Olefin production

Abstract

This invention relates to a method for producing at least one olefin from at least one ketone, the method comprising the steps of: (a) contacting at least one gaseous ketone with at least one ketation catalyst in the presence of at least one hydrogen-releasing agent or hydrogen at a temperature of at least 350°C to produce the corresponding olefin, wherein the gas has a concentration of 1 to 1000 m 3 / (m 3 The gas hourly space velocity (GHSV) is xh, and the ketation catalyst is a metal oxide catalyst or a mixture thereof.

Description

Invention Field

[0001] This invention relates to a method for producing olefins. Specifically, the method involves producing at least one olefin from at least one ketone in the presence of at least one ketation catalyst. Background of the Invention Various methods have been explored to convert biomass into valuable chemical compounds that can serve as sustainable alternatives to petroleum. Petroleum, a primary source of chemical building blocks and transportation fuels, is dwindling and its price fluctuates. Therefore, there is a need to find alternative energy sources. One such energy source is olefins.

[0003] For example, short-chain and medium-chain alpha-olefins are used not only as biofuels but also as building blocks for polymers. Specifically, olefins are widely used in the manufacture of lubricants, polymers, and detergents.

[0004] Fatty acids are preferred starting materials for olefin production because they contain carbon in low oxidation states. Furthermore, fatty acids are generally readily available in large quantities from natural resources such as fats at low cost. However, there is always a need to find other new olefin-forming starting materials to provide alternative means of olefin production should fatty acids become too expensive or depleted.

[0005] Furthermore, current methods for producing olefins from fatty acids are essentially chemical processes, where α-olefins are formed from saturated unbranched fatty acids (≥ C11). These methods typically require expensive and / or toxic metal-based catalysts as well as high temperatures (>130°C).

[0006] Therefore, there is a need in the art for an improved and efficient method for producing olefins from alternative starting materials.

[0007] Invention Description The method according to any aspect of the invention solves the aforementioned problems by using at least one ketone as a starting material for the production of at least one corresponding olefin. Specifically, the ketone is in a gaseous state, and the method is carried out at a temperature of at least 350°C in the presence of at least one ketation catalyst and a hydrogen-releasing agent or hydrogen agent. Surprisingly, it has been found that at this temperature, the olefin is formed from the gaseous ketone. Furthermore, raising the temperature above 350°C results in a higher olefin yield and a reduction in the ketone in the reaction mixture containing the ketone and the ketation catalyst.

[0008] According to one aspect of the present invention, a method for producing at least one olefin from at least one ketone is provided, the method comprising the following steps: • In the presence of at least one hydrogen release agent or hydrogen, at a temperature of at least 350°C, at least one gaseous ketone is contacted with at least one ketation catalyst to produce the corresponding olefin.

[0009] As used herein, the term "gaseous ketone" refers to a ketone in a gaseous state. At room temperature, ketones are typically in a solid or liquid state depending on the size of the ketone molecule. For example, low molecular weight ketones such as acetone are liquids at room temperature, while higher molecular weight ketones may be solids. However, the methods according to any aspect of the invention are carried out at a temperature of at least 350°C. This high temperature is above the boiling point of most ketones; therefore, the ketones used in the methods according to any aspect of the invention are in a gaseous state.

[0010] Specifically, the method according to any aspect of the invention is carried out in a reactor, and the gas in the reactor is in a flow rate of 1 to 1000 m³. 3The gas hourly space velocity (GHSV) is the velocity of the gas moving within the reactor per hour, specifically the velocity of the gas moving above the catalyst. Specifically, the gas in the reactor is at least a ketone and / or a hydrogen-releasing agent. More specifically, the gas in the reactor is at least a ketone and hydrogen.GHSV is 2 to 1000, 3 to 1000, 4 to 1000, 5 to 1000, 10 to 1000, 15 to 1000, 20 to 1000, 25 to 1000, 30 to 1000, 35 to 1000, 40 to 1000, 45 to 1000, 50 to 1000, 55 to 1000, 60 to 1000, 65 to 1000, 70 to 1000, 75 to 1000, 80 to 1000, 85 to 1000, 90 to 1000, 95 to 1000, 100 to 1000, 5 to 900, 10 to 900, 15 to 900, 20 to 900, 25 to 900, 3 0 to 900, 35 to 900, 40 to 900, 45 to 900, 50 to 900, 55 to 900, 60 to 900, 65 to 900, 70 to 900, 75 to 900, 80 to 900, 85 to 900, 90 to 900, 95 to 900, 100 to 900, 5 to 800, 10 to 800, 15 to 800, 20 to 800, 25 to 800, 30 to 800, 35 to 800, 40 to 800, 45 to 800, 50 to 800, 55 to 800, 60 to 800, 65 to 800, 70 to 800, 75 to 800, 80 to 800, 85 to 800 0, 90 to 800, 95 to 800, 100 to 800, 5 to 700, 10 to 700, 15 to 700, 20 to 700, 25 to 700, 30 to 700, 35 to 700, 40 to 700, 45 to 700, 50 to 700, 55 to 700, 60 to 700, 65 to 700, 70 to 700, 75 to 700, 80 to 700, 85 to 700, 90 to 700, 95 to 700, 100 to 700, 5 to 600, 10 to 600, 15 to 600, 20 to 600, 25 to 600, 30 to 600, 35 to 600, 40 to 600, 45 Up to 600, 50 to 600, 55 to 600, 60 to 600, 65 to 600, 70 to 600, 75 to 600, 80 to 600, 85 to 600, 90 to 600, 95 to 600, 100 to 600, 5 to 500, 10 to 500, 15 to 500, 20 to 500, 25 to 500, 30 to 500, 35 to 500, 40 to 500, 45 to 500, 50 to 500, 55 to 500, 60 to 500, 65 to 500, 70 to 500, 75 to 500, 80 to 500, 85 to 500, 90 to 500, 95 to 500 or 100 to 500 m. 3 / (mxh). Specifically, GHSV is 5 to 500, 5 to 400, 10 to 400, 15 to 400, 20 to 400, 25 to 400, 30 to 400, 35 to 400, 40 to 400, 45 to 400, 50 to 400, 55 to 400, 60 to 400, 65 to 400, 70 to 400, 75 to 400, 80 to 400, 85 to 400, 90 to 400, 95 to 400 or 100 to 400, 5 to 300, 10 to 300, 15 to 300, 20 to 300, 25 to 300, 30 to 300, 35 to 300, 40 to 300, 45 to 300, 50 to 300, 55 to 300, 60 to 300, 65 to 300, 70 to 300, 75 to 300, 80 to 300, 85 to 300, 90 to 300, 95 to 300 or 100 to 300, 5 to 200, 10 to 200, 15 to 200, 20 to 200, 25 to 200, 30 to 200, 35 to 200, 40 to 200, 45 to 200, 50 to 200, 55 to 200, 60 to 200, 65 to 200, 70 to 200, 75 to 200, 80 to 200, 85 to 200, 90 to 200, 95 to 200 or 100 Up to 200, 5 to 150, 10 to 150, 15 to 150, 20 to 150, 25 to 150, 30 to 150, 35 to 150, 40 to 150, 45 to 150, 50 to 150, 55 to 150, 60 to 150, 65 to 150, 70 to 150, 75 to 150, 80 to 150, 85 to 150, 90 to 150, 95 to 150 or 100 to 150 m 3 / (mxh). Specifically, GHSV is 5 to 500 m. 3 / (m 3 / (mxh). More specifically, GHSV is 10 to 150 m 3 / (m 3 (xh). It is particularly advantageous when the gas in the reactor moves at this velocity, as this allows sufficient time for the ketone to contact the catalyst and convert to olefins. The GHSV of gaseous ketones can be measured using any method known in the art. Specifically, GHSV can be measured using a flow indicator, i.e., an indicator that can be used to measure the volume or mass of gas in a reactor performing the method according to any aspect of the invention.

[0011] Any ketone can be used as a starting material in the method according to any aspect of the invention. Specifically, the ketone has the structure RC(=O)-R', wherein R and R' can be various carbon-containing substituents. The ketone contains a carbonyl group -C(=O)- (which contains a carbon-oxygen double bond C=O). Specifically, the ketone may contain at least three carbon atoms. More specifically, the ketone in the method according to any aspect of the invention may be C3 to C4.31 Ketone. In one example, the ketone is at least one 6-undecane ketone, which is a dialkyl ketone having the formula (CH3(CH2)4)2CO.

[0012] The ketation catalyst used according to any aspect of the invention can be a heterogeneous catalyst. Specifically, the ketation catalyst can be any metal oxide catalyst or a mixture thereof. More specifically, the catalyst may be selected from heteropolyacids (H3PW). 12 O 40 Catalysts, including niobium oxide (Nb₂O₅) catalysts, titanium oxide (TiO₂) catalysts, cerium oxide (CeO₂) catalysts, zinc-chromium (Zn-Cr) mixed oxide catalysts, and manganese oxide (MnO₂) catalysts. x Catalysts, including lanthanum oxide (La₂O₃) catalysts, magnesium oxide (MgO) catalysts, iron oxides (FeO, FeO₂, Fe₂O₃, Fe₃O₄, Fe₄O₅, Fe₅O₆, Fe₅O₇), and silicon-aluminum (Si). y Al z O) mixed oxide catalyst, alumina (Al2O3) catalyst and zirconium oxide (ZrO2) catalyst. MnO x In this context, 'x' can be 1, 2, or 4. Si y Al z In O, 'y' and 'z' can refer to any number, where the ratio z / y is any number between 0 and 1. As demonstrated in the examples, the metal oxide ketation catalyst did not produce products with hydrogenated double bonds. Instead, surprisingly, when using these metal oxide ketation catalysts in methods according to any aspect of the invention, olefin formation due to Norrish-type cleavage was observed.

[0013] Within the knowledge of those skilled in the art, suitable conditions for using different ketation catalysts in the methods according to any aspect of the invention will be determined. Specifically, the ketation catalyst may be a zirconium oxide catalyst and may be used to convert ketones to their corresponding olefins. Specifically, the temperature must be at least 350°C to convert the ketone to its corresponding olefin. More specifically, the temperature may be maintained at about 350, 355, 360, 365, 370, 375, 380, 385, 390, 395, or 400°C during the methods according to any aspect of the invention. More specifically, the reaction temperature can be 350-420, 350-415, 350-410, 350-405, 350-400, 350-395, 350-390, 350-385, 350-380, 350-375, 350-370, 350-365, 350-360, 355-420, 355-415, 355-410, 355-405, 355-400, 355-395, 355-390, 355-385, 355-380, 355-375, 35 5-370, 355-365, 355-360, 360-420, 360-415, 360-410, 360-405, 360-400, 360-395, 360-390, 360-385, 360-380, 360-375, 360-370, 360-365, 365-420, 365-415, 365-410, 365-405, 365-400, 365-395, 365-390, 365-385, 365-380, 365-375, 36 5-370, 370-420, 370-415, 370-410, 370-405, 370-400, 370-395, 370-390, 370-385, 370-380, 370-375, 375-420, 375-415, 375-410, 375-405, 375-400, 375-395, 375-390, 375-385, 375-380, 380-420, 380-415, 380-410, 380-405, 380-400, 3 80-395, 380-390, 380-385, 385-420, 385-415, 385-410, 385-405, 385-400, 385-395, 385-390, 390-420, 390-415, 390-410, 390-405, 390-400, 390-395, 395-420, 395-415, 395-410, 395-405, 395-400, 400-420, 400-415, 400-410 or 400-405℃.More specifically, the method according to any aspect of the invention is carried out at a temperature between 350°C and 390°C. Even more specifically, a zirconium oxide catalyst is used as a ketation catalyst to produce olefins from ketones at a reaction temperature between 350°C and 390°C. The zirconium oxide catalyst is preferably prepared by granulation, having a diameter of 0.5 to 3 mm and a length of 1 to 5 mm. The surface area is between 10 and 300 m². 2 Within the range of / g.

[0014] The method according to any aspect of the invention further includes a hydrogen-releasing agent or hydrogen gas. The hydrogen-releasing agent can be any compound that provides H atoms to a ketone to produce a corresponding alcohol and thereby an olefin. Specifically, the hydrogen-releasing agent can be hydrogen gas or at least one carboxylic acid or organic acid. More specifically, the hydrogen-releasing agent is at least one alkanoic acid containing 1 to 22 carbon atoms. Therefore, the hydrogen-releasing agent can be at least one alkanoic acid containing 1 to 22 carbon atoms or hydrogen gas. Specifically, the alkanoic acid is selected from straight-chain alkanoic acids containing 4 to 18, preferably 5 to 12, carbon atoms. More specifically, the alkanoic acid is hexanoic acid.

[0015] Hydrogen-releasing agents can be supplied together with ketones.

[0016] The ketone can be any ketone having 3-31 carbon atoms. In one example, the ketone is undecanetone, and the alkene is undecene.

[0017] The method according to any aspect of the invention may include a step of further extracting the produced olefins. Any method known in the art can be used to extract the olefins. Specifically, distillation can be used to extract the olefins.

[0018] According to another aspect of the invention, a method is provided to improve the yield of at least one olefin from at least one ketone compared to the method performed at different temperatures and at different gas hourly space velocities (GHSV) in the reactor, using the method according to any aspect of the invention.

[0019] As used herein, the term "contact" refers to the direct contact between a gaseous ketone and at least one ketation catalyst according to any aspect of the invention in the medium of step (a). For example, the ketone and the ketation catalyst may be located in different compartments and combined in step (a).

[0020] According to another aspect of the invention, an olefin produced by any aspect of the invention is provided.

[0021] According to another aspect of the invention, a ketation catalyst is provided for use in the production of at least one olefin from at least one ketone. Specifically, the ketone is undecanetone, and the olefin is undecene. The ketone is a gaseous ketone and has a reaction temperature of 1 to 1000 m. 3 / (m 3The gas hourly space velocity (GHSV) is xh. Specifically, the ketation catalyst is a zirconium oxide catalyst.

[0022] Unless otherwise stated, all percentages (%) given are mass percentages.

[0023] As used in this paper, the term "about" refers to a variation within a 20% range. Specifically, as used in this paper, "about" means ±20% of a given measurement or value, more specifically ±10%, or even more specifically ±5%.

[0024] The following examples illustrate the invention and are not intended to limit the invention or its scope (which is obvious from the whole description and claims) to the embodiments specified in the examples. Example

[0025] Example 1 GHSV instance: 121 m 3 / (m 3 xh), T>350℃ The reaction was carried out in a heated continuous fluidized bed reactor. Gaseous hexanoic acid (1.2 m...) was... 3 Continuous feeding ( / h) to the container filled with zirconia on silica (95 wt%, 10.2 kg or 0.01 m) 3 The reaction was carried out in a reactor at 365 °C. The catalyst had a diameter of 1 mm and a length of 3 mm. The gaseous effluent was collected and its composition was analyzed by nuclear magnetic resonance spectroscopy (NMR). A total of 3 kg of hexanoic acid was fed into the reactor, yielding 2.3 kg of a mixture consisting of 15% undecene, 75% 6-undecane, and 10% byproducts, in addition to 0.5 kg of carbon dioxide and 0.2 kg of water. The residual amount of hexanoic acid was below the detection limit. Figure 1 and Table 1 show the reaction results before any derivatization and confirm that no undecane formation was observed. All structures were proposed from the NIST database, and the isomers were not further specified in terms of any functional group positions. Figure 2 and Table 2 show the reaction results after subsequent hydrogenation. Table 1 provides detailed information about the products in the chromatogram of Figure 1. Table 2 provides detailed information about the products in the chromatogram of Figure 2.

[0026] Example 2 GHSV instance: 117 m 3 / (m 3 xh), T<350℃ The reaction was carried out in a heated continuous fluidized bed reactor. Gaseous hexanoic acid (1.2 m...) was... 3 A continuous feed ( / h) was introduced into a reactor containing zirconia-coated silica (95 wt%, 10.15 kg) at 343 °C. The gaseous effluent was collected and its composition was analyzed by gas chromatography (GC). A total of 3 kg of hexanoic acid was fed into the reactor, yielding a mixture of 2.2 kg consisting of 99% 6-undecanetone and <1% hexanoic acid, in addition to 0.6 kg of carbon dioxide and 0.2 kg of water.

[0027] Example 3 GHSV instance: 4.6 m 3 / (m 3 xh), T<350℃ The reaction was carried out in a heated continuous fluidized bed reactor. Gaseous hexanoic acid (3.6 x 10⁻⁶) was added. -5 m 3 / h) Continuous feeding to a container filled with zirconia on silica (95 wt%, 7.9 x 10) -6 m 3 The gaseous effluent was collected and its composition was analyzed by nuclear magnetic resonance spectroscopy (NMR). A total of 89 mg of hexanoic acid was fed into the reactor, yielding a mixture of 66 mg consisting of 9% undecene, 13% 6-undecane, and 78% hexanoic acid, in addition to 17 mg of carbon dioxide and 7 mg of water.

[0028] Example 4 GHSV instance: 4.6 m 3 / (m 3 xh), T>350℃ The reaction was carried out in a heated continuous fluidized bed reactor. Gaseous hexanoic acid (3.6 x 10⁻⁶) was added. -5 m 3 / h) Continuous feeding to a container filled with zirconia on silica (95 wt%, 7.9 x 10) -6 m 3 The gaseous effluent was collected and its composition was analyzed by nuclear magnetic resonance spectroscopy (NMR). A total of 89 mg of hexanoic acid was fed into the reactor, yielding a mixture of 66 mg consisting of 20% undecene, 1% 6-undecane, and 79% hexanoic acid, in addition to 17 mg of carbon dioxide and 7 mg of water.

[0029] Example 5 GHSV instance: 4.6 x 10 4 m 3 / (m 3 xh), T>350℃ The reaction was carried out in a heated continuous fluidized bed reactor. Gaseous hexanoic acid (0.36 m³ / h) was continuously fed into a reactor packed with zirconia-coated silica (95 wt%, 7.9 x 10⁻⁶ m³ / h). -6 m 3 The mixture was fed into a reactor at 355°C. The gaseous effluent was collected and its composition was analyzed by nuclear magnetic resonance (NMR) spectroscopy. A total of 893 g of hexanoic acid was fed into the reactor, yielding a 655 g mixture consisting of 96% 6-undecanene and 4% hexanoic acid, along with 169 g of carbon dioxide and 69 g of water. The amount of undecanene was below the detection limit.

[0030] Example 6 GHSV instance: 0.3 m 3 / (m 3 xh), T>350℃ The reaction was carried out in a heated continuous fluidized bed reactor. Gaseous hexanoic acid (2.2 x 10⁻⁶) was added. -6 m 3 / h) Continuous feeding to a container filled with zirconia on silica (95 wt%, 7.9 x 10) -6 m 3 The product was fed into a reactor at 355°C. The gaseous effluent was collected after 72 hours and its composition was analyzed by gas chromatography. A total of 0.14 mg of hexanoic acid was fed into the reactor, yielding a product mixture consisting of 80% 6-undecane and 9% undecane, along with carbon dioxide and water.

Claims

1. A method for producing at least one olefin from at least one ketone, the method comprising the following steps: (a) To produce the corresponding olefin by contacting at least one gaseous ketone with at least one ketation catalyst in the presence of at least one hydrogen-releasing agent or hydrogen at a temperature of at least 350°C. The gas has a range of 1 to 1000 m 3 / (m 3 The air space velocity (GHSV) of xh) and The ketation catalyst is a metal oxide catalyst or a mixture thereof.

2. The method according to claim 1, wherein the temperature is 350°C to 390°C.

3. The method according to claim 1 or 2, wherein the metal oxide catalyst or a mixture thereof is selected from heteropolyacids (H3PW). 12 O 40 Catalysts include titanium oxide (TiO2) catalysts, cerium oxide (CeO2) catalysts, zinc-chromium (Zn-Cr) mixed oxide catalysts, manganese oxide (MnO2) catalysts, lanthanum oxide (La2O3) catalysts, magnesium oxide (MgO) catalysts, iron oxides (FeO, FeO2, Fe2O3, Fe3O4, Fe4O5, Fe5O6, Fe5O7), silicon-aluminum (Si-Al) mixed oxide catalysts, and zirconium oxide (ZrO2) catalysts.

4. The method according to any one of the preceding claims, wherein the ketation catalyst is a zirconium oxide catalyst.

5. The method according to any one of the preceding claims, wherein the hydrogen-releasing agent is an acid, preferably a carboxylic acid or an inorganic acid.

6. The method according to claim 5, wherein the acid is at least one alkanoic acid comprising 1 to 22 carbon atoms.

7. The method according to any one of claims 1 to 6, wherein in step (a), the gaseous ketone is contacted with the ketation catalyst in the presence of hydrogen.

8. The method according to claim 7, wherein at least one alkanoic acid comprising 1 to 22 carbon atoms is introduced in step (a).

9. The method according to any one of the preceding claims, wherein the alkyl acid is hexanoic acid.

10. The method according to any one of the preceding claims, wherein the ketone is undecanetone and the olefin is undecene.

11. An olefin produced by the method according to any one of claims 1 to 10.

12. Use of ketation catalysts for the production of at least one olefin from at least one ketone.

13. The use according to claim 12, wherein the ketone is undecanetone and the olefin is undecene.

14. The use according to claim 12 or 13, wherein the ketone is a gaseous ketone and has a concentration of 1 to 1000 m in the reaction. 3 / (mxh) air space velocity (GHSV).

15. The use according to any one of claims 12 to 14, wherein the ketation catalyst is a zirconium oxide catalyst.

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