Method for Preparing High-Value Chemicals by Activating Alkanes

Abstract

The present invention relates to the field of chemical engineering technology, and particularly to a method for activating alkanes to prepare high-value-added chemicals. The method for activating alkanes to prepare high-value-added chemicals includes: contacting an alkane with an oxidant in the presence of a catalyst and a solvent, wherein the catalyst comprises a copper-containing material, the solvent is an acidic solution, and the molar concentration of H+ in the acidic solution is greater than 1.0×10 ‑7 mol / L. The method for activating alkanes to prepare high-value-added chemicals provided by the present invention allows for the conversion of alkanes to high-value-added chemicals under normal temperature and pressure, avoiding the use of high-temperature and high-pressure equipment, having high reaction selectivity, being easy to scale up, and the catalyst used being cheap and easily available.

Description

Technical Field

[0001] The present invention relates to the field of chemical engineering technology, and particularly to a method for activating alkanes to prepare high-value chemicals. Background Art

[0002] Alkanes are a class of relatively stable organic compounds, and the activation of alkanes to prepare high-value chemicals has important economic value. For example, alkanes can be reformed with carbon dioxide or water vapor to produce hydrogen and carbon monoxide, and further synthesize a series of liquid alkanes, olefins, and oxygen-containing compounds through Fischer-Tropsch synthesis. However, existing activation methods often require large-scale production equipment, and the reactions are carried out at high temperature, high pressure, in organic solvents or corrosive solvents, which cause great pressure on the environment and relatively high production costs. For example, the main utilization method of light alkanes is to convert light alkanes into syngas or hydrogen under high temperature and high pressure for further conversion and utilization. Such extreme reaction conditions result in the need for large-scale and centralized chemical equipment for this process. A production scale of 700,000 - 1,000,000 tons of natural gas processed annually is required to achieve profitability, which often requires investments in the billions and several years to put into production. In addition, since light alkanes are gases at room temperature, their transportation often requires large-scale pipeline facilities or special transportation tools, which also brings additional costs. These are very unfavorable for dispersed gas fields and oil fields. Therefore, if the conversion of alkanes under mild conditions can be achieved, the dependence on large-scale centralized equipment can be eliminated, and decentralized and efficient utilization of alkanes can be realized.

[0003] In view of this, this invention is specifically proposed. Summary of the Invention

[0004] Based on this, it is necessary to provide a new method for activating alkanes to prepare high-value chemicals.

[0005] On the one hand, the present invention provides a method for activating alkanes to prepare high-value chemicals, including:

[0006] In the presence of a catalyst and a solvent, contacting an alkane with an oxidant, wherein the catalyst includes a copper-containing material, the solvent is an acidic solution, and the molar concentration of H + in the acidic solution is greater than 1.0×10 -7 mol / L.

[0007] In one embodiment, the copper-containing material is selected from one or more of pure copper, copper-containing alloys, copper-containing intermetallic compounds, and copper metal complexes.

[0008] In one embodiment, the shape of the copper-containing material is sheet, block, particle or nanostructure.

[0009] In one embodiment, the mass content of copper element in the copper-containing material is greater than 15%.

[0010] In one embodiment, the acidic solution is selected from one or more of sulfuric acid solution, perchloric acid solution, phosphoric acid solution, hydrochloric acid solution, hydrobromic acid solution and hydroiodic acid solution.

[0011] In one embodiment, the molar concentration of H+ in the acidic solution is greater than or equal to 0.1 mol / L.

[0012] In one embodiment, the acidic solution contains H + with a molar concentration of 0.5 mol / L to 2 mol / L.

[0013] In one embodiment, the oxidant is selected from one or more of organic peroxides, ozone, hydrogen peroxide, oxygen and air.

[0014] In one embodiment, the alkane is selected from lower alkanes with 1 to 4 carbon atoms, polycarbon alkanes with 5 to 20 carbon atoms, and cycloalkanes with 3 to 20 carbon atoms.

[0015] In one embodiment, based on the total volume of the alkane and the oxidant being 100%, the amount of the oxidant used is 5% vol to 30% vol.

[0016] In one embodiment, based on the mass of the catalyst per unit volume of the acidic solution, the amount of the catalyst used is greater than or equal to 5 mg / mL.

[0017] In one embodiment, based on the mass of the catalyst per unit volume of the acidic solution, the amount of the catalyst used is 10 mg / mL to 40 mg / mL.

[0018] Compared with the prior art, the present invention has at least the following beneficial effects:

[0019] The method for preparing high-value-added chemicals by activating alkanes provided by the present invention allows the conversion of alkanes to high-value-added chemicals at normal temperature and pressure, avoiding the use of high-temperature and high-pressure equipment, having high reaction selectivity, being easy to scale up, and the catalysts used being cheap and easily available. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following will briefly introduce the drawings required for use in the description of the specific embodiments or the prior art. Obviously, the drawings in the following description are some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0021] Figure 1 It is a graph showing the relationship between the oxygen ratio and the product formation rate in Examples 1 to 4;

[0022] Figure 2 It is a graph showing the relationship between the amount of copper powder added and the product formation rate in Examples 5 to 8;

[0023] Figure 3 It is a graph showing the relationship between the molar concentration of H + in the acidic solution and the product formation rate in Examples 9 to 12;

[0024] Figure 4 It is a graph showing the relationship between the oxygen ratio and the product formation rate in Examples 13 to 16. Detailed implementation manners

[0025] For the convenience of understanding the present invention, the present invention will be described more comprehensively below with reference to the relevant drawings. Preferred embodiments of the present invention are shown in the drawings. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, these embodiments are provided to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0026] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which the present invention belongs. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more of the related listed items.

[0027] Except as shown in the operating examples or otherwise indicated, all numbers representing the amounts of components, physical and chemical properties, etc. in the specification and claims are understood to be adjusted by the term "about" in all cases. For example, therefore, unless otherwise stated, the numerical parameters listed in the above specification and the appended claims are approximate values, and those skilled in the art can appropriately change these approximate values to obtain the required characteristics by using the teachings disclosed herein. The use of numerical ranges represented by endpoints includes all numbers within that range and any range within that range. For example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, etc.

[0028] An embodiment of the present invention provides a method for preparing high-value-added chemicals by activating alkanes, including:

[0029] In the presence of a catalyst and a solvent, an alkane is contacted with an oxidant, wherein the catalyst includes a copper-containing material, the solvent is an acidic solution, and the acidic solution contains H +The molar concentration is greater than 1.0×10 -7 mol / L.

[0030] In the method for preparing high-value-added chemicals by activating alkanes provided in the embodiments of the present invention, the inventors have discovered for the first time that in the presence of a catalyst containing a copper material and an acidic solution with a certain concentration, alkanes and oxidants can undergo reactions such as dehydrogenation, partial oxidation, and hydration to obtain high-value-added chemicals (including corresponding olefins, alkynes, alcohols, phenols, ethers, aldehydes and ketones, carboxylic acids, esters and other chemicals of alkanes). This method allows the conversion of alkanes to high-value-added chemicals at normal temperature and pressure, avoiding the use of high-temperature and high-pressure equipment, having high reaction selectivity, being easy to scale up, and the catalysts used being cheap and easily available.

[0031] The copper-containing material can be selected from one or more of pure copper, copper-containing alloys, copper-containing intermetallic compounds, and copper metal complexes. Specific examples of the copper-containing material can include, but are not limited to, pure copper with a copper element content greater than 99%, copper-zinc alloy, copper-silver alloy, copper-aluminum alloy, Al4Cu9, Cu3Sn, Cu(InGa)Se2, [Cu(TMEDA)2](NO3)2, [Cu(MIM)4](DCA)2, [Cu(NMIM)4](DCA)2, and combinations thereof.

[0032] The shape of the copper-containing material can be sheet-like, block-like, granular or nanostructured. The thickness of the sheet-like copper-containing material is not limited, and it can be a metal sheet with a thickness of more than 1 mm, a metal foil with a thickness of less than 0.02 mm, or a sheet-like metal between the two. The specific shape of the block-like copper-containing material is also not limited, and it can be a cube, a triangle, or an irregular shape, as long as it is a solid block on a macroscopic scale. The granular copper-containing material can be large particles (particle size greater than 1000 microns), micron particles (particle size between 25 microns and 1000 microns), submicron particles (particle size between 0.1 micron and 1 micron), and ultrafine particles (particle size between 1 micron and 25 microns). The nanostructure includes structures such as nanoparticles, nanotubes, nanorods, and nanowires.

[0033] In some embodiments, the mass content of copper element in the copper-containing material is greater than 15%.

[0034] In some embodiments, the copper-containing material is copper foil, copper powder, or copper nanoparticles. It should be noted that copper powder is granular metallic copper, and its particle size is larger than that of copper nanoparticles. It can be one or more of large particles (particle size greater than 1000 microns), micron particles (particle size between 25 microns and 1000 microns), submicron particles (particle size between 0.1 micron and 1 micron), and ultrafine particles (particle size between 1 micron and 25 microns).

[0035] In some embodiments, in addition to the copper-containing material, the catalyst further includes a carrier for supporting the copper-containing material. For example, when the copper-containing material is a nanostructure (such as copper nanoparticles), porous materials such as activated carbon can be used to support the copper-containing material to avoid its agglomeration and affect the catalytic efficiency.

[0036] In some embodiments, the acidic solution is selected from one or more of sulfuric acid solution, perchloric acid solution, phosphoric acid solution, hydrochloric acid solution, hydrobromic acid solution, and hydroiodic acid solution.

[0037] In some embodiments, the acidic solution is selected from perchloric acid solution.

[0038] Preferably, the molar concentration of H + in the acidic solution is greater than or equal to 0.1 mol / L, and more preferably greater than 0.1 mol / L.

[0039] More preferably, the molar concentration of H + in the acidic solution is any value between 0.5 mol / L and 2 mol / L. It can be understood that the molar concentration of H + in the acidic solution can be 0.5 mol / L, 0.6 mol / L, 0.7 mol / L, 0.8 mol / L, 0.9 mol / L, 1 mol / L, 1.1 mol / L, 1.2 mol / L, 1.3 mol / L, 1.4 mol / L, 1.5 mol / L, 1.6 mol / L, 1.7 mol / L, 1.8 mol / L, 1.9 mol / L, 2.0 mol / L. Even more preferably, the molar concentration of H + in the acidic solution is 0.5 mol / L.

[0040] In some embodiments, the oxidant is selected from one or more of organic peroxides, ozone, hydrogen peroxide, oxygen, and air.

[0041] In some embodiments, the alkane is selected from lower alkanes having 1 to 4 carbon atoms, multi-carbon alkanes having 5 to 20 carbon atoms, and cycloalkanes having 3 to 20 carbon atoms.

[0042] In some embodiments, based on the total volume of the alkane and the oxidant being 100%, the amount of the oxidant is 5% vol to 30% vol. It can be understood that based on the total volume of the alkane and the oxidant being 100%, the amount of the oxidant can be 5% vol, 10% vol, 15% vol, 20% vol, 25% vol, 30% vol.

[0043] In some embodiments, based on the mass of the catalyst per unit volume of the acidic solution, the amount of the catalyst is greater than or equal to 5 mg / mL, preferably greater than 5 mg / mL.

[0044] In some embodiments, based on the mass of the catalyst per unit volume of the acidic solution, the amount of the catalyst is 10 mg / mL to 40 mg / mL. Understandably, based on the volume of the acidic solution, the amount of the catalyst can be 10 mg / mL, 15 mg / mL, 20 mg / mL, 25 mg / mL, 30 mg / mL, 35 mg / mL, 40 mg / mL. Specifically, "mg / mL" represents the amount of the catalyst used per 1 mL of the acidic solution in the reaction system. For example, "5 mg / mL" means that for every 1 mL of the acidic solution, the amount of the catalyst is 5 mg.

[0045] In some embodiments, the method for preparing high-value-added chemicals by activating alkanes further includes

[0046] a step of pretreating the catalyst.

[0047] The purpose of the step of pretreating the catalyst is to remove impurities such as oxides on the surface of the catalyst to improve the catalytic efficiency of the catalyst. Available methods include washing with an acid solution, etc.

[0048] The following are specific examples. The purpose is to further elaborate on the present invention to help those skilled in the art and researchers further understand the present invention. Relevant technical conditions do not constitute any limitation to the present invention. Any form of modification within the scope of the claims of the present invention is within the protection scope of the claims of the present invention. Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods. The experimental methods without specific conditions noted in the examples are carried out under conventional conditions, such as the conditions described in the literature, books, or the methods recommended by the manufacturers.

[0049] Example 1

[0050] 1. Pretreatment of the catalyst

[0051] Weigh 200 mg of copper powder, add 10 mL of 0.1 mol / L perchloric acid aqueous solution, and stir for 15 minutes. Let it stand for 10 minutes. After the copper powder has completely settled, discard the supernatant. Repeat the above steps three to five times.

[0052] 2. Catalytic reaction

[0053] Take the copper powder processed in the above step 1, add 10 mL of 1 mol / L perchloric acid aqueous solution, and while stirring, introduce a mixture of ethane and oxygen. In the mixture, ethane is 95% vol and oxygen is 5% vol. Control the gas flow rate at 10 mL / min and conduct aeration for 1 h. The outlet gas is converted into gases such as ethylene, and the reaction solution is converted into products such as acetic acid.

[0054] Example 2

[0055] 1. Pretreatment of the catalyst

[0056] Weigh 200 mg of copper powder, add 10 mL of 0.1 mol / L perchloric acid aqueous solution, and stir for 15 minutes. Let it stand for 10 minutes. After the copper powder has completely settled, discard the supernatant. Repeat the above steps three to five times.

[0057] 2. Catalytic reaction

[0058] Take the copper powder processed in the above step 1, add 10 mL of 1 mol / L perchloric acid aqueous solution, and while stirring, introduce a mixture of ethane and oxygen. In the mixture, ethane is 90% vol and oxygen is 10% vol. Control the gas flow rate at 10 mL / min and conduct aeration for 1 h. The outlet gas is converted into gases such as ethylene, and the reaction solution is converted into products such as acetic acid.

[0059] Example 3

[0060] 1. Pretreatment of the catalyst

[0061] Weigh 200 mg of copper powder, add 10 mL of 0.1 mol / L perchloric acid aqueous solution, and stir for 15 minutes. Let it stand for 10 minutes. After the copper powder has completely settled, discard the supernatant. Repeat the above steps three to five times.

[0062] 2. Catalytic reaction

[0063] Take the copper powder processed in the above step 1, add 10 mL of 1 mol / L perchloric acid aqueous solution, and while stirring, introduce a mixture of ethane and oxygen. In the mixture, ethane is 80% vol and oxygen is 20% vol. Control the gas flow rate at 10 mL / min and conduct aeration for 1 h. The outlet gas is converted into gases such as ethylene, and the reaction solution is converted into products such as acetic acid.

[0064] Example 4

[0065] 1. Pretreatment of the catalyst

[0066] Weigh 200 mg of copper powder, add 10 mL of 0.1 mol / L perchloric acid aqueous solution, and stir for 15 minutes. Let it stand for 10 minutes. After the copper powder has completely settled, discard the supernatant. Repeat the above steps three to five times.

[0067] 2. Catalytic Reaction

[0068] Take the copper powder treated in the above step 1, add 10 mL of 1 mol / L perchloric acid aqueous solution, and introduce a mixture of ethane and oxygen under stirring. In the mixture, ethane is 70% vol and oxygen is 30% vol. Control the gas flow rate at 10 mL / min and ventilate for 1 h. The outlet gas is converted into gases such as ethylene, and the reaction solution is converted into products such as acetic acid.

[0069] Example 5

[0070] 1. Pretreatment of the Catalyst

[0071] Weigh 50 mg of copper powder, add 10 mL of 0.1 mol / L perchloric acid aqueous solution, and stir for 15 minutes. Let it stand for 10 minutes, and discard the supernatant after the copper powder has completely settled. Repeat the above steps three to five times.

[0072] 2. Catalytic Reaction

[0073] Take the copper powder treated in the above step 1, add 10 mL of 1 mol / L perchloric acid aqueous solution, and introduce a mixture of ethane and oxygen under stirring. In the mixture, ethane is 80% vol and oxygen is 20% vol. Control the gas flow rate at 10 mL / min and ventilate for 1 h. The outlet gas is converted into gases such as ethylene, and the reaction solution is converted into products such as acetic acid.

[0074] Example 6

[0075] 1. Pretreatment of the Catalyst

[0076] Weigh 100 mg of copper powder, add 10 mL of 0.1 mol / L perchloric acid aqueous solution, and stir for 15 minutes. Let it stand for 10 minutes, and discard the supernatant after the copper powder has completely settled. Repeat the above steps three to five times.

[0077] 2. Catalytic Reaction

[0078] Take the copper powder treated in the above step 1, add 10 mL of 1 mol / L perchloric acid aqueous solution, and introduce a mixture of ethane and oxygen under stirring. In the mixture, ethane is 80% vol and oxygen is 20% vol. Control the gas flow rate at 10 mL / min and ventilate for 1 h. The outlet gas is converted into gases such as ethylene, and the reaction solution is converted into products such as acetic acid.

[0079] Example 7

[0080] 1. Pretreatment of the Catalyst

[0081] Weigh 400 mg of copper powder, add 10 mL of 0.1 mol / L perchloric acid aqueous solution, and stir for 15 minutes. Let it stand for 10 minutes. After the copper powder has settled completely, discard the supernatant. Repeat the above steps three to five times.

[0082] 2. Catalytic reaction

[0083] Take the copper powder treated in Step 1 above, add 10 mL of 1 mol / L perchloric acid aqueous solution, and while stirring, introduce a mixture of ethane and oxygen. In the mixture, ethane is 80% vol and oxygen is 20% vol. Control the gas flow rate at 10 mL / min and ventilate for 1 h. Gases such as ethylene are obtained from the outlet gas conversion, and products such as acetic acid are obtained from the reaction liquid conversion.

[0084] Example 8

[0085] 1. Pretreatment of the catalyst

[0086] Weigh 200 mg of copper powder, add 10 mL of 0.1 mol / L perchloric acid aqueous solution, and stir for 15 minutes. Let it stand for 10 minutes. After the copper powder has settled completely, discard the supernatant. Repeat the above steps three to five times.

[0087] 2. Catalytic reaction

[0088] Take the copper powder treated in Step 1 above, add 10 mL of 0.1 mol / L perchloric acid aqueous solution, and while stirring, introduce a mixture of ethane and oxygen. In the mixture, ethane is 80% vol and oxygen is 20% vol. Control the gas flow rate at 10 mL / min and ventilate for 1 h. Gases such as ethylene are obtained from the outlet gas conversion, and products such as acetic acid are obtained from the reaction liquid conversion.

[0089] Example 9

[0090] 1. Pretreatment of the catalyst

[0091] Weigh 200 mg of copper powder, add 10 mL of 0.1 mol / L perchloric acid aqueous solution, and stir for 15 minutes. Let it stand for 10 minutes. After the copper powder has settled completely, discard the supernatant. Repeat the above steps three to five times.

[0092] 2. Catalytic reaction

[0093] Take the copper powder treated in Step 1 above, add 10 mL of 0.5 mol / L perchloric acid aqueous solution, and while stirring, introduce a mixture of ethane and oxygen. In the mixture, ethane is 80% vol and oxygen is 20% vol. Control the gas flow rate at 10 mL / min and ventilate for 1 h. Gases such as ethylene are obtained from the outlet gas conversion, and products such as acetic acid are obtained from the reaction liquid conversion.

[0094] Example 10

[0095] 1. Pretreatment of the catalyst

[0096] Weigh 200 mg of copper powder, add 10 mL of 0.1 mol / L perchloric acid aqueous solution, stir for 15 minutes. Let it stand for 10 minutes, and discard the supernatant after the copper powder has completely settled. Repeat the above steps three to five times.

[0097] 2. Catalytic reaction

[0098] Take the copper powder treated in step 1 above, add 10 mL of 2.0 mol / L perchloric acid aqueous solution, and introduce a mixture of ethane and oxygen under stirring. In the mixture, ethane is 80% vol and oxygen is 20% vol. Control the gas flow rate at 10 mL / min and ventilate for 1 h. Gases such as ethylene are obtained from the converted outlet gas, and products such as acetic acid are obtained from the converted reaction solution.

[0099] Example 11

[0100] 1. Pretreatment of the catalyst

[0101] Weigh 200 mg of copper powder, add 10 mL of 0.1 mol / L perchloric acid aqueous solution, stir for 15 minutes. Let it stand for 10 minutes, and discard the supernatant after the copper powder has completely settled. Repeat the above steps three to five times.

[0102] 2. Catalytic reaction

[0103] Take the copper powder treated in step 1 above, add 10 mL of 1 mol / L perchloric acid aqueous solution, and introduce a mixture of propane and oxygen under stirring. In the mixture, propane is 95% vol and oxygen is 5% vol. Control the gas flow rate at 10 mL / min and ventilate for 1 h. Gases such as propylene are obtained from the converted outlet gas, and products such as propionic acid are obtained from the converted reaction solution.

[0104] Example 12

[0105] 1. Pretreatment of the catalyst

[0106] Weigh 200 mg of copper powder, add 10 mL of 0.1 mol / L perchloric acid aqueous solution, stir for 15 minutes. Let it stand for 10 minutes, and discard the supernatant after the copper powder has completely settled. Repeat the above steps three to five times.

[0107] 2. Catalytic reaction

[0108] Take the copper powder processed in the above step 1, add 10 mL of 1 mol / L perchloric acid aqueous solution, and introduce a mixture of propane and oxygen under stirring. In the mixture, propane is 90% vol and oxygen is 10% vol. Control the gas flow rate at 10 mL / min and ventilate for 1 h. Propylene and other gases are obtained by conversion of the outlet gas, and propionic acid and other products are obtained by conversion in the reaction solution.

[0109] Example 13

[0110] 1. Pretreatment of the catalyst

[0111] Weigh 200 mg of copper powder, add 10 mL of 0.1 mol / L perchloric acid aqueous solution, and stir for 15 minutes. Let it stand for 10 minutes, and discard the supernatant after the copper powder has settled completely. Repeat the above steps three to five times.

[0112] 2. Catalytic reaction

[0113] Take the copper powder processed in the above step 1, add 10 mL of 1 mol / L perchloric acid aqueous solution, and introduce a mixture of propane and oxygen under stirring. In the mixture, propane is 80% vol and oxygen is 20% vol. Control the gas flow rate at 10 mL / min and ventilate for 1 h. Propylene and other gases are obtained by conversion of the outlet gas, and propionic acid and other products are obtained by conversion in the reaction solution.

[0114] Example 14

[0115] 1. Pretreatment of the catalyst

[0116] Weigh 200 mg of copper powder, add 10 mL of 0.1 mol / L perchloric acid aqueous solution, and stir for 15 minutes. Let it stand for 10 minutes, and discard the supernatant after the copper powder has settled completely. Repeat the above steps three to five times.

[0117] 2. Catalytic reaction

[0118] Take the copper powder processed in the above step 1, add 10 mL of 1 mol / L perchloric acid aqueous solution, and introduce a mixture of propane and oxygen under stirring. In the mixture, propane is 70% vol and oxygen is 30% vol. Control the gas flow rate at 10 mL / min and ventilate for 1 h. Propylene and other gases are obtained by conversion of the outlet gas, and propionic acid and other products are obtained by conversion in the reaction solution.

[0119] Comparative Example 1

[0120] 1. Pretreatment of the catalyst

[0121] Weigh 200 mg of copper powder, add 10 mL of 0.1 mol / L perchloric acid aqueous solution, and stir for 15 minutes. Let it stand for 10 minutes, and discard the supernatant after the copper powder has settled completely. Repeat the above steps three to five times.

[0122] 2. Catalytic Reaction

[0123] Take the copper powder treated in the above step 1, add 10 mL of 1.0×10 -7 mol / L perchloric acid aqueous solution, and introduce a mixture of ethane and oxygen under stirring. In the mixture, ethane is 80% vol and oxygen is 20% vol. Control the gas flow rate at 10 mL / min and ventilate for 1 h. Gases such as ethylene are obtained from the converted outlet gas, and products such as acetic acid are obtained from the converted reaction solution.

[0124] Measure the production rates of the reaction process products in the above-mentioned examples and Comparative Example 1. The results are as Figures 1 to 4 shown:

[0125] Examples 1 to 4 are the reaction comparisons of 20 mg / mL copper powder, 1 M perchloric acid aqueous solution, and introducing different proportions of oxygen and ethane. As Figure 1 shown, with the increase in the proportion of oxygen, the product production rate also gradually increases.

[0126] Examples 5 to 7 and Example 3 are the reaction comparisons of 1 M perchloric acid aqueous solution, 80% vol ethane, 20% vol oxygen, and adding different amounts of copper powder. As Figure 2 shown, when the amount of copper powder added is between 10 mg / mL and 40 mg / mL, with the increase in the amount of copper powder added, the product production rate changes little.

[0127] Examples 8 to 10, Example 3, and Comparative Example 1 are the reaction comparisons of 20 mg / mL copper powder, 80% vol ethane, 20% vol oxygen, and different concentrations of acidic solutions. As Figure 3 shown, when the molar concentration of H + in the acidic solution is 1.0×10 -7 mol / L, the product production rate is very slow, almost none; when the molar concentration of H + in the acidic solution is 0.1 mol / L, the product production rate is better, and when the molar concentration of H + in the acidic solution is greater than 0.1 mol / L, the product production rate increases significantly. When the molar concentration of H + in the acidic solution rises to 0.5 mol / L and then up to 2 mol / L, with the increase in the molar concentration of H + the product production rate changes little.

[0128] Examples 11 to 14 are the reaction comparisons of 20 mg / mL copper powder, 1 M HClO4, and introducing different proportions of oxygen and propane. As Figure 4As shown, with the increase in the proportion of oxygen, the product formation rate also gradually increases.

[0129] The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity of description, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered as falling within the scope described in this specification.

[0130] The above-described embodiments merely represent several implementation manners of the present invention, which are convenient for understanding the technical solution of the present invention specifically and in detail, but should not be construed as a limitation on the protection scope of the invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made, and these all belong to the protection scope of the present invention. It should be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments based on the technical solutions provided by the present invention are all within the protection scope of the appended claims of the present invention. Therefore, the protection scope of the present invention patent shall be subject to the content of the appended claims, and the description and drawings can be used to explain the content of the claims.

Claims

1. A method for activating alkanes to prepare high-value-added chemicals, characterized in that, Including: Pre-treating the catalyst; wherein, the pre-treatment is to wash with an aqueous perchloric acid solution; In the presence of the catalyst and the solvent, an alkane and an oxidant are contacted at normal temperature and pressure, wherein the catalyst is a copper-containing material, the solvent is an acidic solution; wherein the alkane is selected from lower alkanes having 2 to 4 carbon atoms; the oxidant is selected from oxygen; the copper-containing material is selected from pure copper; the acidic solution is selected from perchloric acid solution, and the molar concentration of H + in the acidic solution is greater than or equal to 0.1 mol / L.

2. The method for activating alkanes to prepare high-value-added chemicals according to claim 1, characterized in that, The shape of the copper-containing material is sheet, block, particle or nanostructure.

3. The method for activating alkanes to prepare high-value-added chemicals according to claim 1, characterized in that, The copper-containing material is copper foil, copper powder or copper nanoparticles; wherein, the particle size of the copper powder is larger than that of the copper nanoparticles.

4. The method for activating alkanes to prepare high-value-added chemicals according to claim 3, characterized in that, The copper powder is one or more of large particles with a particle size greater than 1000 microns, micron particles with a particle size of 25 microns to 1000 microns, submicron particles with a particle size of 0.1 microns to 1 micron, and ultrafine particles with a particle size of 1 micron to 25 microns.

5. The method for activating alkanes to prepare high-value-added chemicals according to claim 1, characterized in that, The molar concentration of H in the acidic solution + is 0.5 mol / L to 2 mol / L.

6. The method for activating alkanes to prepare high-value-added chemicals according to claim 1, characterized in that, The molar concentration of H + in the acidic solution is 1 mol / L to 2.0 mol / L.

7. The method for activating alkanes to prepare high-value-added chemicals according to claim 1, characterized in that, The alkane is selected from lower alkanes having 2 or 3 carbon atoms.

8. The method for activating alkanes to prepare high-value-added chemicals according to any one of claims 1 to 7, characterized in that, Based on the total volume of the alkane and the oxidant being 100%, the dosage of the oxidant is 5%vol to 30%vol.

9. The method for activating alkanes to prepare high-value-added chemicals according to any one of claims 1 to 7, characterized in that, Based on the mass of the catalyst per unit volume of the acidic solution, the dosage of the catalyst is greater than or equal to 5 mg / mL.

10. The method for activating alkanes to prepare high-value-added chemicals according to any one of claims 1 to 7, characterized in that, Based on the mass of the catalyst per unit volume of the acidic solution, the dosage of the catalyst is 10 mg / mL to 40 mg / mL.

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