A process for heterogeneous catalytic deoxygenation

Abstract

The present application provides a method for heterogeneous catalytic deoxidation. The method comprises the step of deoxidizing the gas to be deoxidized by reacting the reaction compound with the gas to be deoxidized through a heterogeneous catalyst. The method of the present application can be used to replace the existing mature deoxidation process by removing oxygen from the gas to be deoxidized to an extremely low concentration at room temperature through a heterogeneous catalyst and an organic compound, and has the advantages of mild reaction conditions, high selectivity, universality, and suitability for industrialized gas, semiconductor industry, lithium ion battery manufacturing industry, laboratory analysis and other application scenarios.

Description

Technical Field

[0001] This invention relates to a method for catalytic deoxygenation, and more particularly to a method for heterogeneous catalytic deoxygenation, belonging to the field of heterogeneous catalysis technology. Background Technology

[0002] Oxygen removal technology has a wide range of applications and plays a crucial role in many biotechnological and industrial synthesis processes. In the industrial sector, the use of gases with excessively high residual oxygen concentrations can lead to a series of production and safety problems. In Fischer-Tropsch synthesis, an oxygen concentration of less than 10 ppm in the crude synthesis gas effectively prevents the poisoning of the Fischer-Tropsch catalyst, extending the cycle life of the expensive catalyst. In industrial gas pipeline transportation, low oxygen concentrations reduce pipeline corrosion and prevent accidental leaks. The semiconductor manufacturing and processing industry requires ultra-high purity gases with oxygen concentrations below 0.01 ppm; the lithium-ion battery industry requires inert gases with oxygen concentrations below 0.1 ppm to ensure an anhydrous and oxygen-free operating environment; fuel cell and green hydrogen industry standards require oxygen concentrations below 5 ppm; and instrumental analysis requires high-purity gases with oxygen concentrations below 0.5 ppm to achieve higher precision analytical testing. In short, given the current demand for low-oxygen-concentration gases, green and efficient oxygen removal technology is a fundamental and critical technology that urgently needs to be addressed and developed.

[0003] Oxygen removal technologies are generally divided into physical and chemical methods. Physical deoxygenation methods utilize the physical adsorption of O2 by porous materials for separation. Although this requires no additives and produces no byproducts, the cost of the adsorbent materials is high, and the adsorption of trace amounts of oxygen is very difficult, limiting its application in purifying high-purity gases. Chemical deoxygenation methods involve the chemical conversion of oxygen through catalysis or chemisorption to achieve the purpose of removing oxygen. However, the high cost of adsorbents and the complexity of regeneration make the chemisorption method difficult to widely apply.

[0004] In the field of catalytic deoxygenation technology, Kolb reported a deoxygenation method that uses methane oxidation and employs alumina (Al2O3) supported on noble metals (Pt, Pa, Rh, Cu, Ag / Al2O3) as a catalyst to remove oxygen from biogas streams. Although this catalytic deoxygenation method has the advantage of high efficiency, it still has disadvantages such as high operating cost, high temperature and pressure, and high energy consumption (F. Ortloff, J. Bohnau, F. Graf, T. Kolb, Appl. Catal. B 2016, 182, 375-384.).

[0005] Therefore, research on novel catalytic deoxygenation technologies that are efficient, green, safe, and inexpensive is of great value. Summary of the Invention

[0006] To achieve the above-mentioned technical objectives, the present invention provides a method for heterogeneous catalytic deoxygenation, which includes the step of reacting a reaction compound with the gas to be deoxygenated using a heterogeneous catalyst to complete the deoxygenation of the gas; wherein...

[0007] The reactive compound has the structure shown in Formula I:

[0008]

[0009] Among them, R 1 The substituents are 1, 2, 3, 4 or 5 attached to the benzene ring, each of which is independently selected from hydrogen, halogen, C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C6-C20 aryl, -OR', -OCF3, -NHR', -C(=O)OR', -NHC(=O)R' and -C(=O)R', wherein R' is any one of H, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, phenyl and benzyl;

[0010] n is a C0-C10 alkyl group connected to a benzene ring and a mercapto group;

[0011] R2 represents carbon, nitrogen, oxygen, sulfur, silicon, phosphorus, and boron.

[0012] The heterogeneous catalytic deoxygenation method of the present invention has the following reaction mechanism:

[0013]

[0014] In one specific embodiment of the present invention, the method includes:

[0015] The reactant compound is dispersed with the added catalyst to obtain a mixed suspension;

[0016] The mixed suspension is stirred in the gas to be deoxygenated, and the reaction temperature is controlled between -50°C and 200°C.

[0017] In one specific embodiment of the present invention, the method includes the step of mixing the reaction compound with a solvent, and then adding a catalyst for dispersion to obtain a mixed suspension.

[0018] In one specific embodiment of the present invention, the concentration of the reactant compound in the mixed suspension is 1-1000 mmol / L, and the concentration of the catalyst is 1-100 mg / mL.

[0019] For example, the concentrations of the reacting compounds in the mixed suspension are 50 mmol / L, 100 mmol / L, 200 mmol / L, 300 mmol / L, 400 mmol / L, 500 mmol / L, 600 mmol / L, 700 mmol / L, 800 mmol / L, 900 mmol / L, and 1000 mmol / L.

[0020] For example, the concentration of the catalyst in the mixed suspension is 10 mg / mL, 20 mg / mL, 30 mg / mL, 40 mg / mL, 50 mg / mL, 60 mg / mL, 70 mg / mL, 80 mg / mL, 90 mg / mL, or 100 mg / mL.

[0021] In one specific embodiment of the present invention, the heterogeneous catalyst is a metal-organic framework material;

[0022] Preferably, the heterogeneous catalyst is a mixture of one or more of the following: metals, alloys, metal oxides, metal nitrogen compounds, metal sulfides, perovskites, copper-iron ore, carbon-based and nitrogen-based polymer materials.

[0023] In one specific embodiment of the present invention, the reaction compound is selected from one or a combination of several of the following: p-fluorophenol, p-chlorobenzyl mercaptan, 2-methylbenzylamine, phenylpropanol, benzyl mercaptan, N,N-dimethylphenylethylamine, p-bromophenol, p-bromobenzyl mercaptan, phenylethylamine, benzyl alcohol, and phenylethyl mercaptan.

[0024] In one specific embodiment of the present invention, the gas to be deoxygenated is oxygen and one or more of the following: He, Ar, N2, CO2, CO, O2, H2, NH3, methane, ethane, propane, ethylene, propylene, butene, acetylene, propyne, and silane. The volume content of oxygen in the gas to be deoxygenated is 0.0001%-100%.

[0025] The heterogeneous catalytic deoxygenation method of the present invention uses a reaction compound as a reactant and can rapidly deoxygenate to extremely low concentrations (<0.01ppm) at room temperature and pressure. Furthermore, this heterogeneous catalytic deoxygenation method has advantages such as being non-toxic, safe, highly stable, and recyclable.

[0026] This invention discloses a heterogeneous catalytic high-efficiency deoxygenation method, which achieves high-efficiency deoxygenation by using a catalyst to enable the reaction compound to chemically react with oxygen. It can be used to replace the deoxygenation technology system and has the advantages of high efficiency (mild conditions, high selectivity), low cost, and long-term stability, making it suitable for large-scale industrial applications. Detailed Implementation

[0027] Example 1

[0028] This embodiment provides a method for efficient heterogeneous catalytic deoxygenation, including the following steps:

[0029] (a) 50 mg of aluminum-based organometallic framework catalyst (the synthesis of aluminum-based organometallic framework catalyst is as follows: 133 mg of aluminum chloride and 166 mg of terephthalic acid are dispersed in 5 mL of N,N'-dimethylformamide (DMF), and magnetically stirred at room temperature for 30 min. After magnetic stirring until a transparent solution is obtained, the solution is transferred to a polytetrafluoroethylene autoclave and kept at 150 °C for 12 h in an oven. After natural cooling, the obtained sample is centrifuged and washed three times with DMF, methanol, and deionized water, respectively. Finally, the obtained orange powder is dried in a vacuum drying oven at 120 °C for 24 h).

[0030] (b) The metal framework catalyst was mixed with p-fluorophenol, ground and mixed thoroughly and then loaded into a deoxygenation tube; at room temperature, a nitrogen-oxygen mixed reaction gas was introduced, in which the oxygen content was 500 ppm; by mass spectrometry analysis, the oxygen volume content of the reaction gas decreased from 500 ppm to 0.01 ppm.

[0031] Example 2

[0032] This embodiment provides a heterogeneous catalytic high-efficiency deoxygenation method, which is basically the same as that in Example 1, except that in step (a), the reaction gas is a mixture of oxygen, ethylene, propyne, hydrogen and nitrogen, wherein the oxygen content is 500 ppm; the final result is that the oxygen volume content of the reaction gas decreased from 500 ppm to 0.01 ppm by micro oxygen sensor analysis.

[0033] Example 3

[0034] This embodiment provides a heterogeneous catalytic high-efficiency deoxygenation method, which is basically the same as that in Example 1, except that in step (a), the reaction gas is a mixture of oxygen, methane, ethane, propane and nitrogen, wherein the oxygen content is 500 ppm; the final result is that, according to the analysis of the micro oxygen sensor, the oxygen volume content of the reaction gas decreased from 500 ppm to 0.01 ppm.

[0035] Example 4

[0036] This embodiment provides a heterogeneous catalytic high-efficiency deoxygenation method, which is basically the same as that in Example 1, except that in step (a), the reaction gas is a mixture of oxygen, ethylene, propylene, acetylene, propyne and nitrogen, wherein the oxygen content is 500 ppm; the final result is that the oxygen volume content of the reaction gas decreased from 500 ppm to 0.01 ppm by micro oxygen sensor analysis.

[0037] Example 5

[0038] This embodiment provides a heterogeneous catalytic high-efficiency deoxygenation method, which is basically the same as that in Example 1, except that in step (a), the reaction gas is a mixture of oxygen, hydrogen and nitrogen, with an oxygen content of 500 ppm; the final result is that, according to the analysis of the micro oxygen sensor, the oxygen volume content of the reaction gas decreased from 500 ppm to 0.01 ppm.

[0039] Example 6

[0040] This embodiment provides a heterogeneous catalytic high-efficiency deoxygenation method, which is basically the same as that in Example 1, except that in step (a), the reaction gas is a mixture of oxygen, helium, neon and argon, with an oxygen content of 500 ppm; the final result is that, according to the analysis of the micro oxygen sensor, the oxygen volume content of the reaction gas decreased from 500 ppm to 0.01 ppm.

[0041] Example 7

[0042] This embodiment provides a heterogeneous catalytic high-efficiency deoxygenation method, which is basically the same as that in Example 1, except that in step (a), the reaction temperature is 150°C and the oxygen content is 500 ppm; the final result is that, according to the micro oxygen sensor analysis, the oxygen volume content of the reaction gas decreased from 500 ppm to 0.01 ppm.

[0043] Example 8

[0044] This embodiment provides a heterogeneous catalytic high-efficiency deoxygenation method, which is basically the same as that in Example 1, except that in step (a), the reaction temperature is -50°C and the oxygen content is 500 ppm; the final result is that the oxygen volume content of the reaction gas is reduced from 500 ppm to 1 ppm by micro oxygen sensor analysis.

[0045] Example 9

[0046] This embodiment provides a heterogeneous catalytic high-efficiency deoxygenation method, which is basically the same as that in Example 1, except that: the raw material used is p-chlorobenzyl mercaptan, which is ground and mixed with the catalyst and loaded into the deoxygenation tube; the reaction gas is a nitrogen-oxygen mixture with an oxygen content of 500 ppm; the final result is that, according to the micro-oxygen sensor analysis, the oxygen volume content of the reaction gas decreased from 500 ppm to 0.01 ppm.

[0047] Example 10

[0048] This embodiment provides a method for efficient deoxygenation via heterogeneous catalysis, which is basically the same as that in Example 1, except that: the catalyst obtained in Example 1, 1 mmol of benzylamine and acetonitrile organic solution are mixed evenly and then ultrasonically dispersed (electric power 80W) for 10 min to obtain a suspension; then the dispersed suspension is purged with air and stirred at room temperature for 10 h; by mass spectrometry analysis, the oxygen volume content of the reaction gas decreased from 20% to 0.1%.

[0049] Example 11

[0050] This embodiment provides a heterogeneous catalytic high-efficiency deoxygenation method, which is basically the same as that in Example 8, except that: in step (a), the reaction concentration of the reactant used is 100 mmol of benzylamine; and the result of the final step (b) is that, by mass spectrometry analysis, the oxygen volume content of the reaction gas decreased from 20% to 0.02%.

[0051] Example 12

[0052] This embodiment provides a heterogeneous catalytic high-efficiency deoxygenation method, which is basically the same as that in Example 8, except that: in step (a), the oxygen volume content used is 10%; and the result of the final step (b) is that, through mass spectrometry analysis, the oxygen volume content of the reaction gas is reduced from 10% to 0.01%.

[0053] Example 13

[0054] This embodiment provides a heterogeneous catalytic high-efficiency deoxygenation method, which is basically the same as that in Example 8, except that: in step (a), the oxygen volume content used is 1%; and the result of the final step (b) is that, through mass spectrometry analysis, the oxygen volume content of the reaction gas is reduced from 1% to 0.005%.

[0055] Example 14

[0056] This embodiment provides a heterogeneous catalytic method for efficient deoxygenation, which is basically the same as that in Example 8, except that: in step (a), the catalyst used is Pt / CdS (400mg cadmium sulfide, 97.3mg chloroplatinic acid hexahydrate, 2ml ethanol, and 50ml water are mixed evenly, stirred at room temperature for 2-3 hours under simulated sunlight LED light irradiation and nitrogen protection, centrifuged, and then dried in an oven at 60°C for 24 hours); the final result of step (b) is that, according to mass spectrometry analysis, the oxygen volume content of the reaction gas decreased from 20% to 13%.

[0057] Example 15

[0058] This embodiment provides a heterogeneous catalytic method for efficient deoxygenation, which is basically the same as that in Example 8, except that: in step (a), the catalyst used is Au / ZnS (400mg zinc sulfide, 40.0mg tetrachloroauric acid trihydrate, 2ml ethanol, and 50ml water are mixed evenly, stirred at room temperature for 2-3 hours under simulated sunlight LED light irradiation and nitrogen protection, centrifuged, and then dried in an oven at 60℃ for 24 hours); the final result of step (b) is that, according to mass spectrometry analysis, the oxygen volume content of the reaction gas decreased from 20% to 10%.

[0059] Example 16

[0060] This embodiment provides a heterogeneous catalytic method for efficient deoxygenation, which is basically the same as that in Example 8, except that the raw material used is 80 μmol of 2-methylbenzylamine. Mass spectrometry analysis showed that the oxygen volume content of the reaction gas decreased from 20% to 0.2%.

[0061] Example 17

[0062] This embodiment provides a heterogeneous catalytic method for efficient deoxygenation, which is basically the same as that in Example 8, except that the raw material used is 1 mmol of phenylpropanol. Mass spectrometry analysis showed that the oxygen volume content of the reaction gas decreased from 20% to 0.1%.

[0063] Example 18

[0064] This embodiment provides a heterogeneous catalytic method for efficient deoxygenation, which is basically the same as that in Example 8, except that the raw material used is 1 mmol of benzyl mercaptan. Mass spectrometry analysis showed that the oxygen volume content of the reaction gas decreased from 20% to 0.5%.

[0065] Example 19

[0066] This embodiment provides a heterogeneous catalytic method for efficient deoxygenation, which is basically the same as that in Example 8, except that the raw material used is 1 mmol N,N-dimethylphenylethylamine. Mass spectrometry analysis showed that the oxygen volume content of the reaction gas decreased from 20% to 0.1%.

[0067] Comparative Example 1

[0068] This example is basically the same as that in Example 1, except that the catalyst used is ZrO2, and the final step (c) results in the inability to obtain the target product. Mass spectrometry analysis shows that the oxygen volume content of the reaction gas remains unchanged.

[0069] Comparative Example 2

[0070] This example is essentially the same as that in Example 1, except that no catalyst was used, and the final step (c) resulted in the inability to obtain the target product. Mass spectrometry analysis showed that the oxygen volume content of the reaction gas remained unchanged.

[0071] Table 1

[0072]

[0073] As can be seen from the above examples and comparative examples, the heterogeneous catalytic deoxygenation method of the present invention can be used to replace existing mature deoxygenation processes. It has mild reaction conditions, high selectivity, and universality, and is suitable for application scenarios such as industrial gases, semiconductor industry, lithium-ion battery manufacturing, and laboratory analysis.

[0074] The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it accordingly. They should not be construed as limiting the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A method for heterogeneous catalytic deoxygenation, the method comprising the step of reacting a reaction compound with a gas to be deoxygenated using a heterogeneous catalyst to complete the deoxygenation of the gas; wherein, The reacting compound is p-fluorophenol. The heterogeneous catalyst is an aluminum-based organometallic framework catalyst, which is synthesized according to the following steps: 133 mg of aluminum chloride and 166 mg of terephthalic acid were dispersed in 5 mL of N,N'-dimethylformamide and magnetically stirred at room temperature for 30 min. After stirring until a clear solution was obtained, the solution was transferred to a polytetrafluoroethylene autoclave and kept at 150 °C for 12 h in an oven. After natural cooling, the obtained sample was centrifuged and washed three times with DMF, methanol and deionized water respectively; the obtained orange powder was placed in a vacuum drying oven and dried at 120℃ for 24h.

2. The method according to claim 1, wherein, The method includes: The reactant compound and the catalyst were dispersed to obtain a mixed suspension; The mixed suspension is stirred in the gas to be deoxygenated, and the reaction temperature is controlled between -50°C and 200°C.

3. The method according to claim 2, wherein, The concentration of the reactant compound in the mixed suspension is 1-1000 mmol / L, and the concentration of the catalyst is 1-100 mg / mL.

4. The method according to claim 2, wherein, The method includes the steps of mixing the reaction compound with a solvent, then adding a catalyst for dispersion to obtain a mixed suspension.

5. The method according to claim 1, wherein, The gas to be deoxygenated is a mixture of oxygen and one or more of the following: He, Ar, N2, CO2, CO, H2, NH3, methane, ethane, propane, ethylene, propylene, butene, acetylene, propyne, and silane.

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