Monofluoromethane purification and adsorption material as well as preparation method and application thereof

Abstract

The invention relates to a monofluoromethane purification and adsorption material, a preparation method and application, the preparation method comprises the following steps: dipping carrier powder in a transition metal salt solution, and drying to obtain a solid material; and roasting the obtained solid material at 250-350 DEG C in a nitrogen atmosphere to obtain the monofluoromethane purification and adsorption material. The monofluoromethane purification and adsorption material obtained by the invention can effectively improve the removal effect of fluorocarbon impurities and hydrocarbon impurities in the gas phase method monofluoromethane feed gas, and greatly reduces the difficulty of subsequent purification.

Description

Technical Field

[0001] This invention belongs to the field of electronic special gas purification technology, and relates to an adsorption material, particularly a monofluoromethane purification adsorption material, its preparation method, and its application. Background Technology

[0002] Monofluoromethane (CH3F), a key fluorine-containing compound, demonstrates irreplaceable value in several core fields, and its importance is growing daily. In the semiconductor industry, as chip manufacturing processes advance towards the nanometer scale, the requirements for the precision and purity of etching gases are becoming increasingly stringent. Due to its unique chemical reactivity, monofluoromethane enables precise atomic-level manipulation during etching, ensuring the fineness and performance stability of chip circuitry, thus becoming one of the core materials supporting the continuous innovation and development of the semiconductor industry.

[0003] However, the synthesis and purification of monofluoromethane currently face numerous challenges, severely restricting its industrial expansion and in-depth application. Traditional methods for synthesizing monofluoromethane include halogenated hydrocarbon fluorination and methanol fluorination. Halogenated hydrocarbon fluorination typically involves the reaction of chloromethane and hydrogen fluoride with a catalyst to produce monofluoromethane. However, this process requires high temperatures (300℃~500℃) and high pressures (3MPa~10MPa), placing high demands on the materials of the reaction equipment, making precise reaction control difficult, and generating large quantities of difluoromethane, trifluoromethane, and their byproducts. The conversion rate of monofluoromethane using this method is typically only 10%, with a selectivity of approximately 85%, leading to complex subsequent raw material recovery and byproduct treatment processes. While methanol fluorination offers relatively milder reaction conditions, the use of oxygen presents challenges such as low catalyst activity, short catalyst lifespan, and difficulties in product separation, similarly resulting in high production costs for monofluoromethane and hindering the demand for large-scale, low-cost production.

[0004] Crude monofluoromethane contains unreacted feedstock, byproducts, moisture, acidic gases, and other trace impurities. Traditional purification methods, mainly distillation and ordinary adsorption, are insufficient to meet the requirements for deep removal of trace impurities from crude monofluoromethane. During distillation, the boiling points of monofluoromethane and some impurities are extremely close; for example, the boiling point difference between some byproducts and monofluoromethane is less than 2°C, making efficient separation difficult with traditional distillation columns. Ordinary adsorbents have limited adsorption capacity and insufficient selectivity for specific impurities when processing crude monofluoromethane, resulting in poor adsorption of trace impurities. Furthermore, alkanes, alkenes, and other impurities in the monofluoromethane feedstock readily react chemically with the adsorbent, leading to adsorbent poisoning and deactivation. Frequent adsorbent replacement not only increases costs but also disrupts production continuity. Traditional purification methods can only produce monofluoromethane products with a purity of 99.5% to 99.9%, which cannot meet the stringent requirements of semiconductor, high-end electronics and other fields for ultra-high purity (above 99.999%) monofluoromethane, and seriously restricts the application expansion of monofluoromethane in the high-end market.

[0005] Although some studies have attempted to combine different types of adsorbents and achieved some success in removing some difficult-to-separate impurities from crude monofluoromethane, the actual operating conditions have shown that while removing these impurities, it has also significantly reduced the yield of high-purity electronic-grade monofluoromethane, increasing the burden on production costs and waste gas treatment.

[0006] Therefore, it is necessary to develop an adsorption material capable of removing fluorocarbon and hydrocarbon impurities from monofluoromethane synthesis gas. Summary of the Invention

[0007] To address the shortcomings of existing technologies, the present invention aims to provide a fluoromethane purification adsorption material, its preparation method, and its application. The fluoromethane purification adsorption material obtained by the present invention can effectively improve the removal efficiency of fluorocarbon and hydrocarbon impurities in gas-phase fluoromethane feed gas, and significantly reduce the difficulty of subsequent purification.

[0008] To achieve this objective, the present invention adopts the following technical solution:

[0009] In a first aspect, the present invention provides a method for preparing a monofluoromethane purification adsorbent material, the preparation method comprising the following steps:

[0010] The carrier powder is impregnated in a transition metal salt molten solution and dried to obtain a solid material; the obtained solid material is calcined at 250℃~350℃ in a nitrogen atmosphere to obtain the monofluoromethane purification adsorbent material.

[0011] The monofluoromethane purification adsorption material obtained by this invention can effectively improve the removal efficiency of fluorocarbon and hydrocarbon impurities in the gas-phase monofluoromethane feed gas, significantly reducing the difficulty of subsequent purification and making it easier to purify monofluoromethane to a purity of 5N or higher.

[0012] In some embodiments, the oxygen content in the nitrogen atmosphere is 100ppm to 10000ppm, preferably 1000ppm to 3000ppm.

[0013] In some embodiments, the roasting time is 1h to 24h, preferably 2h to 4h.

[0014] In some embodiments, the carrier powder includes any one or a combination of at least two of activated carbon, carbon nanotubes, molecular sieves, or γ-Al2O3 powder.

[0015] In some embodiments, the transition metal salt in the transition metal salt solution includes any one or a combination of at least two of ferric nitrate, cobalt nitrate, nickel nitrate, copper nitrate, zinc nitrate, ferric chloride, cobalt chloride, nickel chloride, copper chloride, zinc chloride, ferric sulfate, cobalt sulfate, nickel sulfate, copper sulfate, or zinc sulfate.

[0016] In some embodiments, the mass concentration of the transition metal salt solution is 1 wt% to 30 wt%, preferably 10 wt% to 20 wt%.

[0017] In some embodiments, the mass ratio of the carrier powder to the transition metal salt solution is 1:1 to 1:20, preferably 1:1 to 1:2.

[0018] In some embodiments, the drying temperature is 10°C to 200°C, preferably 100°C to 150°C.

[0019] In some embodiments, the drying time is 1 hour to 20 hours, preferably 3 hours to 8 hours.

[0020] In a second aspect, the present invention relates to a fluoromethane purification adsorption material, which is prepared by the preparation method described in the first aspect.

[0021] Thirdly, the present invention provides an application of the monofluoromethane purification adsorbent material described in the second aspect, the application including: purifying monofluoromethane feed gas using the monofluoromethane purification adsorbent material.

[0022] In some embodiments, the monofluoromethane purification adsorption material adsorbs fluorocarbon impurities and hydrocarbon impurities in the monofluoromethane feed gas.

[0023] The numerical range described in this invention includes not only the point values ​​listed above, but also any point values ​​within the numerical ranges not listed above. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific point values ​​included in the range.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] The monofluoromethane purification adsorption material obtained by this invention can effectively improve the removal efficiency of fluorocarbon and hydrocarbon impurities in the gas-phase monofluoromethane feed gas, significantly reducing the difficulty of subsequent purification and making it easier to purify monofluoromethane to a purity of 5N or higher. Detailed Implementation

[0026] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0027] The "range" disclosed in this invention can be defined in the form of a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of the specific range. This type of range definition can include or exclude endpoints; any endpoint can be independently included or excluded, and they can be arbitrarily combined, meaning any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60~120 and 80~110 are listed for specific parameters, it is understood that ranges of 60~110 and 80~120 are also expected. Furthermore, if minimum range values ​​1 and 2 are listed, and maximum range values ​​3, 4, and 5 are also listed, then the following ranges are all expected: 1~3, 1~4, 1~5, 2~3, 2~4, and 2~5. In this invention, unless otherwise stated, the numerical range "a~b" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0~5" indicates that all real numbers between "0" and "5" have been listed in this article; "0~5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is described as an integer ≥2, it is equivalent to listing integers such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc. For instance, when a parameter is described as an integer selected from "2~10", it is equivalent to listing the integers 2, 3, 4, 5, 6, 7, 8, 9, and 10.

[0028] In this invention, "a combination of at least two" refers to a quantity greater than or equal to two, unless otherwise specified. For example, "any combination of one or at least two" means one or more or more items. It can be understood that when referring to "a combination of at least two," it refers to any suitable combination of multiple items, that is, a combination of "at least two" items carried out in a manner that does not conflict with and enables the implementation of this invention.

[0029] Unless otherwise specified, all embodiments and optional embodiments of the present invention can be combined with each other to form new technical solutions.

[0030] The term "embodiment" as used in this invention means that a specific feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment or implementation of the invention. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a mutually exclusive, independent, or alternative embodiment. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described in this invention can be combined with other embodiments.

[0031] Those skilled in the art will understand that the order in which the steps are written in the methods of the various embodiments does not imply a strict execution order. The detailed execution order of each step should be determined by its function and possible internal logic. Unless otherwise specified, all steps of the present invention may be performed sequentially or randomly, but are preferably performed sequentially. For example, if the method includes steps (a) and (b), it means that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the method may also include step (c), meaning that step (c) can be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0032] In this invention, open-ended technical features or solutions described using terms such as "comprising" do not exclude additional members beyond those listed unless otherwise specified. They can be considered as providing both closed-ended features or solutions comprised of the listed members and open-ended features or solutions that include additional members beyond the listed members. For example, A includes a1, a2, and a3. Unless otherwise specified, it may also include other members or exclude additional members. This can be considered as providing both technical features or solutions where "A is composed of a1, a2, and a3" or "A is selected from a1, a2, and a3," and technical features or solutions where "A includes not only a1, a2, and a3, but also other members."

[0033] In this invention, unless otherwise specified, the features or solutions corresponding to "and / or" include any one of two or more of the related listed items, as well as any and all combinations of the related listed items. These arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. For example, "A and / or B" represents a group consisting of A, B, and "a combination of A and B". "Containing A and / or B" can mean "containing A, containing B, and containing A and B", or "containing A, containing B, or containing A and B", and can be appropriately understood according to the context.

[0034] In this invention, the terms "first aspect," "second aspect," "third aspect," "fourth aspect," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first," "second," "third," "fourth," etc., serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on the quantity.

[0035] In this invention, "optional" means that something is optional, that is, it refers to any one of the two parallel solutions of "having" or "not having". If there are multiple "optional" options in a technical solution, unless otherwise specified, and there are no contradictions or mutual constraints, then each "optional" option is independent.

[0036] In this invention, "room temperature" generally refers to 4℃~35℃, and can refer to 20℃±5℃. In some embodiments of this invention, room temperature refers to 20℃~30℃.

[0037] An embodiment of the present invention provides a method for preparing a monofluoromethane purification adsorbent, the method comprising the following steps:

[0038] The carrier powder is impregnated in a transition metal salt molten solution and dried to obtain a solid material; the obtained solid material is calcined at 250℃~350℃ in a nitrogen atmosphere to obtain the monofluoromethane purification adsorbent material.

[0039] The monofluoromethane purification adsorption material obtained by this invention can effectively improve the removal efficiency of fluorocarbon and hydrocarbon impurities in the gas-phase monofluoromethane feed gas, significantly reducing the difficulty of subsequent purification and making it easier to purify monofluoromethane to a purity of 5N or higher.

[0040] Specifically, in the method provided by this invention, the carrier powder is calcined at 250℃~350℃ in a nitrogen atmosphere, exhibiting excellent stability. The transition metal salt can gradually decompose and transform into uniformly dispersed active species, while also avoiding the aggregation of transition metal ions caused by high temperatures. This preserves highly dispersed active centers and enhances the chemical adsorption capacity for fluorocarbon and hydrocarbon impurities. At this calcination temperature, the interaction between the carrier powder and the transition metal is more gentle, synergistically achieving an impurity removal rate of over 99%.

[0041] In some embodiments, the oxygen content in the nitrogen atmosphere is 100ppm to 10000ppm, for example, it can be 100ppm, 500ppm, 1000ppm, 2000ppm, 3000ppm, 5000ppm, 6000ppm, 8000ppm or 10000ppm, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable, preferably 1000ppm to 3000ppm.

[0042] In this invention, oxygen content refers to the volume percentage of oxygen in a nitrogen atmosphere.

[0043] In some embodiments, the roasting time is 1h to 24h, for example, it can be 1h, 2h, 3h, 4h, 5h, 10h, 15h, 20h or 24h, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable, preferably 2h to 4h.

[0044] In some embodiments, the carrier powder includes any one or a combination of at least two of activated carbon, carbon nanotubes, molecular sieves or γ-Al2O3 powder, preferably activated carbon and / or carbon nanotubes.

[0045] Activated carbon and / or carbon nanotubes, as a preferred technical solution, have a stable structure at a calcination temperature of 250℃~350℃. Their framework structure is not destroyed by high temperature, and their abundant pores and large specific surface area are completely preserved, providing sufficient physical adsorption space for impurities.

[0046] In some embodiments, the transition metal salt in the transition metal salt solution includes any one or a combination of at least two of ferric nitrate, cobalt nitrate, nickel nitrate, copper nitrate, zinc nitrate, ferric chloride, cobalt chloride, nickel chloride, copper chloride, zinc chloride, ferric sulfate, cobalt sulfate, nickel sulfate, copper sulfate, or zinc sulfate, preferably a combination of cobalt nitrate and cobalt chloride.

[0047] When cobalt nitrate and cobalt chloride are calcined at 250℃~350℃, they are converted into different cobalt-based active substances. The nitrate ions in cobalt nitrate are easily decomposed into gaseous nitrogen oxides, which helps to prevent the agglomeration of cobalt-based active substances. The chloride ions in cobalt chloride can regulate the surface charge of the carrier powder, enhance the anchoring effect of cobalt ions and carrier defect sites, and reduce the shedding of active groups. The combined use of the two cobalt salts can make the cobalt-based active substances more uniformly dispersed in the carrier powder, with more adsorption sites, and improve the adsorption capacity for fluorocarbon and hydrocarbon impurities.

[0048] In some embodiments, the mass concentration of the transition metal salt solution is 1wt% to 30wt%, for example, it can be 1wt%, 5wt%, 10wt%, 15wt%, 20wt%, 25wt% or 30wt%, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable, preferably 10wt% to 20wt%.

[0049] In some embodiments, the mass ratio of the carrier powder to the transition metal salt solution is 1:1 to 1:20, for example, it can be 1:1, 1:2, 1:5, 1:8, 1:10, 1:15 or 1:20, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable, preferably 1:1 to 1:2.

[0050] In some embodiments, the drying temperature is 10°C to 200°C, for example, it can be 10°C, 50°C, 100°C, 120°C, 150°C, 180°C or 200°C, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable, preferably 100°C to 150°C.

[0051] In some embodiments, the drying time is 1h to 20h, for example, it can be 1h, 3h, 5h, 8h, 10h, 15h or 20h, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable, preferably 3h to 8h.

[0052] One embodiment of the present invention provides a fluoromethane purification adsorbent material, which is prepared by the preparation method described in any embodiment.

[0053] The present invention provides an application of the monofluoromethane purification adsorbent material according to any embodiment, the application including: purifying monofluoromethane feed gas using the monofluoromethane purification adsorbent material.

[0054] In some embodiments, the monofluoromethane purification adsorption material adsorbs fluorocarbon impurities and hydrocarbon impurities in the monofluoromethane feed gas.

[0055] Optionally, the feed gas velocity can be 0.01 s. -1 ~100s -1 For example, it could be 0.01s -1 0.1s -1 1s -1 2s -1 4s -1 5s -1 6s -1 8s -1 10s -1 12s -1 16s -1 20s -1 30s -1 50s -1 60s -1 80s -1 Or 100s -1 However, this does not limit the listed values; any unlisted values ​​within the range are also applicable, with 2s being the preferred value. -1 ~16s -1 .

[0056] The feed temperature of the raw gas can be -50℃ to 150℃, for example, -50℃, -40℃, 0℃, 10℃, 30℃, 50℃, 60℃, 80℃, 100℃, 120℃ or 150℃, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable, with -40℃ to 10℃ being the preferred value.

[0057] The relative pressure of adsorption can be 0 MPa to 2 MPa, for example, 0 MPa, 0.1 MPa, 0.2 MPa, 0.5 MPa, 1 MPa, 1.5 MPa or 2 MPa, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable, with 0.1 MPa to 0.2 MPa being the preferred value.

[0058] To clearly illustrate the technical solution of this invention, the main components of the monofluoromethane feed gas used in the following specific embodiments of this invention include 97.55% CH3F by volume, 800 ppmv CH3Cl, 6100 ppmv hydrocarbon impurities, and 10400 ppmv fluorocarbon impurities. This composition is only for the purpose of clearly illustrating the technical solution of this invention and is not considered as a further limitation of this invention.

[0059] Example 1

[0060] This embodiment provides a method for preparing a monofluoromethane purification adsorbent material, including the following steps:

[0061] (1) Carrier powder (coconut shell activated carbon, specific surface area of ​​800 m²) 2 (800 mg / g iodine value) was impregnated in a transition metal salt molten liquid and dried at 120℃ for 5 h to obtain a solid material;

[0062] The transition metal salt in the transition metal salt solution includes cobalt nitrate and cobalt chloride in a molar ratio of 1:1, with a concentration of 15 wt%; the mass ratio of the carrier powder to the transition metal salt solution is 1:1.5.

[0063] (2) The obtained solid material was calcined at 300°C for 3 hours in a nitrogen atmosphere (oxygen content of 2000ppm) to obtain the monofluoromethane purification adsorption material.

[0064] Example 2

[0065] This embodiment provides a method for preparing a monofluoromethane purification adsorbent material, including the following steps:

[0066] (1) The carrier powder (coconut shell activated carbon, the same as in Example 1) was impregnated in the transition metal salt molten liquid and dried at 100°C for 8 hours to obtain solid material;

[0067] The transition metal salt in the transition metal salt solution includes cobalt nitrate and cobalt chloride in a molar ratio of 1:1, with a concentration of 10 wt%; the mass ratio of the carrier powder to the transition metal salt solution is 1:1.

[0068] (2) The obtained solid material was calcined at 250°C for 4 hours in a nitrogen atmosphere (oxygen content of 1000ppm) to obtain the monofluoromethane purification adsorption material.

[0069] Example 3

[0070] This embodiment provides a method for preparing a monofluoromethane purification adsorbent material, including the following steps:

[0071] (1) The carrier powder (coconut shell activated carbon, the same as in Example 1) was impregnated in the transition metal salt molten liquid and dried at 150°C for 3 hours to obtain solid material;

[0072] The transition metal salt in the transition metal salt solution includes cobalt nitrate and cobalt chloride in a molar ratio of 1:1, with a concentration of 20 wt%; the mass ratio of the carrier powder to the transition metal salt solution is 1:2.

[0073] (2) The obtained solid material was calcined at 350°C for 2 hours in a nitrogen atmosphere (oxygen content of 3000ppm) to obtain the monofluoromethane purification adsorption material.

[0074] Example 4

[0075] This embodiment provides a method for preparing a monofluoromethane purification adsorbent material, including the following steps:

[0076] (1) The carrier powder (coconut shell activated carbon, the same as in Example 1) was impregnated in the transition metal salt molten liquid and dried at 10°C for 20 h to obtain solid material;

[0077] The transition metal salt in the transition metal salt solution includes cobalt nitrate and cobalt chloride in a molar ratio of 1:1, with a concentration of 1 wt%; the mass ratio of the carrier powder to the transition metal salt solution is 1:20.

[0078] (2) The obtained solid material was calcined at 300°C for 1 hour in a nitrogen atmosphere (oxygen content of 100 ppm) to obtain the monofluoromethane purification adsorption material.

[0079] Example 5

[0080] This embodiment provides a method for preparing a monofluoromethane purification adsorbent material, including the following steps:

[0081] (1) The carrier powder (coconut shell activated carbon, the same as in Example 1) was impregnated in the transition metal salt molten liquid and dried at 200°C for 1 hour to obtain solid material;

[0082] The transition metal salt in the transition metal salt solution includes cobalt nitrate and cobalt chloride in a molar ratio of 1:1, with a concentration of 30 wt%; the mass ratio of the carrier powder to the transition metal salt solution is 1:1.

[0083] (2) The obtained solid material was calcined at 300°C for 24 hours in a nitrogen atmosphere (oxygen content of 10000ppm) to obtain the monofluoromethane purification adsorption material.

[0084] Comparative Example 1

[0085] This comparative example provides a method for preparing a monofluoromethane purification adsorbent material, comprising the following steps:

[0086] (1) The carrier powder (coconut shell activated carbon, the same as in Example 1) was impregnated in the transition metal salt molten liquid and dried at 120°C for 5 hours to obtain solid material;

[0087] The transition metal salt in the transition metal salt solution includes cobalt nitrate and cobalt chloride in a molar ratio of 1:1, with a concentration of 15 wt%; the mass ratio of the carrier powder to the transition metal salt solution is 1:1.5.

[0088] (2) The obtained solid material was calcined at 200°C for 3 hours in a nitrogen atmosphere (oxygen content of 2000ppm) to obtain the monofluoromethane purification adsorption material.

[0089] Comparative Example 2

[0090] This comparative example provides a method for preparing a monofluoromethane purification adsorbent material, comprising the following steps:

[0091] (1) The carrier powder (coconut shell activated carbon, the same as in Example 1) was impregnated in the transition metal salt molten liquid and dried at 120°C for 5 hours to obtain solid material;

[0092] The transition metal salt in the transition metal salt solution includes cobalt nitrate and cobalt chloride in a molar ratio of 1:1, with a concentration of 15 wt%; the mass ratio of the carrier powder to the transition metal salt solution is 1:1.5.

[0093] (2) The obtained solid material was calcined at 400°C for 3 hours in a nitrogen atmosphere (oxygen content of 2000ppm) to obtain the monofluoromethane purification adsorption material.

[0094] Application Example 1-1

[0095] This application example provides the application of a fluoromethane purification adsorption material for purifying fluoromethane feed gas, including: filling the fluoromethane purification adsorption material prepared in Example 1 into an adsorption column to adsorb fluoromethane feed gas;

[0096] The feed space velocity of the monofluoromethane feed gas is 10 s. -1The feed temperature is 0℃ and the relative adsorption pressure is 0.15MPa.

[0097] Application Example 1-2

[0098] This application example provides the application of a fluoromethane purification adsorption material for purifying fluoromethane feed gas, including: filling the fluoromethane purification adsorption material prepared in Example 1 into an adsorption column to adsorb fluoromethane feed gas;

[0099] The feed space velocity of the monofluoromethane feed gas is 2s. -1 The feed temperature is -40℃ and the relative adsorption pressure is 0.1MPa.

[0100] Application Examples 1-3

[0101] This application example provides the application of a fluoromethane purification adsorption material for purifying fluoromethane feed gas, including: filling the fluoromethane purification adsorption material prepared in Example 1 into an adsorption column to adsorb fluoromethane feed gas;

[0102] The feed space velocity of the monofluoromethane feed gas is 16 s. -1 The feed temperature is 10℃ and the relative adsorption pressure is 0.2MPa.

[0103] Application Examples 1-4

[0104] This application example provides the application of a fluoromethane purification adsorption material for purifying fluoromethane feed gas, including: filling the fluoromethane purification adsorption material prepared in Example 1 into an adsorption column to adsorb fluoromethane feed gas;

[0105] The feed space velocity of the monofluoromethane feed gas is 0.01 s. -1 The feed temperature is -50℃ and the relative adsorption pressure is 0MPa.

[0106] Application Examples 1-5

[0107] This application example provides the application of a fluoromethane purification adsorption material for purifying fluoromethane feed gas, including: filling the fluoromethane purification adsorption material prepared in Example 1 into an adsorption column to adsorb fluoromethane feed gas;

[0108] The feed space velocity of the monofluoromethane feed gas is 100 s. -1 The feed temperature is 150℃ and the relative adsorption pressure is 2MPa.

[0109] Application Example 2

[0110] This application example provides the application of a monofluoromethane purification adsorption material for purifying monofluoromethane feed gas, including: filling the monofluoromethane purification adsorption material prepared in Example 2 into an adsorption column to adsorb monofluoromethane feed gas;

[0111] The feed space velocity of the monofluoromethane feed gas is 10 s. -1 The feed temperature is 0℃ and the relative adsorption pressure is 0.15MPa.

[0112] Application Example 3

[0113] This application example provides the application of a monofluoromethane purification adsorption material for purifying monofluoromethane feed gas, including: filling the monofluoromethane purification adsorption material prepared in Example 3 into an adsorption column to adsorb monofluoromethane feed gas;

[0114] The feed space velocity of the monofluoromethane feed gas is 10 s. -1 The feed temperature is 0℃ and the relative adsorption pressure is 0.15MPa.

[0115] Application Example 4

[0116] This application example provides the application of a fluoromethane purification adsorption material for purifying fluoromethane feed gas, including: filling the fluoromethane purification adsorption material prepared in Example 4 into an adsorption column to adsorb fluoromethane feed gas;

[0117] The feed space velocity of the monofluoromethane feed gas is 10 s. -1 The feed temperature is 0℃ and the relative adsorption pressure is 0.15MPa.

[0118] Application Example 5

[0119] This application example provides the application of a fluoromethane purification adsorption material for purifying fluoromethane feed gas, including: filling the fluoromethane purification adsorption material prepared in Example 5 into an adsorption column to adsorb fluoromethane feed gas;

[0120] The feed space velocity of the monofluoromethane feed gas is 10 s. -1 The feed temperature is 0℃ and the relative adsorption pressure is 0.15MPa.

[0121] Comparative Application Example 1

[0122] This comparative application example provides the application of the monofluoromethane purification adsorbent material for purifying monofluoromethane feed gas, including: the monofluoromethane purification adsorbent material prepared in Comparative Example 1 is filled into an adsorption column to adsorb monofluoromethane feed gas.

[0123] The feed space velocity of the monofluoromethane feed gas is 10 s. -1 The feed temperature is 0℃ and the relative adsorption pressure is 0.15MPa.

[0124] Comparative Application Example 2

[0125] This comparative application example provides the application of a monofluoromethane purification adsorbent material for purifying monofluoromethane feed gas, including: the monofluoromethane purification adsorbent material prepared in Comparative Example 2 is filled into an adsorption column to adsorb monofluoromethane feed gas.

[0126] The feed space velocity of the monofluoromethane feed gas is 10 s. -1 The feed temperature is 0℃ and the relative adsorption pressure is 0.15MPa.

[0127] Performance Characterization

[0128] The removal rates of fluorocarbon impurities, hydrocarbon impurities, fluorocarbon impurity content, and hydrocarbon impurity content in the above application examples were measured, and the results are shown in Table 1.

[0129] Table 1

[0130]

[0131] In summary, the monofluoromethane purification adsorption material obtained by this invention can effectively improve the removal efficiency of fluorocarbon and hydrocarbon impurities in the gas-phase monofluoromethane feed gas, significantly reducing the difficulty of subsequent purification and making it easier to purify monofluoromethane to a purity of 5N or higher.

[0132] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A method for preparing a monofluoromethane purification adsorbent, characterized in that, The preparation method includes the following steps: The carrier powder is impregnated in a transition metal salt molten solution and dried to obtain a solid material; the obtained solid material is calcined at 250℃~350℃ in a nitrogen atmosphere to obtain the monofluoromethane purification adsorbent material.

2. The preparation method according to claim 1, characterized in that, The oxygen content in the nitrogen atmosphere is 100ppm to 10000ppm; And / or, the oxygen content in the nitrogen atmosphere is 1000ppm to 3000ppm.

3. The preparation method according to claim 1 or 2, characterized in that, The roasting time is 1 hour to 24 hours; And / or, the calcination time is 2h to 4h.

4. The preparation method according to claim 1, characterized in that, The carrier powder includes any one or a combination of at least two of activated carbon, carbon nanotubes, molecular sieves or γ-Al2O3 powder; And / or, the transition metal salt in the transition metal salt solution includes any one or a combination of at least two of ferric nitrate, cobalt nitrate, nickel nitrate, copper nitrate, zinc nitrate, ferric chloride, cobalt chloride, nickel chloride, copper chloride, zinc chloride, ferric sulfate, cobalt sulfate, nickel sulfate, copper sulfate, or zinc sulfate.

5. The preparation method according to claim 1 or 4, characterized in that, The mass concentration of the transition metal salt solution is 1wt%~30wt%; And / or, the mass concentration of the transition metal salt solution is 10wt%~20wt%.

6. The preparation method according to claim 5, characterized in that, The mass ratio of the carrier powder to the transition metal salt solution is 1:1 to 1:20; And / or, the mass ratio of the carrier powder to the transition metal salt solution is 1:1 to 1:

2.

7. The preparation method according to claim 1, characterized in that, The drying temperature is 10℃~200℃; And / or, the drying temperature is 100℃~150℃; And / or, the drying time is 1 hour to 20 hours; And / or, the drying time is 3h to 8h.

8. A monofluoromethane purification adsorption material, characterized in that, The monofluoromethane purification adsorbent material is prepared by the preparation method described in any one of claims 1 to 7.

9. An application of the monofluoromethane purification adsorbent material according to claim 8, characterized in that, The application includes: purifying monofluoromethane feed gas using monofluoromethane purification adsorbent materials.

10. The application according to claim 9, characterized in that, The monofluoromethane purification adsorption material adsorbs fluorocarbon and hydrocarbon impurities in the monofluoromethane feed gas.

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