CN117443431A - Supported deoxidizing catalyst and preparation method and application thereof - Google Patents

Abstract

The invention relates to the field of oxygen-containing organic gas deoxidization catalysts, and discloses a supported deoxidization catalyst, and a preparation method and application thereof. The preparation method of the supported deoxidizing catalyst comprises the following steps: 1) A silicon source calculated as silicon dioxide, a template agent, molecular sieve seeds calculated as silicon dioxide, alkali and water are mixed according to the following ratio of 1:0.01-0.5:0.01-0.2:0-0.5: mixing at a molar ratio of 1-10; 2) Crystallizing the mixed product; 3) Performing first roasting on the crystallized product to obtain a molecular sieve carrier; 4) And 3) loading active ingredient precursors on the molecular sieve carrier obtained in the step 3) or a carrier containing the molecular sieve carrier by using an impregnation method, and then carrying out second roasting, wherein the active ingredient precursors are one or more of platinum compounds, palladium compounds and ruthenium compounds. The supported deoxidizing catalyst has the advantages of higher dispersity of active species, long reaction service life and good deoxidizing effect.

Description

Supported deoxygenation catalyst and preparation method and application thereof

Technical field

The invention relates to the field of oxygen-containing organic gas deoxygenation catalysts, and specifically relates to a supported deoxygenation catalyst and its preparation method and application.

Background technique

Chemical production units often face high temperatures and pressures, explosive mixtures, and hazardous materials, which pose many potential safety hazards to chemical production safety. Among them, the presence of oxygen-containing organic gases is a common safety hazard. When the oxygen content is within the explosion range or when the oxygen content continues to accumulate and increase, a gas-phase explosion accident occurs, which has an impact on people's production and life.

There are several methods for achieving deoxygenation of oxygen-containing organic gases. Such as adsorption method, cryogenic method, catalytic method, etc. Among them, the catalytic oxidation method for deoxidizing oxygen in organic gases has the characteristics of simple operation, low price, and wide adaptability, making it a deoxygenation method with broad application prospects. In this method, the development of deoxygenation catalysts is a core task and is also a common concern of many scientific researchers around the world.

Hou Lei et al. (Industrial Catalysis, 2020, 28, 11) disclosed a deoxygenation catalyst that is resistant to trace amounts of chlorine in hydrogen. It uses titanium dioxide as a carrier, the precious metal Pt as an active component, and adds a corresponding amount of additives. It can be used in Deoxidation is achieved in a hydrogen atmosphere containing trace amounts of oxygen, and it has certain chlorine resistance. Wang Haiyang et al. (Natural Gas Chemical Industry, C1 Chemistry and Chemical Engineering, 2021, 46, 28-33) developed a coalbed methane deoxygenation catalyst using a self-sacrificial template method, which was used in the deoxygenation reaction of coalbed methane. The developed catalyst uses oxidation Copper is used as the active component, and the amount of copper oxide can be adjusted by the amount of copper-containing precursor. The prepared catalyst was characterized and tested using a variety of characterization methods. In methane (20%) containing 3% oxygen, A higher deoxygenation rate can be achieved at 400-500°C in nitrogen (rest) mixed gas. CN101664679A discloses a coalbed methane deoxygenation catalyst, which uses precious metals as active components, alkali metals, alkaline earth metals and combinations thereof as auxiliaries, and carries the above materials on an inert carrier in the form of a coating to form a catalyst.

Most of the currently reported catalysts can obtain better reaction performance in the early stages of the reaction or can maintain long-term catalytic reaction activity in systems with low oxygen content. However, in systems with high oxygen content, materials often face defects such as poor dispersion of active components, poor reaction stability, coking and deactivation. How to prepare deoxygenation catalysts with long-term and high stability efficiently and at low cost is still a challenge.

Contents of the invention

The purpose of the present invention is to provide a supported deoxygenation catalyst for oxygen-containing organic gases and chemical exhaust gases and a preparation method thereof. The supported deoxygenation catalyst has higher dispersion of active species, long reaction life, and good deoxidation effect.

In order to achieve the above object, on the one hand, the present invention provides a preparation method of a supported deoxygenation catalyst, which is characterized in that the method includes the following steps:

1) The silicon source calculated as silica, the template agent, the molecular sieve seed crystal calculated as silica, alkali and water are carried out according to the molar ratio of 1:0.01-0.5:0.01-0.2:0-0.5:1-10 mix;

2) Crystallize the mixed product;

3) Perform the first roasting of the crystallized product obtained in step 2) to obtain a molecular sieve carrier;

4) Use an impregnation method to load the active ingredient precursor on the molecular sieve carrier obtained in step 3) or on a carrier containing the molecular sieve carrier, and then perform a second roasting,

The active ingredient precursor is selected from one or more of platinum compounds, palladium compounds and ruthenium compounds.

Preferably, the silicon source calculated as silica, the template agent, the molecular sieve seed crystal calculated as silica, alkali and water are in a molar ratio of 1:0.02-0.3:0.03-0.18:0-0.25:1-8 Mix.

Preferably, the silicon source is one or more of white carbon black, silica gel and attapulgite.

Preferably, the template agent is tetrapropylammonium hydroxide.

Preferably, the base is sodium hydroxide and/or potassium hydroxide.

Preferably, the molecular sieve seed crystal is silicalite-1 molecular sieve.

Preferably, the crystallization conditions include: a temperature of 100-230°C and a time of 10-300 minutes.

Preferably, the method further includes: before step 3), perform the steps of solid-liquid separation, washing and drying on the crystallized product obtained in step 2).

Preferably, the conditions for the first roasting include: a temperature of 500-600°C and a roasting time of 2-10 hours.

Preferably, the conditions for the second roasting include: a temperature of 350-450°C and a roasting time of 1-5 hours.

Preferably, the impregnation method is equal volume impregnation.

Preferably, the mass ratio of the active ingredient precursor to the molecular sieve carrier based on the mass of active ingredient elements is 0.001-0.03:1.

Preferably, the active ingredient precursor is one or more of chloroplatinic acid, palladium nitrate, palladium chloride and ruthenium chloride.

A second aspect of the present invention provides a supported deoxygenation catalyst prepared by the method for preparing a supported deoxygenation catalyst of the first aspect of the present invention.

The third aspect of the present invention provides the application of the supported deoxygenation catalyst of the second aspect of the present invention in the deoxidation of oxygen-containing organic gases and chemical exhaust gases.

Through the above technical solution, the catalyst carrier prepared in the preparation method of the present invention is a silicalite-1 molecular sieve with a hierarchical pore structure. Silicalite-1 with high crystallinity can be prepared in a short time by adjusting the synthesis ratio. Molecular sieves. Moreover, in the preparation of the carrier of the present invention, subsequent processes such as acid and alkali treatment are avoided to ensure high crystallinity of the material. Furthermore, the introduction of active centers is carried out using the impregnation method. The rich pore structure of Silicalite-1 molecular sieve promotes dispersion during the introduction of active centers and also provides many landing sites for active centers, which allows the preparation of materials with high metal dispersion. The catalyst provides the possibility of exposing more active sites. In addition to the microporous structure, the catalyst of the present invention has a certain degree of mesoporous structure, which allows the materials involved to have a higher diffusion rate during the deoxygenation reaction, which can reduce coking and carbon deposition during the reaction process and increase the service life of the catalyst. .

Description of the drawings

Figure 1 is the XRD spectrum of the molecular sieve obtained in Example 1.

Figure 2 is a transmission electron microscope image of the molecular sieve obtained in Example 1.

Figure 3 is a scanning electron microscope image of the molecular sieve obtained in Example 1.

Detailed ways

The endpoints of ranges and any values disclosed herein are not limited to the precise range or value, but these ranges or values are to be understood to include values approaching such ranges or values. For numerical ranges, the endpoint values of each range, the endpoint values of each range and individual point values, and the individual point values can be combined with each other to obtain one or more new numerical ranges. These values The scope shall be deemed to be specifically disclosed herein.

According to a first aspect of the present invention, a method for preparing a supported deoxygenation catalyst is provided, which is characterized in that the method includes the following steps:

1) The silicon source calculated as silica, the template agent, the molecular sieve seed crystal calculated as silica, alkali and water are carried out according to the molar ratio of 1:0.01-0.5:0.01-0.2:0-0.5:1-10 mix;

2) Crystallize the mixed product;

3) Perform the first roasting of the crystallized product obtained in step 2) to obtain a molecular sieve carrier;

4) Use an impregnation method to load the active ingredient precursor on the molecular sieve carrier obtained in step 3) or on a carrier containing the molecular sieve carrier, and then perform a second roasting,

The active ingredient precursor is selected from one or more of platinum compounds, palladium compounds and ruthenium compounds.

According to the present invention, by using the following template agent of the present invention and adding an appropriate amount of molecular sieve seeds to provide crystal nuclei, during the synthesis process, by controlling the composition of the synthetic gel within the scope of the present invention, the crystallization time can be significantly shortened .

In the present invention, in the above formula, water is used in a very small amount, which can significantly reduce the discharge of waste water.

According to the present invention, in order to further shorten the crystallization time, increase the yield of molecular sieve products, and improve the deoxidation performance of the catalyst, preferably, a silicon source calculated as silica, a template agent, a molecular sieve seed crystal calculated as silica, and an alkali are used. and water according to a molar ratio of 1:0.02-0.3:0.03-0.18:0.01-0.3:1-8; more preferably, the silicon source calculated as silica, the template agent, and the molecular sieve calculated as silica Seed crystals, alkali and water are mixed at a molar ratio of 1:0.05-0.25:0.05-0.15:0.05-0.2:1-5.

According to the present invention, preferably, the silicon source is one or more of silica, silica gel and attapulgite; more preferably, the silicon source is silica or silica gel.

According to the present invention, preferably, the template agent is tetrapropylammonium hydroxide. By using the template agent as tetrapropylammonium hydroxide and adding an appropriate amount of molecular sieve seeds to provide crystal nuclei, during the synthesis process, by controlling the composition of the synthetic gel within the scope of the present invention, the crystallization time can be significantly shortened. Improve the deoxidation performance of the catalyst.

According to the present invention, the base can be various inorganic bases commonly used in the art. Preferably, the base is sodium hydroxide and/or potassium hydroxide.

According to the present invention, preferably, the molecular sieve seed crystal is silicalite-1 molecular sieve.

In the preparation process of molecular sieves, there are two stages: induction period and crystallization stage. During the induction period, molecular sieve crystals with a specific topological structure are not formed, but precursors with a certain ring structure can be produced. These precursors are crucial for the synthesis of final porous materials. In the present invention, a certain amount of molecular sieve crystal seeds are added. The seeds can produce more ready-made precursors during the dissolution process, which can directly eliminate the formation process of the precursors, thereby further shortening the crystallization time of the entire molecular sieve material and improving Catalyst deoxygenation performance.

According to the present invention, the crystallization conditions may be various conditions commonly used in the art. Preferably, the crystallization conditions include: a temperature of 100-230°C and a time of 10-300 minutes; more preferably, the crystallization conditions include: a temperature of 180-220°C and a time of 10-180 minutes. ; Further preferably, the crystallization conditions include: temperature is 180-200°C, time is 10-120 minutes, further preferably 10-60 minutes, further preferably 10-30 minutes, still further preferably 10- 20 minutes, more preferably 10-15 minutes.

According to the present invention, in order to further improve the purity of the molecular sieve product, preferably, the method further includes: before step 3), the steps of solid-liquid separation, washing and drying of the crystallized product obtained in step 2).

The above-mentioned solid-liquid separation is not particularly limited, and methods commonly used in the art for separating solids and liquids can be used, such as filtration, centrifugation, and other methods.

The above-mentioned washing liquid is not particularly limited. For example, deionized water can be used for washing.

The above-mentioned drying can be performed at 90-120°C for 1-5 hours, for example.

According to the present invention, in step 3), the conditions for the first roasting include: a temperature of 500-600°C and a roasting time of 2-10 hours; preferably, the conditions for the first roasting include: a temperature of 500-600°C. 550℃, roasting time is 2-6 hours.

According to the present invention, preferably, the active ingredient precursor is one or more of chloroplatinic acid, palladium nitrate, palladium chloride and ruthenium chloride.

According to the present invention, preferably, in step 4), the mass ratio of the active ingredient precursor to the molecular sieve carrier based on the mass of the active ingredient is 0.001-0.03:1; more preferably, the mass ratio based on the mass of the active ingredient The mass ratio of the active ingredient precursor to the molecular sieve carrier is 0.003-0.02:1; further preferably, the mass ratio of the active ingredient precursor to the molecular sieve carrier based on the mass of the active ingredient element is 0.005- 0.01:1.

According to the present invention, in step 4), the active ingredient precursor solution is used for impregnation. The solvent in the active ingredient precursor solution only needs to be able to dissolve the active ingredient precursor well. For example, water can be used. In addition, the content of the active ingredient precursor in the active ingredient precursor solution is preferably 0.5-50% by weight, more preferably 0.1-10% by weight.

The impregnation is preferably an equal volume impregnation.

According to the present invention, the impregnation conditions are not particularly limited as long as the active ingredient precursor can be fully adhered. Preferably, the impregnation conditions include standing at 20-40°C (room temperature) for 1-5 hours, preferably 2-3 hours.

According to the present invention, preferably, the method further includes: after the impregnation, drying the impregnated carrier. The drying conditions are not particularly limited. For example, the drying conditions may be at 100-180°C for 1-10 hours.

According to the present invention, the second roasting conditions include: a temperature of 350-450°C and a roasting time of 1-5 hours; preferably, the second roasting conditions include: a temperature of 400-450°C and a roasting time of 2-4 hours.

According to a second aspect of the present invention, there is provided a supported deoxygenation catalyst prepared by the method for preparing a supported deoxygenation catalyst of the first aspect of the present invention.

According to the third aspect of the present invention, the application of the supported deoxygenation catalyst of the second aspect of the present invention in the deoxidation of oxygen-containing organic gases and chemical exhaust gases is provided.

The present invention will be described in detail through examples below, but the present invention is not limited to the following examples.

In the examples and comparative examples of the present invention, the room temperature was about 25°C.

In the following examples and comparative examples, unless otherwise specified, all medicines are commercially available.

Example 1

After mixing 10g of white carbon black (silicon source) and 10g of tetrapropylammonium hydroxide (40% by weight aqueous solution) evenly, add silicalite-1 molecular sieve seed crystal and 1.0g of sodium hydroxide and stir evenly (silicon based on silica) The molar ratio of source, template agent, molecular sieve seed crystal based on silica, alkali and water is 1:0.12:0.05:0.15:2), transfer to a stainless steel reactor or stainless steel tube lined with polytetrafluoroethylene , crystallize at 200°C for 10 min. After the crystallization is completed, the obtained product is washed with deionized water and centrifuged. After removing the water, it is dried at 100°C. Then it was calcined at 550°C for 5 hours. The XRD results showed that all-silica silicalite-1 molecular sieve was prepared.

Use the equal volume impregnation method to impregnate the chloroplatinic acid aqueous solution into the calcined silicalite-1 molecular sieve (the mass ratio of Pt (based on elemental mass) to molecular sieve carrier is 0.005:1), let it stand at room temperature for 2 hours, and then dry at 150°C. The moisture was removed for 5 hours, and the obtained solid material was roasted at 400°C for 3 hours to obtain a supported deoxidation catalyst.

The oxygen-containing organic gas deoxygenation reaction is carried out under the conditions of a propylene feed gas with an oxygen content of 3% by volume, a pressure of 0.3MPa, a temperature of 250°C, and a volume space velocity of 3000h ^-1 , and the oxygen content of the outlet gas is detected to be less than 0.1% by volume.

Example 2

After mixing 10g of white carbon black (silicon source) and 10g of tetrapropylammonium hydroxide (20% by weight aqueous solution), add silicalite-1 molecular sieve seed crystal and 1.0g of sodium hydroxide and stir evenly (silicon based on silica) Source, template agent, molecular sieve seed based on silica, alkali and water (the molar ratio of alkali and water is 1:0.06:0.05:0.15:2.7), transfer to a stainless steel reactor or stainless steel tube lined with polytetrafluoroethylene , crystallize at 200°C for 10 minutes. After the crystallization is completed, the obtained product is washed with deionized water and centrifuged. After removing the water, it is dried at 100°C. Then it was calcined at 550°C for 5 hours. The XRD results showed that all-silica silicalite-1 molecular sieve was prepared.

Use the equal volume impregnation method to impregnate the chloroplatinic acid aqueous solution into the calcined silicalite-1 molecular sieve (the mass ratio of Pt (based on elemental mass) and molecular sieve carrier is 0.01:1), let it stand at room temperature for 2 hours, and then dry at 150°C. The moisture was removed for 5 hours, and the obtained solid material was roasted at 600°C for 3 hours to obtain a supported deoxidation catalyst.

The oxygen-containing organic gas deoxygenation reaction is carried out under the conditions of a propylene feed gas with an oxygen content of 5% by volume, a pressure of 0.4MPa, a temperature of 230°C, and a volume space velocity of 5000h ^-1 , and the oxygen content of the outlet gas is detected to be less than 0.2% by volume.

Example 3

After mixing 15g of fine silica gel (silicon source) and 15g of tetrapropylammonium hydroxide (30% by weight aqueous solution) evenly, add silicalite-1 molecular sieve and 0.6g of sodium hydroxide and stir evenly (silicon source calculated as silica, template The molar ratio of agent, molecular sieve seed crystal calculated as silica, alkali and water is 1:0.09:0.07:0.06:2.3), let stand at room temperature for 10h, and then transfer to a stainless steel reactor lined with polytetrafluoroethylene. Or in a stainless steel reactor, crystallize at 180°C for 60 minutes. After the crystallization is completed, the obtained product is washed with deionized water and centrifuged. After removing the water, it is dried at 100°C. Then it was calcined at 550°C for 3 hours. The XRD results showed that silicalite-1 molecular sieve was prepared.

Use the equal volume impregnation method to impregnate the palladium nitrate aqueous solution into the calcined silicalite-1 molecular sieve (the mass ratio of Pd (based on the elemental mass) to the molecular sieve carrier is 0.008:1), let it stand at room temperature for 2 hours, and then dry at 150°C for 5 Remove the moisture for 1 hour, and roast the obtained solid material at 500°C for 3 hours to obtain a supported deoxidation catalyst.

The oxygen-containing organic gas deoxygenation reaction is carried out under the conditions of a chloropropylene raw gas with an oxygen content of 3% by volume, a pressure of 0.3MPa, a temperature of 250°C, and a volume space velocity of 5000h ^-1 , and the oxygen content of the outlet gas is detected to be less than 0.1% by volume.

Example 4

After mixing 15g of fine silica gel (silicon source) and 15g of tetrapropylammonium hydroxide (40% by weight aqueous solution) evenly, add silicalite-1 molecular sieve and 0.6g of sodium hydroxide and stir evenly (silicon source calculated as silica, template The molar ratio of agent, molecular sieve seed crystal calculated as silica, alkali and water is 1:0.12:0.07:0.06:2), let stand at room temperature for 10h, and then transfer to a stainless steel reactor lined with polytetrafluoroethylene. Or in a stainless steel reactor, crystallize at 180°C for 60 minutes. After the crystallization is completed, the obtained product is washed with deionized water and centrifuged. After removing the water, it is dried at 100°C. Then it was calcined at 550°C for 3 hours. The XRD results showed that silicalite-1 molecular sieve was prepared.

Use the equal volume impregnation method to impregnate the palladium chloride aqueous solution into the calcined silicalite-1 molecular sieve (the mass ratio of Pd (in terms of elemental mass) to the molecular sieve carrier is 0.01:1), let it stand at room temperature for 2 hours, and then dry at 150°C. The moisture was removed for 5 hours, and the obtained solid material was roasted at 400°C for 3 hours to obtain a supported deoxidation catalyst.

The oxygen-containing organic gas deoxygenation reaction is carried out under the conditions of a chloropropylene raw gas with an oxygen content of 3% by volume, a pressure of 0.3MPa, a temperature of 250°C, and a volume space velocity of 5000h ^-1 , and the oxygen content of the outlet gas is detected to be less than 0.15% by volume.

Example 5

After mixing 15g of fine silica gel (silicon source) and 30g of tetrapropylammonium hydroxide (25% by weight aqueous solution) evenly, add silicalite-1 molecular sieve seeds and 2.0g of potassium hydroxide and stir evenly (silicon based on silica) The molar ratio of source, template agent, molecular sieve seed crystal based on silica, alkali and water is 1:0.15:0.03:0.2:5), transfer to a stainless steel tube, and crystallize at 200°C for 20 minutes. After the crystallization is completed, the obtained product is washed with deionized water and centrifuged. After removing the water, it is dried at 100°C overnight. Then it was calcined at 550°C for 5 hours to obtain the molecular sieve. The XRD and _N2 adsorption results showed that the all-silica silicalite-1 molecular sieve with an open structure was prepared.

Use the equal volume impregnation method to impregnate the ruthenium chloride aqueous solution into the calcined silicalite-1 molecular sieve (the mass ratio of Ru (based on elemental mass) to the molecular sieve carrier is 0.01:1), let it stand at room temperature for 2 hours, and then dry at 150°C. The moisture was removed for 5 hours, and the obtained solid material was roasted at 400°C for 3 hours to obtain a supported deoxidation catalyst.

The oxygen-containing organic gas deoxygenation reaction is carried out under the conditions of a chloropropylene raw gas with an oxygen content of 3% by volume, a pressure of 0.3MPa, a temperature of 260°C, and a volume space velocity of 3000h ^-1 , and the oxygen content of the outlet gas is detected to be less than 0.2% by volume.

Example 6

Mix 10g fine silica gel (silicon source), 15g tetrapropylammonium hydroxide (40% by weight aqueous solution), silicalite-1 molecular sieve seed crystal and 1.0g sodium hydroxide in a mortar (silicon source calculated as silica) , template agent, molecular sieve seed crystal based on silica, alkali and water (the molar ratio is 1:0.18:0.15:0.15:3), then transferred to a stainless steel tube and crystallized at 200°C for 60 minutes. After the crystallization is completed, the obtained product is washed with deionized water and centrifuged. After removing the water, it is dried at 100°C overnight. Then it was calcined at 550°C for 8 hours to obtain the molecular sieve. The XRD and _N2 adsorption results showed that the all-silica silicalite-1 molecular sieve with an open structure was prepared.

Use the equal volume impregnation method to impregnate the palladium chloride aqueous solution into the calcined silicalite-1 molecular sieve (the mass ratio of Pd (in terms of elemental mass) to the molecular sieve carrier is 0.001:1), let it stand for 2 hours at room temperature, and then at 150°C Dry for 5 hours to remove moisture, and roast the obtained solid material at 550°C for 3 hours to obtain a supported deoxidation catalyst.

The oxygen-containing organic gas deoxygenation reaction is carried out under the conditions of a chloropropylene raw gas with an oxygen content of 3% by volume, a pressure of 0.3MPa, a temperature of 260°C, and a volume space velocity of 3000h ^-1 , and the oxygen content of the outlet gas is detected to be less than 0.2% by volume.

Example 7

After mixing 15g of fine silica gel (silicon source) and 8g of tetrapropylammonium hydroxide (40% by weight aqueous solution) evenly, add silicalite-1 molecular sieve seed crystals and stir evenly (silicon source calculated as silica, template agent, and The molar ratio of molecular sieve seeds and water (silica meter) is 1:0.06:0.13:1.07), transfer to a stainless steel reactor or stainless steel tube lined with polytetrafluoroethylene, and crystallize at 200°C for 15 minutes. After the crystallization is completed, the obtained product is washed with deionized water and centrifuged. After removing the water, it is dried at 100°C. Then it was calcined at 550°C for 5 hours to obtain the molecular sieve. The XRD and _N2 adsorption results showed that the all-silica silicalite-1 molecular sieve with an open structure was prepared.

Use the equal volume impregnation method to impregnate a certain concentration of palladium chloride aqueous solution into the calcined silicalite-1 molecular sieve (the mass ratio of Pd (in terms of elemental mass) to molecular sieve carrier is 0.01:1), let it stand for 2 hours at room temperature, and then immerse it at 150 Dry at ℃ for 5 hours to remove moisture, and roast the obtained solid material at 550℃ for 3 hours to obtain a supported deoxidation catalyst.

The oxygen-containing organic gas deoxygenation reaction is carried out under the conditions of propylene raw gas with an oxygen content of 5% by volume, a pressure of 0.4MPa, a temperature of 250°C, and a volume space velocity of 3000-5000h ^-1 , and the oxygen content of the outlet gas is detected to be less than 0.1% by volume. .

Comparative example 1

After mixing 10g of white carbon black and 1.0g of tetrapropylammonium hydroxide (40% by weight aqueous solution), add 1.0g of sodium hydroxide, stir evenly, and transfer to a stainless steel reactor or stainless steel tube lined with polytetrafluoroethylene. , crystallize at 200°C for 10 minutes. After the crystallization is completed, the obtained product is washed with deionized water and centrifuged. After removing the water, it is dried at 100°C. Then it was calcined at 550°C for 5 hours. The XRD results showed that the all-silica silicalite-1 molecular sieve with an open structure could not be obtained.

Use the equal volume impregnation method to impregnate the chloroplatinic acid aqueous solution into the calcined silicalite-1 molecular sieve (the mass ratio of Pt (based on the mass of the element) to the molecular sieve carrier is 0.005:1), let it stand at room temperature for 2 hours, and then dry at 150°C. The moisture was removed for 5 hours, and the obtained solid material was roasted at 400°C for 3 hours to obtain a supported deoxidation catalyst.

The oxygen-containing organic gas deoxygenation reaction is carried out under the conditions of a propylene feed gas with an oxygen content of 3% by volume, a pressure of 0.3MPa, a temperature of 250°C, and a volume space velocity of 3000h ^-1 , and the oxygen content of the outlet gas is detected to be greater than 0.2% by volume.

Comparative example 2

After mixing 10g of white carbon black and 1.0g of tetrapropylammonium hydroxide (40% by weight aqueous solution), add 15g of sodium hydroxide, stir evenly, and transfer to a stainless steel reactor or stainless steel tube lined with polytetrafluoroethylene. , crystallized at 200°C for 10 min. After the crystallization is completed, the obtained product is washed with deionized water and centrifuged. After removing the water, it is dried at 100°C. Then it was calcined at 550°C for 5 hours. The XRD results showed that the all-silica silicalite-1 molecular sieve could not be obtained.

Use the equal volume impregnation method to impregnate the chloroplatinic acid aqueous solution into the calcined silicalite-1 molecular sieve (the mass ratio of Pt (based on the mass of the element) to the molecular sieve carrier is 0.005:1), let it stand at room temperature for 2 hours, and then dry at 150°C. The moisture was removed for 5 hours, and the obtained solid material was roasted at 400°C for 3 hours to obtain a supported deoxidation catalyst.

The oxygen-containing organic gas deoxygenation reaction is carried out under the conditions of a propylene feed gas with an oxygen content of 3% by volume, a pressure of 0.3MPa, a temperature of 250°C, and a volume space velocity of 3000h ^-1 , and the oxygen content of the outlet gas is detected to be greater than 0.3% by volume.

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical concept of the present invention, many simple modifications can be made to the technical solution of the present invention, including the combination of various technical features in any other suitable manner. These simple modifications and combinations should also be regarded as the disclosed content of the present invention. All belong to the protection scope of the present invention.

Claims (15)

1. A method for preparing a supported deoxygenation catalyst, characterized in that the method includes the following steps: 1) The silicon source calculated as silica, template agent, molecular sieve seed crystal calculated as silica, alkali and water are carried out according to the molar ratio of 1:0.01-0.5:0.01-0.2:0-0.5:1-10 mix; 2) Crystallize the mixed product; 3) Perform the first roasting of the crystallized product obtained in step 2) to obtain a molecular sieve carrier; 4) Use an impregnation method to load the active ingredient precursor on the molecular sieve carrier obtained in step 3) or on a carrier containing the molecular sieve carrier, and then perform a second roasting, The active ingredient precursor is selected from one or more of platinum compounds, palladium compounds and ruthenium compounds. 2. The method according to claim 1, wherein the silicon source calculated as silica, the template agent, the molecular sieve seed crystal calculated as silica, alkali and water are based on 1:0.02-0.3:0.03-0.18: Mix at a molar ratio of 0-0.25:1-8. 3. The method according to claim 1, wherein the silicon source is one or more of white carbon black, silica gel and attapulgite. 4. The method according to any one of claims 1-3, wherein the template agent is tetrapropylammonium hydroxide. 5. The method according to any one of claims 1-3, wherein the base is sodium hydroxide and/or potassium hydroxide. 6. The method according to any one of claims 1-3, wherein the molecular sieve seed crystal is silicalite-1 molecular sieve. 7. The method according to any one of claims 1-3, wherein the crystallization conditions include: a temperature of 100-230°C and a time of 10-300 minutes. 8. The method according to any one of claims 1 to 3, wherein the method further includes: before step 3), the steps of solid-liquid separation, washing and drying of the crystallized product obtained in step 2). 9. The method according to any one of claims 1-3, wherein the first roasting conditions include: a temperature of 500-600°C and a roasting time of 2-10 hours. 10. The method according to any one of claims 1-3, wherein the second roasting conditions include: a temperature of 350-450°C and a roasting time of 1-5 hours. 11. The method according to any one of claims 1-3, wherein the impregnation method is equal volume impregnation. 12. The method according to any one of claims 1 to 3, wherein the mass ratio of the active ingredient precursor to the molecular sieve carrier based on the active ingredient elemental mass is 0.001-0.03:1. 13. The method according to any one of claims 1-3, wherein the active ingredient precursor is one or more of chloroplatinic acid, palladium nitrate, palladium chloride and ruthenium chloride. 14. The supported deoxygenation catalyst prepared by the method for preparing a supported deoxygenation catalyst according to any one of claims 1 to 10. 15. Application of the supported deoxygenation catalyst according to claim 13 in the deoxidation of oxygen-containing organic gases and chemical exhaust gases.