, 2, 2-tetrachloroethane:1H NMR(500MHz，CDCl3)δ5.96(s，2H)。
table 1: experimental parameters for the variation of the composition of heteropolyacids
| Examples | Heteropolyacid catalyst (1 mol%) | P-cymene (%) |
| 1 | H4[PMo11VO40] | 79 |
| 2 | H5[PMo10V2O40] | 66 |
| 3 | H6[PMo9V3O40] | 59 |
For examples 1-3, H is given4[PMo11VO40]The heteropolyacid catalyst has the best catalytic activity.
An example of a liquid nmr calculation of the product p-cymene:
before the reaction was heated, a sample of the initial mixture of the reaction system was subjected to nuclear magnetic analysis (nuclear magnetic spectrum is shown in FIG. 1). After 6 hours of reaction, the reaction mixture was again subjected to nuclear magnetic assay (nuclear magnetic spectrum shown in FIG. 2). The content of eucalyptol can be determined from the methyl signal on eucalyptol in figure 1, based on the internal standard 1, 1, 2, 2-tetrachloroethane, while the exact amount of product can be determined from the methine hydrogen signal on p-cymene in figure 2. From this, the yield of p-cymene at 6 hours of reaction was calculated as:
0.96÷(3.64÷3)×100％＝79％。
examples 4 to 12
Analogously to example 1, the difference is that HOTf and H4[PMo11VO40]The ratio of the heteropoly acid catalyst to tetraethylene glycol dimethyl ether was varied, and is specifically shown in table 2. Under the condition of temperature and solvent fixation, on HOTf and H4[PMo11VO40]The change in the ratio of the heteropolyacid catalyst caused the change in the product yield was investigated.
Table 2: experimental parameters for the ratio change of two catalysts
The optimum catalysts H are given in examples 1 to 124[PMo11VO40]And under the common catalysis of the HOTf, the optimum proportion of the product can be obtained economically and efficiently.
Examples 13 to 16
Analogously to example 1, the difference is the reaction temperature, as shown in Table 3. Temperature as a one-factor variable at 5 mol% HOTf and 0.5 mol% H4[PMo11VO40]The catalyst ratio of (2) was investigated.
Table 3: experimental parameters of temperature variation
| Examples | Temperature (. degree.C.) | P-cymene (%) |
| 13 | 50 | 3 |
| 14 | 60 | 44 |
| 15 | 70 | 78 |
| 16 | 80 | 50 |
Examples 17 to 30
Similar to example 1, except the solvent was different, as shown in table 4. The solvent type is used as a single variable, and a proper reaction solvent is screened.
Table 4: experimental parameters of solvent species variation
From the above examples 17-30, the screening of the solvent gave the best product yields with 1, 2-dichloroethane and diethyl carbonate as solvent. In examples 27 and 28, the yield was significantly better than the additive-containing reaction without the additive tetraglyme. Compared with two solvents, diethyl carbonate is weak in toxicity, environment-friendly, considered as a green solvent and good in reaction performance, so that diethyl carbonate is used as the solvent to research more terpenoids at the temperature of 70 ℃.
Example 31
Conversion of eucalyptol to p-cymene
22.275g H were added sequentially to a 10L flask4[PMo11VO40]Heteropolyacid (0.0125 mol), 3L diethyl carbonate, 11mL trifluoromethanesulfonic acid (0.125 mol) and 418mL eucalyptol (2.5 mol), introducing oxygen as an oxidant, wherein the oxygen flow is 0.78L/min, stirring at 70 ℃ for 6 hours, converting the eucalyptol into p-cymene, and carrying out reduced pressure distillation and separation to obtain a product. The isolated product had a mass of 232.3g and a yield of 69%.
Example 32
Conversion of 1, 4-cineole to p-cymene:
22.275g H were added sequentially to a 10L flask4[PMo11VO40]Heteropolyacid (0.0125 mol), 3L diethyl carbonate, 11mL trifluoromethanesulfonic acid (0.125 mol) and 435mL 1, 4-cineole (2.5 mol), oxygen is introduced as an oxidant, the oxygen flow is 0.78L/min, the mixture is stirred for 6 hours at 70 ℃, the 1, 4-cineole is converted into p-cymene, and the product is obtained by reduced pressure distillation and separation. The isolated product had a mass of 279.5g and a yield of 83%.
Example 33
Terpineol conversion to p-cymene:
22.275g H were added sequentially to a 10L flask4[PMo11VO40]Heteropolyacid (0.0125 mol), 3L diethyl carbonate, 11mL trifluoromethanesulfonic acid (0.125 mol) and 412mL terpineol (2.5 mol), oxygen is introduced as an oxidant, the oxygen flow is (0.78L/min), stirring is carried out at 70 ℃ for 6 hours, the terpineol is converted into p-cymene, and the product is obtained by reduced pressure distillation and separation. The isolated product had a mass of 242.6g and a yield of 72%.
Example 34
Conversion of terpene-4-ol to p-cymene:
22.275g H were added sequentially to a 10L flask4[PMo11VO40]Heteropolyacid (0.0125 mol), 3L diethyl carbonate, 11mL trifluoromethanesulfonic acid (0.125 mol), 415mL terpene-4-ol (2.5 mol), oxygen as an oxidizing agent was introduced at an oxygen flow rate of (0.78L/min), stirring was carried out at 70 ℃ for 6 hours to convert terpene-4-ol into paraumbellic acidAnd (5) distilling and separating the flower hydrocarbon under reduced pressure to obtain a product. The isolated product had a mass of 241.9g and a yield of 72%.
Example 35
Conversion of gamma-terpinene to p-cymene:
22.275g H were added sequentially to a 10L flask4[PMo11VO40]Heteropolyacid (0.0125 mol), 3L diethyl carbonate and 401mL gamma-terpinene (2.5 mol), introducing oxygen as an oxidant, wherein the oxygen flow is 0.78L/min, stirring for 6 hours at 70 ℃, converting the gamma-terpinene into p-cymene, and carrying out reduced pressure distillation and separation to obtain the product. The isolated product had a mass of 292.4g and a yield of 87%.
Example 36
Terpinolene is converted to p-cymene:
22.275g H were added sequentially to a 10L flask4[PMo11VO40]Heteropolyacid (0.0125 mol), 3L diethyl carbonate and 396mL terpinolene (2.5 mol), oxygen is introduced as an oxidant, the flow rate of the oxygen is (0.78L/min), the mixture is stirred for 6 hours at 70 ℃, the terpinolene is converted into p-cymene, and the product is obtained by reduced pressure distillation and separation. The isolated product had a mass of 238.2g and a yield of 71%.
Example 37
Conversion of limonene to p-cymene:
22.275g H were added sequentially to a 10L flask4[PMo11VO40]Heteropolyacid (0.0125 mol), 3L diethyl carbonate and 404mL limonene (2.5 mol), introducing oxygen as an oxidant, wherein the oxygen flow is 0.78L/min, stirring at 70 ℃ for 6 hours, converting the limonene into p-cymene, and carrying out reduced pressure distillation and separation to obtain a product. The isolated product had a mass of 265.1g and a yield of 79%.
Example 38
Conversion of eucalyptol to p-cymene
22.275g H were added sequentially to a 10L flask4[PMo11VO40]Heteropolyacid (0.0125 mol), 3L diethyl carbonate, 35.1g bistrifluoromethanesulfonylimide (0.125 mol), 418mL eucalyptol (2.5 mol), oxygen was introduced as the oxidant at a flow rate of (0.78)L/min), stirring for 6 hours at 70 ℃, converting the eucalyptol into p-cymene, and carrying out reduced pressure distillation and separation to obtain a product. The isolated product had a mass of 245.0g and a yield of 73%.
The substrates of examples 1-38 are shown in FIG. 3.
Claims (6)
1. A combined catalyst for converting terpenoid into aromatic hydrocarbon is characterized by comprising super acid and multi-heteropoly acid, wherein the super acid is trifluoromethanesulfonic acid or bis-trifluoromethanesulfonimide, and the multi-heteropoly acid is H4[PMo11VO40]、H5[PMo10V2O40]Or H6[PMo9V3O40]。
2. A combination catalyst as claimed in claim 1, wherein the heteropolyacid comprises at least two of phosphorus, vanadium, molybdenum and tungsten.
3. The composite catalyst for converting terpenoids into aromatic hydrocarbons according to claim 1, wherein the molar ratio of super acid to heteropoly acid is 0-25: 1, not including 0.
4. A method for converting terpenoids to aromatic hydrocarbons, comprising: charging a reaction substrate terpenoid, the catalyst of any one of claims 1 to 3 and a solvent into a reaction vessel, and introducing oxygen as an oxidizing agent to convert the terpenoid into aromatic hydrocarbons at a temperature of 50 to 80 ℃.
5. The method of converting terpenoids to aromatic hydrocarbons according to claim 4, wherein the molar ratio of terpenoids to super acid is 100: 0 to 15.
6. The method of converting a terpenoid to an aromatic hydrocarbon according to claim 4, wherein said terpenoid is eucalyptol, 1, 4-cineole, terpineol, terpene-4-ol, γ -terpinene, terpinolene or limonene.
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