Regenerated deoxidation catalyst as well as preparation method and application thereof

Abstract

The invention relates to the technical field of organic gas deoxidation, and discloses a regenerated deoxidation catalyst as well as a preparation method and application thereof. The catalyst contains an active noble metal component, an active auxiliary agent component and a carrier, and based on the total weight of the catalyst, the content of the active noble metal component is 0.1-3 wt%, and the content of the carrier is 90-99.9 wt%; wherein the particle size of the active noble metal component is 1-8 nm; wherein the specific surface area of the catalyst is 20-300 m < 2 > / g, the pore volume is 0.1-0.35 cm < 3 > / g, and the average pore size is 7-20 nm. The method specifically comprises the following steps: S1, roasting a deactivated catalyst, then mixing a roasted product, an acidic solution and a dissolving aid, and carrying out solid-liquid separation to obtain a liquid-phase product; and S2, mixing the liquid-phase product with a catalyst auxiliary agent and a carrier, and roasting. The noble metal component of the regenerated deoxidation catalyst has high dispersity, and the activity can be fully recovered.

Description

Technical Field

[0001] The invention relates to the technical field of organic gas deoxidation, and in particular to a regenerative deoxidation catalyst and a preparation method and application thereof. Background Art

[0002] Contemporary chemical processes involve many chemical reaction processes, using oxidants to oxidize specific materials to produce substances that meet people's living needs. Due to incomplete reactions or side reactions, organic mixed gases containing a certain oxygen concentration are often produced, and this tail gas is difficult to dispose of. SH 3009-2013 "Petrochemical Combustible Gas Emission System Design Specification" stipulates that combustible gases with an oxygen content greater than 2% (v%) should not be discharged into the combustible gas emission system of the entire plant. Therefore, the safe disposal of this tail gas has become a common concern of scientific researchers. Among them, catalytic deoxygenation is considered to be a deoxygenation method that is simple to operate, effective, and can deoxygenate continuously.

[0003] The design and screening of catalysts in catalytic deoxygenation technology is a key step in this method. The performance, preparation method and price of the catalyst directly affect the application prospects of catalytic deoxygenation technology. Precious metal deoxygenation catalysts have better reaction performance in catalytic reactions due to the unfilled d orbitals of precious metals. However, precious metals are particularly expensive, and during use, sintering will occur at high temperatures, resulting in a decrease in the activity of the catalyst, requiring the replacement of new catalysts, which increases the cost of the precious metal deoxygenation method.

[0004] Patent application CN105689014A discloses a method for regenerating a precious metal dehydrogenation catalyst, which includes two steps: co-treatment of hydrogen and a hydrogen supply solvent and alkali metal supplementation of the catalyst. This method can achieve sustained catalyst activity, but the operating temperature and pressure are relatively high.

[0005] Patent CN85100109B discloses a method for recovering platinum from waste catalysts by extraction, a process flow for treating waste platinum catalysts mainly by extraction, the extractant used is di(2-ethylhexyl) sulfoxide, and the recovery rate of platinum is >99%. The process includes burning to remove carbon deposits, dissolving with hydrochloric acid, extracting platinum, washing, stripping, and reducing platinum with hydrazine hydrate.

[0006] The deactivated catalyst regeneration methods currently prepared have many problems such as poor regeneration effect, high regeneration energy consumption, and certain solid waste generation, which have certain limitations in the actual industrial application of catalysts. Therefore, it is of great significance to develop a simple, easy-to-operate catalyst regeneration and activation method with practical industrial application prospects. Summary of the invention

[0007] The purpose of the present invention is to overcome the problem in the prior art that the activity of precious metal deoxidation catalysts is difficult to recover through sintering, and to provide a regenerated deoxidation catalyst and a preparation method and application thereof. The precious metal component of the regenerated deoxidation catalyst has a high dispersion and the activity can be fully recovered.

[0008] In order to achieve the above object, the present invention provides a regenerative deoxidation catalyst, which comprises an active precious metal component, an active auxiliary component and a carrier, wherein, based on the total weight of the catalyst, the content of the active precious metal component is 0.1-3% by weight, and the content of the carrier is 90-99.9% by weight; wherein the particle size of the active precious metal component is 1-8 nm; wherein the specific surface area of ​​the catalyst is 20-300 m 2 / g, pore volume is 0.1-0.35cm 3 / g, and the average pore size is 7-20nm.

[0009] Preferably, the active precious metal component is selected from one or more of platinum, palladium, ruthenium, rhodium, gold and silver.

[0010] Preferably, the content of the active auxiliary component is 0-7% by weight.

[0011] Preferably, the co-agent component is selected from alkali metal oxides.

[0012] More preferably, the alkali metal oxide is selected from one or more of lithium oxide, sodium oxide and potassium oxide.

[0013] Preferably, the carrier is selected from one or more of alumina, titania, silica and ceria.

[0014] A second aspect of the present invention provides a method for preparing a regenerated deoxygenation catalyst, the method comprising the following steps:

[0015] S1, calcining the deactivated catalyst, then mixing the calcined product, the acidic solution and the dissolution aid, and obtaining a liquid product after solid-liquid separation;

[0016] S2, mixing the liquid phase product with a catalyst promoter and a carrier, and calcining.

[0017] Preferably, the deactivated catalyst contains carbon deposits, active precious metal components and a carrier.

[0018] Preferably, the carbon deposit content is 1-10 wt % based on the total weight of the deactivated catalyst.

[0019] Preferably, in the deactivated catalyst, based on the total weight of the active precious metal component and the carrier, the content of the active precious metal component is 0.1-3 wt %; and the content of the carrier is 90-99.9 wt %.

[0020] Preferably, the particle size of the active precious metal component in the deactivated catalyst is 3-15 nm.

[0021] Preferably, the active precious metal component in the deactivated catalyst is selected from one or more of platinum, palladium, ruthenium, rhodium, gold and silver.

[0022] Preferably, the carrier in the deactivated catalyst is selected from one or more of alumina, titania, silicon oxide and ceria.

[0023] Preferably, the deactivated catalyst is obtained by deactivating a fresh deoxygenation catalyst through a deoxygenation reaction.

[0024] Preferably, the fresh deoxygenation catalyst contains an active precious metal component and a carrier.

[0025] Preferably, based on the total weight of the fresh catalyst, the content of the active precious metal component is 0.1-3 wt %; and the content of the carrier is 90-99.9 wt %.

[0026] Preferably, the deoxygenation reaction is a reaction between an organic hydrocarbon and oxygen.

[0027] Preferably, the conditions for the deoxygenation reaction include: a temperature of 200-300°C, preferably 230-280°C; a volume space velocity of 1000-5000h -1 , preferably 1500-3500h -1 ; The pressure is 0.1-0.7MPa.

[0028] Preferably, in step S1, the calcination atmosphere is an air atmosphere; the calcination conditions include: a temperature of 300-900°C, preferably 400-800°C; and a time of 2-10 hours, preferably 3-5 hours.

[0029] Preferably, in step S1, the ratio of the calcined product, the acidic solution and the dissolution aid is 1 g: 1-5 mL: 0.01-0.5 g.

[0030] Preferably, the acidic solution is selected from one or more of nitric acid, oxalic acid, hydrochloric acid and sulfuric acid.

[0031] Preferably, the concentration of the acidic solution is 0.05-0.5 mol / L.

[0032] Preferably, the dissolution aid is an organic salt.

[0033] More preferably, the organic salt is selected from one or more of disodium ethylenediaminetetraacetic acid, oxalate and acetate.

[0034] Preferably, the weight ratio of the catalyst promoter, the carrier and the deactivated catalyst used in step S1 is 0.008-0.08:1:0.8-1.5.

[0035] Preferably, in step S2, the catalyst promoter is an alkali metal salt.

[0036] More preferably, the alkali metal salt is selected from one or more of lithium salt, sodium salt and potassium salt.

[0037] Preferably, the carrier is selected from one or more of alumina, titania, silica and ceria.

[0038] Preferably, in step S2, the calcination conditions include: temperature of 300-600°C and time of 1-5h.

[0039] The third aspect of the present invention provides a regenerated deoxygenation catalyst prepared by the method described above.

[0040] A fourth aspect of the present invention provides use of the above-mentioned regenerated deoxygenation catalyst in the reaction of organic hydrocarbons and oxygen.

[0041] Through the above technical solution, the beneficial effects of the present invention are mainly:

[0042] (1) The regenerated deoxygenation catalyst prepared by the present invention contains both an active precious metal component and an active auxiliary component. The particle size of the active precious metal component is controlled within a specific range. Moreover, the catalyst has a specific specific surface area and pore size. The catalyst having such specific properties has a higher catalytic activity in the deoxygenation reaction and a higher deoxygenation rate.

[0043] (2) The present invention calcines the deactivated catalyst to remove carbon deposits on the surface, uses an acidic solution to dissolve the active precious metal components, and adds a dissolving aid while using the acidic solution to stabilize the active precious metal components, so that the aggregated precious metal components can be rapidly dissolved at a lower acidity and lower temperature, thereby reducing material consumption and energy consumption and improving overall efficiency. The stabilized active precious metal components are less blocked by functional groups such as hydroxyl groups in the carrier and can be quickly dispersed in the carrier, which is conducive to obtaining a regenerated deoxygenation catalyst with a high degree of precious metal dispersion, whose activity can be fully restored and has a high stability. The preparation method of the regenerated deoxygenation catalyst described in the present invention is simple to operate, has strong operability, and is more conducive to industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 is the X-ray diffraction (XRD) pattern of the material prepared in Example 1.

[0045] Figure 2 is a scanning electron microscope (SEM) image of the material prepared in Example 1. DETAILED DESCRIPTION

[0046] The specific embodiments of the present invention are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention.

[0047] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0048] The present invention provides a regenerative deoxidation catalyst, which comprises an active precious metal component, an active auxiliary component and a carrier, wherein, based on the total weight of the catalyst, the content of the active precious metal component is 0.1-3% by weight, and the content of the carrier is 90-99.9% by weight; wherein the particle size of the active precious metal component is 1-8 nm; wherein the specific surface area of ​​the catalyst is 20-300 m 2 / g, pore volume is 0.1-0.35cm 3 / g, and the average pore size is 7-20nm.

[0049] In the regenerated deoxygenation catalyst of the present invention, the catalyst may also contain a small amount of carbon deposits. Specifically, based on the total weight of the catalyst, the content of the carbon deposits is ≤0.5% by weight.

[0050] In the present invention, in a specific embodiment, the active precious metal component is selected from one or more of platinum, palladium, ruthenium, rhodium, gold and silver.

[0051] In the present invention, the content of the active auxiliary component is 0-7% by weight, and the active auxiliary component is selected from alkali metal oxides. In a preferred embodiment, the alkali metal oxide is selected from one or more of lithium oxide, sodium oxide and potassium oxide.

[0052] In the present invention, in a specific embodiment, the carrier is selected from one or more of alumina, titania, silicon oxide and ceria. In a preferred embodiment, the carrier is selected from alumina.

[0053] A second aspect of the present invention provides a method for preparing a regenerated deoxygenation catalyst, the method comprising the following steps:

[0054] S1, calcining the deactivated catalyst, then mixing the calcined product, the acidic solution and the dissolution aid, and obtaining a liquid product after solid-liquid separation;

[0055] S2, mixing the liquid phase product with a catalyst promoter and a carrier, and calcining.

[0056] In the method described in the present invention, in a specific embodiment, the active precious metal components are dissolved slowly by an acidic solution. The addition of a dissolution aid while using the acidic solution can change the existence state of the metal atoms in the solution. Specifically, the presence of the dissolution aid is beneficial to the conversion of the precious metal components from a compound state to an ionic state and maintaining a high degree of ionic state, thereby stabilizing the active precious metal components. On the one hand, the aggregated precious metal species can be rapidly dissolved at lower acidity and lower temperature, thereby reducing material consumption and energy consumption and improving overall efficiency. On the other hand, in the subsequent preparation process, the stabilized active precious metal components are less blocked by functional groups such as hydroxyl groups in the carrier and can be quickly dispersed in the carrier, thereby facilitating the acquisition of a regenerated deoxygenation catalyst with a high degree of precious metal dispersion. Highly dispersed active precious metals help to improve the stability of the catalyst.

[0057] In the method of the present invention, the deactivated catalyst contains carbon deposits, active precious metal components and a carrier.

[0058] In the present invention, the carbon deposit content in the deactivated catalyst is relatively high. In a specific embodiment, the carbon deposit content is 1-10% by weight based on the total weight of the deactivated catalyst.

[0059] In the method of the present invention, in the deactivated catalyst, based on the total weight of the active precious metal component and the carrier, the content of the active precious metal component is 0.1-3 wt %; the content of the carrier is 90-99.9 wt %.

[0060] In the present invention, in a preferred embodiment, the particle size of the active precious metal component in the deactivated catalyst is 3-15 nm.

[0061] In the method described in the present invention, the active precious metal component in the deactivated catalyst is selected from one or more of platinum, palladium, ruthenium, rhodium, gold and silver.

[0062] In the present invention, in a specific embodiment, the carrier in the deactivated catalyst is selected from one or more of alumina, titania, ceria and silica. In a preferred embodiment, the carrier is selected from alumina.

[0063] In the method of the present invention, in a specific embodiment, the deactivated catalyst is obtained by deactivating a fresh deoxygenation catalyst by deoxygenation reaction. In the present invention, the fresh deoxygenation catalyst refers to a catalyst that has not been used after preparation; the fresh deoxygenation catalyst contains an active precious metal component and a carrier.

[0064] In the method described in the present invention, in a specific embodiment, based on the total weight of the fresh catalyst, the content of the active precious metal component is 0.1-3 wt %; the content of the carrier is 90-99.9 wt %.

[0065] In the present invention, the deoxygenation reaction can be a reaction between organic hydrocarbons and oxygen. When performing the deoxygenation reaction, in a preferred embodiment, the conditions of the deoxygenation reaction include: a temperature of 200-300°C, preferably 230-280°C; a volume space velocity of 1000-5000h -1 , preferably 1500-3500h -1 ; The pressure is 0.1-0.7 MPa, and the performance evaluation of the catalyst is continued until the deoxygenation rate of the catalyst is reduced to 80% of the fresh catalyst.

[0066] In the method of the present invention, in a specific embodiment, in step S1, the calcination atmosphere is an air atmosphere; the calcination conditions include: a temperature of 300-900°C, preferably 400-800°C; and a time of 2-10h, preferably 3-5h.

[0067] In the method of the present invention, in a specific embodiment, in step S1, the amount ratio of the calcined product, the acidic solution and the dissolution aid is 1 g: 1-5 mL: 0.01-0.5 g.

[0068] In the present invention, the acidic solution can be a conventional choice of those skilled in the art. In a specific embodiment, the acidic solution is selected from one or more of nitric acid, oxalic acid, hydrochloric acid and sulfuric acid; and the concentration of the acidic solution is 0.05-0.5 mol / L.

[0069] In the method of the present invention, the dissolution aid is an organic salt. In a preferred embodiment, the organic salt is selected from one or more of disodium ethylenediaminetetraacetic acid, oxalate and acetate.

[0070] In the method of the present invention, in step S1, the mixing method can be heating and stirring to dissolve, the heating temperature can be 25° C.-60° C.; the stirring time can be 1-5 hours.

[0071] In the method described in the present invention, the mixing in step S2 specifically includes: first, mixing the liquid phase product described in step S1 with the catalyst promoter, and the mixing conditions include: temperature of 25°C-110°C, time of 0.5-2h, and then adding the carrier to the mixed liquid obtained after mixing, immersing at room temperature for 3-6h, and then drying, and the drying temperature is 40°C-110°C.

[0072] In the method described in the present invention, the weight ratio of the catalyst promoter, the carrier and the deactivated catalyst used in step S1 is 0.008-0.08:1:0.8-1.5.

[0073] In the method described in the present invention, the catalyst promoter is an alkali metal salt, which can improve the electron migration performance of the catalyst and enhance the reaction performance of the catalyst after regeneration. In a preferred embodiment, the alkali metal salt is selected from one or more of lithium salts, sodium salts, and potassium salts.

[0074] In the method of the present invention, in a specific embodiment, the carrier is selected from one or more of aluminum oxide, titanium dioxide, silicon oxide and ceria.

[0075] In a preferred embodiment, in step S2, the calcination conditions include: a temperature of 300-600° C. and a time of 1-5 h.

[0076] The third aspect of the present invention provides a regenerated deoxygenation catalyst prepared by the method described above. The catalyst contains an active precious metal component, an active auxiliary component and a carrier, wherein, based on the total weight of the catalyst, the content of the active precious metal component is 0.1-3% by weight, and the content of the carrier is 90-99.9% by weight; wherein the particle size of the active precious metal component is 1-8 nm; wherein the specific surface area of ​​the catalyst is 20-300 m 2 / g, pore volume is 0.1-0.35cm 3 / g, and the average pore size is 7-20nm.

[0077] A fourth aspect of the present invention provides use of the above-mentioned regenerated deoxygenation catalyst in the reaction of organic hydrocarbons and oxygen.

[0078] The present invention will be described in detail below by way of examples. Unless otherwise specified, all methods are conventional in the art. The experimental materials used in the following examples, unless otherwise specified, can be purchased from reagent suppliers.

[0079] In the present invention, the test calculation method of the deoxidation rate n is: n = (1-a1 / a0) * 100%,

[0080] Wherein, a1 is the residual oxygen concentration of the gas after deoxygenation, and a0 is the oxygen concentration of the starting raw gas.

[0081] Example 1

[0082] (1) Composition of the fresh deoxygenation catalyst: the active precious metal component is palladium, and the carrier is alumina; the content of the active precious metal component is 1.5% by weight.

[0083] (2) Deoxygenation test of fresh deoxygenation catalyst:

[0084] The fresh deoxygenation catalyst is subjected to a deoxygenation reaction, including: using propylene gas containing 3 volume % O2 as a raw material, and conducting a deoxygenation reaction in a fixed bed catalytic reaction evaluation device, the reaction temperature is 260°C, the volume space velocity is 3000h -1 The pressure was 0.5 MPa, and the catalyst evaluation was continued until the catalyst deoxygenation rate was reduced to 80% of the fresh catalyst. The deoxygenation rate of the fresh deoxygenated catalyst was tested, and the results are shown in Table 3.

[0085] The composition of the deactivated catalyst is: the active precious metal component is palladium, and the carrier is alumina; the carbon deposit content is 5.6% by weight, and based on the total weight of the active precious metal component and the carrier, the content of the active precious metal component is 1.5% by weight.

[0086] (3) Regeneration of deactivated deoxygenation catalyst, including:

[0087] S1. Weigh 100 g of the sintered deactivated catalyst, calcine it at 500 ° C for 5 h in an air atmosphere, and then immerse the calcined product in 200 mL of 0.2 mol / L nitric acid solution, stir it at 50 ° C for 2 h, then add 10 g of disodium ethylenediaminetetraacetic acid, stir it for 1 h, and then perform solid-liquid separation, take out the supernatant, and then adjust the pH value to 7 with acetic acid to obtain a liquid product;

[0088] S2. Add 1 g of sodium nitrate to the liquid product obtained in step S1, stir and dissolve at 50° C. for 1 h, then add 99 g of alumina, soak at room temperature (25° C.) for 5 h, then dry at 50° C., and finally calcine at 500° C. for 3 h to obtain a regenerated deoxygenation catalyst.

[0089] The deoxygenation reaction of the regenerated deoxygenation catalyst was carried out under the same test conditions as the deoxygenation test of the fresh deoxygenation catalyst. The results are shown in Table 3.

[0090] The composition of the regenerated deoxygenation catalyst is: the active precious metal component is palladium, the carrier is aluminum oxide, and the active auxiliary component is sodium oxide; based on the total weight of the catalyst, the carbon deposit content is 0.1 weight%, the content of the active precious metal component is 1.11 weight%, the content of the active auxiliary component is 0.79 weight%, and the content of the carrier is 98 weight%.

[0091] Example 2

[0092] (1) Composition of the fresh deoxygenation catalyst: the active precious metal component is palladium, and the carrier is alumina; the content of the active precious metal component is 1% by weight.

[0093] (2) Deoxygenation test of fresh deoxygenation catalyst:

[0094] The fresh deoxygenation catalyst is subjected to a deoxygenation reaction, comprising:

[0095] The fresh deoxygenation catalyst is subjected to a deoxygenation reaction, including: using propylene gas containing 3 volume % O2 as a raw material, and conducting a deoxygenation reaction in a fixed bed catalytic reaction evaluation device, the reaction temperature is 260°C, the volume space velocity is 3000h -1 The pressure was 0.5 MPa, and the catalyst evaluation was continued until the catalyst deoxygenation rate was reduced to 80% of the fresh catalyst. The deoxygenation rate of the fresh deoxygenated catalyst was tested, and the results are shown in Table 3.

[0096] The composition of the deactivated catalyst is: the active precious metal component is palladium, and the carrier is alumina; the carbon deposit content is 5.6% by weight, and based on the total weight of the active precious metal component and the carrier, the content of the active precious metal component is 1% by weight.

[0097] (3) Regeneration of deactivated deoxygenation catalyst, including:

[0098] S1. Weigh 100 g of the sintered deactivated catalyst, calcine it at 400 ° C for 5 h in an air atmosphere, and then immerse the calcined product in 200 mL of 0.2 mol / L nitric acid solution, stir it at 50 ° C for 2 h, then add 10 g of disodium ethylenediaminetetraacetic acid, stir it for 2 h, and then perform solid-liquid separation, take out the supernatant, and then adjust the pH value to 7 with acetic acid to obtain a liquid product;

[0099] S2. Add 2 g of potassium nitrate to the liquid product obtained in step S1, stir and dissolve at 50° C. for 1 h, then add 99 g of alumina, soak at room temperature (25° C.) for 5 h, then dry at 50° C., and finally calcine at 500° C. for 3 h to obtain a regenerated deoxygenation catalyst.

[0100] The deoxygenation reaction of the regenerated deoxygenation catalyst was carried out under the same test conditions as the deoxygenation test of the fresh deoxygenation catalyst. The results are shown in Table 3.

[0101] The composition of the regenerated deoxygenation catalyst is: the active precious metal component is palladium, the carrier is aluminum oxide, and the active auxiliary component is potassium oxide; based on the total weight of the catalyst, the carbon deposit content is 0.2 weight%, the content of the active precious metal component is 0.83 weight%, the content of the active auxiliary component is 1.97 weight%, and the content of the carrier is 97 weight%.

[0102] Example 3

[0103] (1) Composition of the fresh deoxygenation catalyst: the active precious metal component is platinum, and the carrier is alumina; the content of the active precious metal component is 1% by weight.

[0104] (2) Deoxygenation test of fresh deoxygenation catalyst:

[0105] The fresh deoxygenation catalyst is subjected to a deoxygenation reaction, comprising:

[0106] Propylene gas containing 3% by volume of O2 was used as a raw material for deoxygenation reaction in a fixed bed catalytic reaction evaluation device at a reaction temperature of 280°C and a volume space velocity of 2500 h -1 The pressure was 0.6 MPa, and the catalyst evaluation was continued until the catalyst deoxygenation rate decreased to 80% of the fresh catalyst. The deoxygenation rate of the fresh deoxygenated catalyst was tested, and the results are shown in Table 3.

[0107] The composition of the deactivated catalyst is: the active precious metal component is platinum, and the carrier is alumina; the carbon deposit content is 7% by weight, and based on the total weight of the active precious metal component and the carrier, the content of the active precious metal component is 1% by weight.

[0108] (3) Regeneration of deactivated deoxygenation catalyst, including:

[0109] S1. Weigh 20 g of the sintered deactivated catalyst, calcine it at 600 ° C for 5 h in an air atmosphere, and then immerse the calcined product in 25 mL of 0.2 mol / L nitric acid solution, stir it at room temperature (25 ° C) for 2 h, then add 10 g of disodium ethylenediaminetetraacetic acid, stir it for 2 h, and then perform solid-liquid separation, take out the supernatant, and then adjust the pH value to 7 with acetic acid to obtain a liquid product;

[0110] S2. Add 0.5 g of potassium carbonate to the liquid product obtained in step S1, stir and dissolve at 100° C. for 1 h, then add 20 g of alumina, soak at room temperature (25° C.) for 5 h, then dry at 50° C., and finally calcine at 400° C. for 2 h to obtain a regenerated deoxygenation catalyst.

[0111] The deoxygenation reaction of the regenerated deoxygenation catalyst was carried out under the same test conditions as the deoxygenation test of the fresh deoxygenation catalyst. The results are shown in Table 3.

[0112] The composition of the regenerated deoxygenation catalyst is: the active precious metal component is platinum, the carrier is aluminum oxide, and the active auxiliary component is potassium oxide; based on the total weight of the catalyst, the carbon deposit content is 0.1 weight%, the content of the active precious metal component is 0.94 weight%, the content of the active auxiliary component is 3.96 weight%, and the content of the carrier is 95 weight%.

[0113] Example 4

[0114] (1) Composition of the fresh deoxygenation catalyst: the active precious metal component is palladium, and the carrier is cerium dioxide; the content of the active precious metal component is 1.3% by weight.

[0115] (2) Deoxygenation test of fresh deoxygenation catalyst:

[0116] The fresh deoxygenation catalyst is subjected to a deoxygenation reaction, comprising:

[0117] The fresh deoxygenation catalyst is subjected to a deoxygenation reaction, including: using propylene gas containing 3 volume % O2 as a raw material, and conducting a deoxygenation reaction in a fixed bed catalytic reaction evaluation device, the reaction temperature is 260°C, the volume space velocity is 1500h -1 The pressure was 0.3 MPa, and the catalyst evaluation was continued until the catalyst deoxygenation rate was reduced to 80% of the fresh catalyst. The deoxygenation rate of the fresh deoxygenated catalyst was tested, and the results are shown in Table 3.

[0118] The composition of the deactivated catalyst is: the active precious metal component is palladium, and the carrier is cerium dioxide; the carbon deposit content is 5.8% by weight, and based on the total weight of the active precious metal component and the carrier, the content of the active precious metal component is 1.3% by weight.

[0119] (3) Regeneration of deactivated deoxygenation catalyst, including:

[0120] S1. Weigh 100 g of the sintered deactivated catalyst, calcine it at 400 ° C for 5 h in an air atmosphere, and then immerse the calcined product in 250 mL of 0.1 mol / L nitric acid solution, stir it at room temperature (25 ° C) for 2 h, then add 10 g of disodium ethylenediaminetetraacetic acid, stir it for 2 h, and then perform solid-liquid separation, take out the supernatant, and then adjust the pH value to 7 with acetic acid to obtain a liquid product;

[0121] S2. Add 4 g of lithium nitrate to the liquid product obtained in step S1, stir and dissolve at room temperature (25°C) for 1 hour, then add 99 g of cerium dioxide, soak at room temperature (25°C) for 5 hours, then dry at 50°C, and finally calcine at 550°C for 2 hours to obtain a regenerated deoxygenation catalyst.

[0122] The deoxygenation reaction of the regenerated deoxygenation catalyst was carried out under the same test conditions as the deoxygenation test of the fresh deoxygenation catalyst. The results are shown in Table 3.

[0123] The composition of the regenerated deoxygenation catalyst is: the active precious metal component is palladium, the carrier is cerium dioxide, and the active auxiliary component is lithium oxide; based on the total weight of the catalyst, the carbon deposit content is 0.1 weight%, the content of the active precious metal component is 1 weight%, the content of the active auxiliary component is 1.9 weight%, and the content of the carrier is 97 weight%.

[0124] Example 5

[0125] (1) Composition of the fresh deoxygenation catalyst: the active precious metal component is gold, the carrier is alumina; the content of the active precious metal component is 1% by weight.

[0126] (2) Deoxygenation test of fresh deoxygenation catalyst:

[0127] The fresh deoxygenation catalyst is subjected to a deoxygenation reaction, comprising:

[0128] Propylene gas containing 3% by volume of O2 was used as a raw material for deoxygenation reaction in a fixed bed catalytic reaction evaluation device at a reaction temperature of 260°C and a volume space velocity of 1500 h -1 The pressure was 0.3 MPa, and the catalyst evaluation was continued until the catalyst deoxygenation rate was reduced to 80% of the fresh catalyst. The deoxygenation rate of the fresh deoxygenated catalyst was tested, and the results are shown in Table 3.

[0129] The composition of the deactivated catalyst is: the active precious metal component is gold, and the carrier is alumina; the carbon deposit content is 6.8% by weight, and based on the total weight of the active precious metal component and the carrier, the content of the active precious metal component is 1% by weight.

[0130] (3) Regeneration of deactivated deoxygenation catalyst, including:

[0131] S1. Weigh 100 g of the sintered deactivated catalyst, calcine it at 500 ° C for 5 h in an air atmosphere, and then immerse the calcined product in 250 mL of 0.1 mol / L nitric acid solution, stir it at room temperature (25 ° C) for 2 h, then add 10 g of disodium ethylenediaminetetraacetic acid, stir it for 2 h, and then perform solid-liquid separation, take out the supernatant, and then adjust the pH value to 7 with acetic acid to obtain a liquid product;

[0132] S2. Add 4 g of sodium nitrate to the liquid product obtained in step S1, stir and dissolve at room temperature (25°C) for 1 hour, then add 99 g of alumina, soak at room temperature (25°C) for 5 hours, then dry at 50°C, and finally calcine at 550°C for 2 hours to obtain a regenerated deoxygenation catalyst.

[0133] The deoxygenation reaction of the regenerated deoxygenation catalyst was carried out under the same test conditions as the deoxygenation test of the fresh deoxygenation catalyst. The results are shown in Table 3.

[0134] The composition of the regenerated deoxygenation catalyst is: the active precious metal component is gold, the carrier is aluminum oxide, and the active auxiliary component is sodium oxide; based on the total weight of the catalyst, the carbon deposit content is 0.1 weight%, the content of the active precious metal component is 0.8 weight%, the content of the active auxiliary component is 4.1 weight%, and the content of the carrier is 95 weight%.

[0135] Example 6

[0136] (1) Composition of the fresh deoxygenation catalyst: the active precious metal component is palladium, and the carrier is silicon dioxide; the content of the active precious metal component is 1% by weight.

[0137] (2) Deoxygenation test of fresh deoxygenation catalyst:

[0138] The fresh deoxygenation catalyst is subjected to a deoxygenation reaction, comprising:

[0139] Propylene gas containing 3% by volume of O2 was used as a raw material for deoxygenation reaction in a fixed bed catalytic reaction evaluation device at a reaction temperature of 260°C and a volume space velocity of 1500 h -1 The pressure was 0.3 MPa, and the catalyst evaluation was continued until the catalyst deoxygenation rate was reduced to 80% of the fresh catalyst. The deoxygenation rate of the fresh deoxygenated catalyst was tested, and the results are shown in Table 3.

[0140] The composition of the deactivated catalyst is: the active precious metal component is palladium, and the carrier is silicon dioxide; the carbon deposit content is 6.9% by weight, and based on the total weight of the active precious metal component and the carrier, the content of the active precious metal component is 1% by weight.

[0141] (3) Regeneration of deactivated deoxygenation catalyst, including:

[0142] S1. Weigh 10 g of the sintered deactivated catalyst, calcine it at 400 ° C for 5 h in an air atmosphere, then immerse the calcined product in 25 mL of 0.1 mol / L nitric acid solution, stir it at room temperature (25 ° C) for 2 h, then add 1 g of disodium ethylenediaminetetraacetic acid, stir it for 2 h, then perform solid-liquid separation, take out the supernatant, and then adjust the pH value to 7 with acetic acid to obtain a liquid product;

[0143] S2. Add 0.2 g of sodium carbonate to the liquid product obtained in step S1, stir and dissolve at room temperature (25°C) for 1 hour, then add 10 g of silicon dioxide, soak at room temperature (25°C) for 5 hours, then dry at 100°C, and finally calcine at 550°C for 2 hours to obtain a regenerated deoxygenation catalyst.

[0144] The deoxygenation reaction of the regenerated deoxygenation catalyst was carried out under the same test conditions as the deoxygenation test of the fresh deoxygenation catalyst. The results are shown in Table 3.

[0145] The composition of the regenerated deoxygenation catalyst is: the active precious metal component is palladium, the carrier is silicon dioxide, and the active auxiliary component is sodium oxide; based on the total weight of the catalyst, the carbon deposit content is 0.2 weight%, the active precious metal component content is 0.8 weight%, the active auxiliary component content is 3 weight%, and the carrier content is 96 weight%.

[0146] Example 7

[0147] (1) Composition of the fresh deoxygenation catalyst: the active precious metal component is platinum, and the carrier is alumina; the content of the active precious metal component is 2% by weight.

[0148] (2) Deoxygenation test of fresh deoxygenation catalyst:

[0149] The fresh deoxygenation catalyst is subjected to a deoxygenation reaction, comprising:

[0150] The fresh deoxygenation catalyst is subjected to a deoxygenation reaction, including: using propylene gas containing 3 volume % O2 as a raw material, and conducting a deoxygenation reaction in a fixed bed catalytic reaction evaluation device, the reaction temperature is 265°C, the volume space velocity is 2500h -1 The pressure was 0.3 MPa, and the catalyst evaluation was continued until the catalyst deoxygenation rate was reduced to 80% of the fresh catalyst. The deoxygenation rate of the fresh deoxygenated catalyst was tested, and the results are shown in Table 3.

[0151] The composition of the deactivated catalyst is: the active precious metal component is platinum, and the carrier is alumina; the carbon deposit content is 8.8% by weight, and based on the total weight of the active precious metal component and the carrier, the content of the active precious metal component is 2% by weight.

[0152] (3) Regeneration of deactivated deoxygenation catalyst, including:

[0153] S1. Weigh 100 g of the sintered deactivated catalyst, calcine it at 700 ° C for 4 h in an air atmosphere, and then immerse the calcined product in 200 mL of 0.2 mol / L nitric acid solution, stir it at 50 ° C for 2 h, then add 10 g of sodium oxalate, stir it for 1 h, and then perform solid-liquid separation, take out the supernatant, and then adjust the pH value to 7 with acetic acid to obtain a liquid product;

[0154] S2. Add 1 g of potassium nitrate to the liquid product obtained in step S1, stir and dissolve at 50° C. for 1 h, then add 99 g of alumina, soak at room temperature (25° C.) for 5 h, then dry at 50° C., and finally calcine at 500° C. for 3 h to obtain a regenerated deoxygenation catalyst.

[0155] The deoxygenation reaction of the regenerated deoxygenation catalyst was carried out under the same test conditions as the deoxygenation test of the fresh deoxygenation catalyst. The results are shown in Table 3.

[0156] The composition of the regenerated deoxygenation catalyst is: the active precious metal component is platinum, the carrier is aluminum oxide, and the active auxiliary component is potassium oxide; based on the total weight of the catalyst, the carbon deposit content is 0.1 weight%, the active precious metal component content is 2 weight%, the active auxiliary component content is 1.9 weight%, and the carrier content is 96 weight%.

[0157] Example 8

[0158] (1) Composition of the fresh deoxygenation catalyst: the active precious metal component is ruthenium, and the carrier is alumina; the content of the active precious metal component is 1.6% by weight.

[0159] (2) Deoxygenation test of fresh deoxygenation catalyst:

[0160] The fresh deoxygenation catalyst is subjected to a deoxygenation reaction, comprising:

[0161] The fresh deoxygenation catalyst is subjected to a deoxygenation reaction, including: using propylene gas containing 3 volume % O2 as a raw material, and conducting a deoxygenation reaction in a fixed bed catalytic reaction evaluation device, the reaction temperature is 280°C, the volume space velocity is 2500h -1 The pressure was 0.3 MPa, and the catalyst evaluation was continued until the catalyst deoxygenation rate was reduced to 80% of the fresh catalyst. The deoxygenation rate of the fresh deoxygenated catalyst was tested, and the results are shown in Table 3.

[0162] The composition of the deactivated catalyst is: the active precious metal component is ruthenium, and the carrier is aluminum oxide; the carbon deposit content is 9.4% by weight, and based on the total weight of the active precious metal component and the carrier, the content of the active precious metal component is 1.6% by weight.

[0163] (3) Regeneration of deactivated deoxygenation catalyst, including:

[0164] S1. Weigh 100 g of the sintered deactivated catalyst, calcine it at 600 ° C for 4 h in an air atmosphere, and then immerse the calcined product in 200 mL of 0.2 mol / L nitric acid solution, stir it at 50 ° C for 2 h, then add 10 g of sodium acetate, stir it for 1 h, and then perform solid-liquid separation, take out the supernatant, and then adjust the pH value to 7 with acetic acid to obtain a liquid product;

[0165] S2. Add 1 g of potassium nitrate to the liquid product obtained in step S1, stir and dissolve at 50° C. for 1 h, then add 99 g of alumina, soak at room temperature (25° C.) for 5 h, then dry at 50° C., and finally calcine at 500° C. for 3 h to obtain a regenerated deoxygenation catalyst.

[0166] The deoxygenation reaction of the regenerated deoxygenation catalyst was carried out under the same test conditions as the deoxygenation test of the fresh deoxygenation catalyst. The results are shown in Table 3.

[0167] The composition of the regenerated deoxygenation catalyst is: the active precious metal component is ruthenium, the carrier is aluminum oxide, the active auxiliary component is potassium oxide, and the carrier is aluminum oxide; based on the total weight of the catalyst, the carbon deposit content is 0.2 weight%, the active precious metal component content is 1.2 weight%, the active auxiliary component content is 3.6 weight%, and the carrier content is 95 weight%.

[0168] Comparative Example 1

[0169] The method of Example 1 is followed, except that in step S1, no dissolution aid is added. The specific method is as follows:

[0170] (1) Composition of the fresh deoxygenation catalyst: the active precious metal component is palladium, and the carrier is alumina; the content of the active precious metal component is 1.5% by weight.

[0171] (2) Deoxygenation test of fresh deoxygenation catalyst:

[0172] The fresh deoxygenation catalyst is subjected to a deoxygenation reaction, comprising:

[0173] The fresh deoxygenation catalyst is subjected to a deoxygenation reaction, including: using propylene gas containing 3 volume % O2 as a raw material, and conducting a deoxygenation reaction in a fixed bed catalytic reaction evaluation device, the reaction temperature is 260°C, the volume space velocity is 3000h -1 The pressure was 0.5 MPa, and the catalyst evaluation was continued until the catalyst deoxygenation rate was reduced to 80% of the fresh catalyst. The deoxygenation rate of the fresh deoxygenated catalyst was tested, and the results are shown in Table 3.

[0174] The composition of the deactivated catalyst is: the active precious metal component is palladium, and the carrier is alumina; the carbon deposit content is 5.6% by weight, and based on the total weight of the active precious metal component and the carrier, the content of the active precious metal component is 1.5% by weight.

[0175] (3) Regeneration of deactivated deoxygenation catalyst, including:

[0176] S1. Weigh 100 g of the sintered deactivated catalyst, calcine it at 500° C. for 5 h in an air atmosphere, and then immerse the calcined product in 200 mL of 0.2 mol / L nitric acid solution, stir it at 50° C. for 2 h, and then perform solid-liquid separation, take out the supernatant, and then adjust the pH value to 7 with acetic acid to obtain a liquid product;

[0177] S2. Add 1 g of sodium nitrate to the liquid product obtained in step S1, stir and dissolve at 50° C. for 1 h, then add 99 g of alumina, soak at room temperature (25° C.) for 5 h, then dry at 50° C., and finally calcine at 500° C. for 3 h to obtain a regenerated deoxygenation catalyst.

[0178] The deoxygenation reaction of the regenerated deoxygenation catalyst was carried out under the same test conditions as the deoxygenation test of the fresh deoxygenation catalyst. The results are shown in Table 3.

[0179] The composition of the regenerated deoxygenation catalyst is: the active precious metal component is palladium, the carrier is aluminum oxide, the active auxiliary component is sodium oxide, and the carrier is aluminum oxide; based on the total weight of the catalyst, the carbon deposit content is 0.2 weight%, the active precious metal component content is 0.8 weight%, the active auxiliary component content is 1 weight%, and the carrier content is 98 weight%.

[0180] Comparative Example 2

[0181] The method of Example 1 is followed, except that in step S2, no catalyst aid is added. The specific method is as follows:

[0182] (1) Composition of the fresh deoxygenation catalyst: the active precious metal component is palladium, and the carrier is alumina; the content of the active precious metal component is 1.5% by weight.

[0183] (2) Deoxygenation test of fresh deoxygenation catalyst:

[0184] The fresh deoxygenation catalyst is subjected to a deoxygenation reaction, comprising:

[0185] The fresh deoxygenation catalyst is subjected to a deoxygenation reaction, including: using propylene gas containing 3 volume % O2 as a raw material, and conducting a deoxygenation reaction in a fixed bed catalytic reaction evaluation device, the reaction temperature is 260°C, the volume space velocity is 3000h -1 The pressure was 0.5 MPa, and the catalyst evaluation was continued until the catalyst deoxygenation rate was reduced to 80% of the fresh catalyst. The deoxygenation rate of the fresh deoxygenated catalyst was tested, and the results are shown in Table 3.

[0186] The composition of the deactivated catalyst is: the active precious metal component is palladium, and the carrier is alumina; the carbon deposit content is 5.6% by weight, and based on the total weight of the active precious metal component and the carrier, the content of the active precious metal component is 1.5% by weight.

[0187] (3) Regeneration of deactivated deoxygenation catalyst, including:

[0188] S1. Weigh 100 g of the sintered deactivated catalyst, calcine it at 500 ° C for 5 h in an air atmosphere, and then immerse the calcined product in 200 mL of 0.2 mol / L nitric acid solution, stir it at 50 ° C for 2 h, then add 10 g of disodium ethylenediaminetetraacetic acid, stir it for 1 h, and then perform solid-liquid separation, take out the supernatant, and then adjust the pH value to 7 with acetic acid to obtain a liquid product;

[0189] S2. Add 99 g of alumina to the liquid product obtained in step S1, soak at room temperature (25° C.) for 5 h, then dry at 50° C., and finally calcine at 500° C. for 3 h to obtain a regenerated deoxygenation catalyst.

[0190] The deoxygenation reaction of the regenerated deoxygenation catalyst was carried out under the same test conditions as the deoxygenation test of the fresh deoxygenation catalyst. The results are shown in Table 3.

[0191] The composition of the regenerated deoxygenation catalyst is: the active precious metal component is palladium, and the carrier is alumina; based on the total weight of the catalyst, the carbon deposit content is 0.1% by weight, the active precious metal component content is 1.9% by weight, and the carrier content is 98% by weight.

[0192] Test Example 1

[0193] (1) The regenerated deoxygenation catalyst prepared in Example 1 was tested by X-ray diffraction (XRD). The results are as follows: Figure 1 As shown. Figure 1 It can be seen that the diffraction peaks of the sample correspond to the standard card of γ-alumina, indicating that the prepared regenerated deoxygenation catalyst retains the crystal structure of the original carrier γ-alumina.

[0194] (2) The particle sizes of the active precious metal components in the materials prepared in Examples 1-8 and Comparative Examples 1-2 were measured using a scanning electron microscope (SEM). The results are shown in Table 1. Figure 2 As shown, Figure (a) is a deactivated catalyst and Figure (b) is a regenerated catalyst.

[0195] Table 1

[0196]

[0197]

[0198] Test Example 2

[0199] The regenerated deoxygenation catalysts prepared in Examples 1-8 and Comparative Examples 1-2 were tested using an adsorption instrument. The pretreatment method before the material test was as follows: the regenerated deoxygenation catalysts prepared in Examples 1-8 and Comparative Examples 1-2 were vacuum treated at 30° C. for 10 h. The results of the specific surface area, pore volume and average pore size of the regenerated deoxygenation catalysts are shown in Table 2.

[0200] Table 2

[0201]

[0202]

[0203] Test Example 3

[0204] The deoxygenation rates of the fresh deoxygenation catalysts and the regenerated deoxygenation catalysts in Examples 1-8 and Comparative Examples 1-2 were tested, and the test results are shown in Table 3.

[0205] Table 3

[0206]

[0207] It can be seen from the results in Table 3 that the regenerated deoxygenation catalyst prepared by the present invention has a good deoxygenation effect, the activity of the catalyst can be fully restored, and has high stability.

[0208] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A regenerated deoxygenation catalyst, characterized in that: The catalyst comprises an active noble metal component, an active auxiliary component and a carrier, wherein, based on the total weight of the catalyst, the content of the active noble metal component is 0.1-3% by weight, and the content of the carrier is 90-99.9% by weight; wherein the particle size of the active noble metal component is 1-8 nm; wherein the specific surface area of ​​the catalyst is 20-300 m 2 / g, pore volume is 0.1-0.35cm 3 / g, and the average pore size is 7-20nm.

2. The catalyst according to claim 1, characterized in that The active precious metal component is selected from one or more of platinum, palladium, ruthenium, rhodium, gold and silver.

3. The catalyst according to claim 1 or 2, characterized in that The content of the active auxiliary component is 0-7% by weight; Preferably, the co-agent component is selected from alkali metal oxides; Preferably, the alkali metal oxide is selected from one or more of lithium oxide, sodium oxide and potassium oxide.

4. The catalyst according to any one of claims 1 to 3, characterized in that The carrier is selected from one or more of alumina, titania, ceria and silicon oxide.

5. A method for preparing a regenerated deoxygenation catalyst, characterized in that: The method comprises the following steps: S1, calcining the deactivated catalyst, then mixing the calcined product, the acidic solution and the dissolution aid, and obtaining a liquid product after solid-liquid separation; S2, mixing the liquid phase product with a catalyst promoter and a carrier, and calcining.

6. The method according to claim 5, characterized in that The deactivated catalyst contains carbon deposits, active precious metal components and a carrier; Preferably, the carbon deposit content is 1-10 wt % based on the total weight of the deactivated catalyst; Preferably, in the deactivated catalyst, based on the total weight of the active precious metal component and the carrier, the content of the active precious metal component is 0.1-3 wt %; the content of the carrier is 90-99.9 wt %; Preferably, the particle size of the active precious metal component in the deactivated catalyst is 3-15 nm.

7. The method according to claim 6, characterized in that The active precious metal component in the deactivated catalyst is selected from one or more of platinum, palladium, ruthenium, rhodium, gold and silver.

8. The method according to claim 7, characterized in that The carrier in the deactivated catalyst is selected from one or more of alumina, titania, cerium dioxide and silicon oxide.

9. The method according to any one of claims 5 to 8, wherein the deactivated catalyst is obtained by deactivating a fresh deoxygenation catalyst by deoxygenation reaction; Preferably, the fresh deoxygenation catalyst contains an active precious metal component and a carrier; Preferably, based on the total weight of the fresh catalyst, the content of the active precious metal component is 0.1-3 wt %; and the content of the carrier is 90-99.9 wt %.

10. The method according to claim 9, characterized in that The deoxygenation reaction is a reaction between organic hydrocarbons and oxygen; Preferably, the conditions for the deoxygenation reaction include: a temperature of 200-300°C, preferably 230-280°C; a volume space velocity of 1000-5000h -1 , preferably 1500-3500h -1 ; The pressure is 0.1-0.7MPa.

11. The method according to claim 10, characterized in that In step S1, the calcination atmosphere is an air atmosphere; the calcination conditions include: a temperature of 300-900°C, preferably 400-800°C; and a time of 2-10 hours, preferably 3-5 hours.

12. The method according to claim 11, characterized in that In step S1, the amount ratio of the calcined product, the acidic solution and the dissolution aid is 1 g: 1-5 mL: 0.01-0.5 g.

13. The method according to claim 12, characterized in that The acidic solution is selected from one or more of nitric acid, hydrochloric acid, oxalic acid and sulfuric acid; Preferably, the concentration of the acidic solution is 0.05-0.5 mol / L.

14. The method according to claim 13, characterized in that The dissolution aid is an organic salt; Preferably, the organic salt is selected from one or more of disodium ethylenediaminetetraacetate, oxalate and acetate.

15. The method according to claim 14, characterized in that The weight ratio of the catalyst promoter, the carrier and the deactivated catalyst used in step S1 is 0.008-0.08:1:0.8-1.

5.

16. The method according to claim 15, characterized in that In step S2, the catalyst promoter is an alkali metal salt; Preferably, the alkali metal salt is selected from one or more of lithium salt, sodium salt and potassium salt.

17. The method according to claim 16, characterized in that The carrier is selected from one or more of alumina, titania, ceria and silicon oxide.

18. The method according to claim 17, characterized in that In step S2, the calcination conditions include: temperature of 300-600°C and time of 1-5h.

19. A regenerated deoxygenation catalyst prepared by the method of any one of claims 5 to 18.

20. Use of the regenerated deoxygenation catalyst according to any one of claims 1 to 4 and 19 in the reaction of organic hydrocarbons and oxygen.

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