Modified organic metal ligand and preparation method thereof, adsorbent for removing methane and phosphine in recycle hydrogen and preparation method of adsorbent
The problem of difficult removal of methane and phosphine in circulating hydrogen is solved by modified organometallic ligands and hydrothermal method, and efficient removal and improved polysilicon quality.
Patent Information
- Application Number
- CN202411245977.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-05
- Publication Date
- 2024-12-13
AI Technical Summary
In the existing polycrystalline silicon production process, methane and phosphine in the circulating hydrogen are difficult to efficiently remove, affecting the quality of polycrystalline silicon.
Modified organometallic ligands and preparation methods are adopted to generate 2-sulfonate terephthalephthalicarboxyl modified organometallic ligands with developed pore structure and high specific surface area as adsorbent carriers, and pass hydrothermal The active components are supported by the method and combined with chemical reactions to improve the removal efficiency of methane and phosphine.
It realizes efficient adsorption and removal of methane and phosphine in circulating hydrogen, maintains the structural integrity of the adsorbent, and improves the quality of polycrystalline silicon products.
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Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of polysilicon production, and specifically relates to a modified organic metal ligand and a preparation method thereof, and an adsorbent for removing methane and phosphine from circulating hydrogen and a preparation method thereof. Background Art
[0002] Polysilicon is an important raw material used in the photovoltaic power generation field, chip semiconductor and other industries. As the industry's requirements for polysilicon purity increase, how to effectively remove impurities in polysilicon to achieve stable production of high-quality products has become a research focus in polysilicon production.
[0003] At present, the modified Siemens process is still the main application technology for polysilicon production. In the modified Siemens process for polysilicon production, circulating hydrogen is one of the main materials for producing silicon rods in the reduction furnace and is used in large quantities. Therefore, reducing the content of impurities in circulating hydrogen is of great significance to improving the grade of polysilicon products.
[0004] The current recycling and purification process of circulating hydrogen is as follows: the reduction tail gas is first separated out of chlorosilane through low-pressure multi-stage condensation, and the non-condensable mixed gas is separated from the hydrogen chloride through the absorption process to obtain hydrogen at the top of the absorption tower. The hydrogen is purified by the activated carbon adsorption column and then circulated to the reduction furnace for reaction. This process is relatively mature, but the problem is that the methane and phosphine in the hydrogen cannot be efficiently removed by the currently commonly used activated carbon adsorption due to their own characteristics. As the hydrogen is continuously recycled and circulated, they will gradually accumulate in the system and affect the quality of polysilicon.
[0005] In the existing circulating hydrogen adsorption process, activated carbon is usually used as an adsorbent. Activated carbon itself has a poor adsorption effect on methane and phosphine in hydrogen. Usually, the purity of the circulating hydrogen is improved as much as possible by increasing equipment investment. Summary of the invention
[0006] The technical problem to be solved by the present invention is to provide a modified organic metal ligand and a preparation method thereof, an adsorbent and a preparation method thereof for removing methane and phosphine from circulating hydrogen in view of the above-mentioned deficiencies in the prior art. The adsorbent prepared by the scheme has a developed pore structure, a large number of micropores, a large specific surface area, and a small and uniformly distributed active component particle size, and can efficiently purify methane and phosphine in circulating hydrogen, thereby achieving the purpose of simultaneously and efficiently removing methane and phosphine.
[0007] The technical solution adopted to solve the technical problem of the present invention is to provide a method for preparing a modified organic metal ligand, comprising the following steps:
[0008] 1) adding a first metal salt and terephthalic acid into a first solvent, heating and reacting to generate an organic metal ligand MOF;
[0009] 2) Separate the organic metal ligand MOF, mix it with the N,N-dimethylformamide DMF solution of 2-sulfonatoterephthalic acid monosodium, and react it to generate the organic metal ligand MOF modified with 2-sulfonatoterephthalic acid carboxyl group. The organic metal ligand MOF modified with 2-sulfonatoterephthalic acid carboxyl group is an adsorbent carrier.
[0010] Preferably, the first metal salt in step 1) is one or more of aluminum nitrate, aluminum chloride, ferric nitrate, ferric chloride, chromium nitrate, and chromium chloride. The first metal salt contains crystal water or does not contain crystal water.
[0011] Preferably, the molar ratio of the first metal salt to terephthalic acid in step 1) is (1-5):1.
[0012] Preferably, the first solvent in step 1) is one or more of water, hydrofluoric acid, and N,N-dimethylformamide (DMF). The water is deionized water.
[0013] Preferably, the heating temperature in step 1) is 100-250° C., and the heating time is 1-12 hours.
[0014] Preferably, in step 1), the temperature is raised to 100-250° C. at a rate of 0.5-15° C. / min.
[0016] Preferably, the concentration of the N,N-dimethylformamide (DMF) solution of monosodium 2-sulfonate terephthalate in step 2) is 1 to 5 g / L.
[0017] Preferably, the reaction temperature in step 2) is 60-80° C. and the reaction time is 4-12 h.
[0018] Preferably, the step 2) further comprises the following step f) separating the product after the reaction is completed, and then soaking in a hydrochloric acid solution, separating the solid, washing, and drying to obtain an organic metal ligand MOF modified with 2-sulfonatoterephthalic acid carboxyl.
[0019] Preferably, the concentration of the hydrochloric acid solution used for soaking in step f) is 1-4 mol / L, and the soaking time is 15-40 min.
[0020] Preferably, in step f), the washing operation is firstly performed with water until neutral, and then sequentially with N,N-dimethylformamide DMF and ethanol for 6 to 10 times, and the drying operation is vacuum drying at a drying temperature of 60 to 120° C. for a drying time of 4 to 12 hours. The washing water is deionized water.
[0021] The present invention also provides a modified organic metal ligand, which is prepared by the above method.
[0022] The present invention also provides a method for preparing an adsorbent for removing methane and phosphine from circulating hydrogen, comprising the following steps:
[0023] a) adding a second metal salt and the modified organometallic ligand MOF prepared by the above method into a second solvent, heating and reacting the mixture to generate an adsorbent for removing methane and phosphine from circulating hydrogen.
[0024] Preferably, the second metal salt is a copper metal salt, and the copper metal salt is one or more of copper acetate, copper nitrate, copper chloride, copper sulfate, and copper carbonate.
[0025] Preferably, the second metal salt in the solution in step a) has a metal element mass fraction of 5% to 15%.
[0026] Preferably, the second solvent is one or more of water, methanol, ethanol and ethylene glycol.
[0027] Preferably, the reaction in step a) is a hydrothermal reaction, the heating temperature is 100 to 250° C., and the heating time is 4 to 12 hours.
[0028] Preferably, in step a), the temperature is increased to 100-250° C. at a rate of 0.5-15° C. / min.
[0029] Preferably, the step a) further comprises the following step b) after the reaction is completed, cooling to room temperature, washing with water, filtering and drying to obtain an adsorbent for removing methane and phosphine from circulating hydrogen.
[0030] Preferably, the drying in step b) is vacuum drying, the drying temperature is 60 to 120° C., and the drying time is 4 to 12 hours.
[0031] The present invention also provides an adsorbent for removing methane and phosphine from circulating hydrogen, which is prepared by the above method.
[0032] Compared with the prior art, the modified organic metal ligand and its preparation method, the adsorbent for removing methane and phosphine from circulating hydrogen and its preparation method in the present invention have the advantages of
[0033] The following beneficial effects:
[0034] (1) The material structure is maintained and the methane adsorption effect is good. According to the adsorption requirements, the pore structure and other characteristics of the metal organic framework can be controlled by the solvent ratio during the synthesis process, and the metal salt is loaded by the hydrothermal method to avoid the damage to the structure of the adsorbent itself by high-temperature calcination in the conventional impregnation loading method. The structure and pore size of the metal organic framework are maintained, so the adsorbent of the present invention can show high efficiency in the adsorption of methane.
[0035] (2) High efficiency in removing phosphine. The process of removing phosphine is as follows: phosphine first enters the pores of the adsorbent and is adsorbed, and then the adsorbed phosphine reacts chemically with the active components loaded on the adsorbent. The present invention first synthesizes a metal organic framework material, and then introduces electrophilic functional groups such as sulfonic acid and carboxyl to modify the metal organic framework. This process of introducing electrophilic functional groups not only ensures that the pores and structure of the metal organic framework are not changed, but also strengthens the adsorption process of the adsorbent for phosphine. The directly loaded active components or the decomposition products of the metal salt loaded during the hydrothermal process can react chemically with the adsorbed phosphine. The method of combining efficient adsorption with chemical reaction of the present invention can fully improve the removal rate of phosphine.
[0036] (3) Good loading effect of active components. The hydrothermal method can load the active components more evenly on the metal organic framework to avoid the agglomeration of active components caused by conventional impregnation methods. In addition, the active components have small particle size and do not block the pore structure of the metal organic framework material. DETAILED DESCRIPTION
[0037] In order to enable those skilled in the art to better understand the technical solution of the present invention, the present invention is further described in detail below in conjunction with specific implementation methods.
[0038] Example 1
[0039] This embodiment provides a method for preparing a modified organometallic ligand, comprising:
[0040] Next steps:
[0041] 1) adding a first metal salt and terephthalic acid into a first solvent, heating and reacting to generate an organic metal ligand MOF;
[0042] 2) Separating the organic metal ligand MOF, mixing it with the N,N-dimethylformamide DMF solution of 2-sulfonato terephthalic acid monosodium, and reacting it to generate the organic metal ligand MOF modified with 2-sulfonato terephthalic acid carboxyl group.
[0043] This embodiment also provides a modified organic metal ligand, which is prepared by the above method.
[0044] This embodiment also provides a method for preparing an adsorbent for removing methane and phosphine from circulating hydrogen, comprising the following steps:
[0045] a) adding a second metal salt and the modified organometallic ligand MOF prepared by the above method into a second solvent, heating and reacting the mixture to generate an adsorbent for removing methane and phosphine from circulating hydrogen.
[0046] This embodiment also provides an adsorbent for removing methane and phosphine from circulating hydrogen, which is prepared by the above method.
[0047] Compared with the prior art, the modified organic metal ligand and the preparation method thereof in this embodiment, the adsorbent for removing methane and phosphine from circulating hydrogen and the preparation method thereof have the following beneficial effects:
[0048] (1) The material structure is maintained and the methane adsorption effect is good. According to the adsorption requirements, the pore structure and other characteristics of the metal organic framework can be controlled by the solvent ratio during the synthesis process, and the metal salt loading by the hydrothermal method can avoid the damage to the structure of the adsorbent itself by high temperature calcination in the conventional impregnation loading method. The structure and pore size of the metal organic framework are maintained, so the adsorbent of this embodiment can show efficient adsorption of methane.
[0049] (2) High efficiency in removing phosphine. The process of removing phosphine is as follows: phosphine first enters the pores of the adsorbent and is adsorbed, and then the adsorbed phosphine reacts chemically with the active components loaded on the adsorbent. In this embodiment, a metal organic framework material is first synthesized, and then electrophilic functional groups such as sulfonic acid group and carboxyl group are introduced to modify the metal organic framework. This process of introducing electrophilic functional groups not only ensures that the pores and structure of the metal organic framework are not changed, but also strengthens the adsorption process of phosphine by the adsorbent. The directly loaded active components or the decomposition products of the metal salt loaded during the hydrothermal process can react chemically with the adsorbed phosphine. The combination of efficient adsorption and chemical reaction in this embodiment can fully improve the removal rate of phosphine.
[0050] (3) Good loading effect of active components. The hydrothermal method can load the active components more evenly on the metal organic framework to avoid the agglomeration of active components caused by conventional impregnation methods. In addition, the active components have small particle size and do not block the pore structure of the metal organic framework material.
[0051] Example 2
[0052] This embodiment provides a method for preparing a modified organometallic ligand, comprising the following steps:
[0053] 1) adding a first metal salt and terephthalic acid into a first solvent, heating and reacting to generate an organic metal ligand MOF;
[0054] 2) Separate the organic metal ligand MOF, mix it with the N,N-dimethylformamide DMF solution of 2-sulfonatoterephthalic acid monosodium, and react it to generate the organic metal ligand MOF modified with 2-sulfonatoterephthalic acid carboxyl group. The organic metal ligand MOF modified with 2-sulfonatoterephthalic acid carboxyl group is an adsorbent carrier.
[0055] Preferably, the first metal salt in step 1) is one or more of aluminum nitrate, aluminum chloride, ferric nitrate, ferric chloride, chromium nitrate, and chromium chloride. The first metal salt contains crystal water or does not contain crystal water.
[0056] Preferably, the molar ratio of the first metal salt to terephthalic acid in step 1) is (1-5):1.
[0057] Preferably, the first solvent in step 1) is one or more of water, hydrofluoric acid, and N,N-dimethylformamide (DMF). The water is deionized water.
[0058] Preferably, the heating temperature in step 1) is 100-250° C., and the heating time is 1-12 hours.
[0059] Preferably, in step 1), the temperature is raised to 100-250° C. at a rate of 0.5-15° C. / min.
[0060] Preferably, the concentration of the N,N-dimethylformamide (DMF) solution of monosodium 2-sulfonate terephthalate in step 2) is 1 to 5 g / L.
[0061] Preferably, the reaction temperature in step 2) is 60-80° C. and the reaction time is 4-12 h.
[0062] Preferably, the step 2) further comprises the following step f) separating the product after the reaction is completed, and then soaking in a hydrochloric acid solution, separating the solid, washing, and drying to obtain an organic metal ligand MOF modified with 2-sulfonatoterephthalic acid carboxyl.
[0063] Preferably, the concentration of the hydrochloric acid solution used for soaking in step f) is 1-4 mol / L, and the soaking time is 15-40 min.
[0064] Preferably, in step f), the washing operation is firstly performed with water until neutral, and then sequentially with N,N-dimethylformamide DMF and ethanol for 6 to 10 times, and the drying operation is vacuum drying at a drying temperature of 60 to 120° C. for a drying time of 4 to 12 hours. The washing water is deionized water.
[0065] This embodiment also provides a modified organic metal ligand, which is prepared by the above method.
[0066] This embodiment also provides a method for preparing an adsorbent for removing methane and phosphine from circulating hydrogen, comprising the following steps:
[0067] a) adding a second metal salt and the modified organometallic ligand MOF prepared by the above method into a second solvent, heating and reacting the mixture to generate an adsorbent for removing methane and phosphine from circulating hydrogen.
[0068] Preferably, the second metal salt is a copper metal salt, and the copper metal salt is one or more of copper acetate, copper nitrate, copper chloride, copper sulfate, and copper carbonate.
[0069] Preferably, the second metal salt in the solution in step a) has a metal element mass fraction of 5% to 15%.
[0070] Preferably, the second solvent is one or more of water, methanol, ethanol and ethylene glycol.
[0071] Preferably, the reaction in step a) is a hydrothermal reaction, the heating temperature is 100 to 250° C., and the heating time is 4 to 12 hours.
[0072] Preferably, in step a), the temperature is increased to 100-250° C. at a rate of 0.5-15° C. / min.
[0073] Preferably, the step a) further comprises the following step b) after the reaction is completed, cooling to room temperature, washing with water, filtering and drying to obtain an adsorbent for removing methane and phosphine from circulating hydrogen.
[0074] Preferably, the drying in step b) is vacuum drying, the drying temperature is 60 to 120° C., and the drying time is 4 to 12 hours.
[0075] This embodiment also provides an adsorbent for removing methane and phosphine from circulating hydrogen, which is prepared by the above method.
[0076] Specifically, this embodiment provides a method for preparing an adsorbent for removing methane and phosphine from circulating hydrogen, comprising the following steps:
[0077] (1) Aluminum chloride hexahydrate and terephthalic acid in a molar ratio of 3:1 were added to a solvent in which deionized water and hydrofluoric acid were in a volume ratio of 10:1, and the mixture was ultrasonically dispersed, stirred at room temperature until the mixture was uniformly mixed, and then transferred to a reactor, and the temperature was raised to 200°C at a rate of 5°C / min for 6 hours to generate an organometallic ligand MOF;
[0078] (2) After the reaction is completed, the temperature is lowered to 60°C, the organic metal ligand MOF is obtained by filtration, and placed in a reactor. A DMF solution of 2-sulfonato terephthalate monosodium with a concentration of 1.9 g / L is added to the reactor, and the mixture is stirred evenly and then reacted at 60°C for 8 hours to generate an organic metal ligand MOF modified with 2-sulfonato terephthalic acid carboxyl. After the reaction is completed, the mixture is cooled to room temperature and filtered, and then soaked in 1 mol / L hydrochloric acid for 15 minutes. After soaking, the mixture is washed with deionized water until neutral, and then washed with DMF and ethanol in turn, and finally dried under vacuum at 100°C for 6 hours to obtain an organic metal ligand MOF modified with 2-sulfonato terephthalic acid carboxyl, which is an adsorbent carrier;
[0079] (3) The active component copper acetate is placed in ethanol and stirred until completely dissolved, and then the adsorbent carrier obtained in step (2) is placed in the solution, with the mass fraction of copper acetate being 10% based on copper. After stirring and mixing evenly at room temperature, the mixture is placed in a reactor for reaction, and the temperature is raised to 200° C. at a rate of 5° C. / min for reaction for 6 h. After the reaction is completed, the mixture is cooled to room temperature, washed with deionized water, filtered, and then the product is vacuum dried at 100° C. for 6 h to obtain an adsorbent product, which is recorded as MIL-1.
[0080] Compared with the prior art, the modified organic metal ligand and the preparation method thereof in this embodiment, the adsorbent for removing methane and phosphine from circulating hydrogen and the preparation method thereof have the following beneficial effects:
[0081] (1) The material structure is maintained and the methane adsorption effect is good. According to the adsorption requirements, the pore structure and other characteristics of the metal organic framework can be controlled by the solvent ratio during the synthesis process, and the metal salt loading by the hydrothermal method can avoid the damage to the structure of the adsorbent itself by high temperature calcination in the conventional impregnation loading method. The structure and pore size of the metal organic framework are maintained, so the adsorbent of this embodiment can show efficient adsorption of methane.
[0082] (2) High efficiency in removing phosphine. The process of removing phosphine is as follows: phosphine first enters the pores of the adsorbent and is adsorbed, and then the adsorbed phosphine reacts chemically with the active components loaded on the adsorbent. In this embodiment, a metal organic framework material is first synthesized, and then electrophilic functional groups such as sulfonic acid group and carboxyl group are introduced to modify the metal organic framework. This process of introducing electrophilic functional groups not only ensures that the pores and structure of the metal organic framework are not changed, but also strengthens the adsorption process of phosphine by the adsorbent. The directly loaded active components or the decomposition products of the metal salt loaded during the hydrothermal process can react chemically with the adsorbed phosphine. The combination of efficient adsorption and chemical reaction in this embodiment can fully improve the removal rate of phosphine.
[0083] (3) Good loading effect of active components. The hydrothermal method can load the active components more evenly on the metal organic framework to avoid the agglomeration of active components caused by conventional impregnation methods. In addition, the active components have small particle size and do not block the pore structure of the metal organic framework material.
[0084] Example 3
[0085] The preparation steps of the adsorbent in Example 3 are the same as those in Example 2, except that the solvent in step (1) is replaced with DMF. The obtained adsorbent product is recorded as MIL-2.
[0086] Compared with the prior art, the modified organic metal ligand and the preparation method thereof in this embodiment, the adsorbent for removing methane and phosphine from circulating hydrogen and the preparation method thereof have the following beneficial effects:
[0087] (1) The material structure is maintained and the methane adsorption effect is good. According to the adsorption requirements, the pore structure and other characteristics of the metal organic framework can be controlled by the solvent ratio during the synthesis process, and the metal salt loading by the hydrothermal method can avoid the damage to the structure of the adsorbent itself by high temperature calcination in the conventional impregnation loading method. The structure and pore size of the metal organic framework are maintained, so the adsorbent of this embodiment can show efficient adsorption of methane.
[0088] (2) High efficiency in removing phosphine. The process of removing phosphine is as follows: phosphine first enters the pores of the adsorbent and is adsorbed, and then the adsorbed phosphine reacts chemically with the active components loaded on the adsorbent. In this embodiment, a metal organic framework material is first synthesized, and then electrophilic functional groups such as sulfonic acid group and carboxyl group are introduced to modify the metal organic framework. This process of introducing electrophilic functional groups not only ensures that the pores and structure of the metal organic framework are not changed, but also strengthens the adsorption process of phosphine by the adsorbent. The directly loaded active components or the decomposition products of the metal salt loaded during the hydrothermal process can react chemically with the adsorbed phosphine. The combination of efficient adsorption and chemical reaction in this embodiment can fully improve the removal rate of phosphine.
[0089] (3) Good loading effect of active components. The hydrothermal method can load the active components more evenly on the metal organic framework to avoid the agglomeration of active components caused by conventional impregnation methods. In addition, the active components have small particle size and do not block the pore structure of the metal organic framework material.
[0090] Example 4
[0091] The preparation steps of the adsorbent in Example 4 are the same as those in Example 2, except that the metal salt in step (1) is replaced with ferric chloride hexahydrate. The obtained adsorbent product is recorded as MIL-3.
[0092] Compared with the prior art, the modified organic metal ligand and the preparation method thereof in this embodiment, the adsorbent for removing methane and phosphine from circulating hydrogen and the preparation method thereof have the following beneficial effects:
[0093] (1) The material structure is maintained and the methane adsorption effect is good. According to the adsorption requirements, the pore structure and other characteristics of the metal organic framework can be controlled by the solvent ratio during the synthesis process, and the metal salt loading by the hydrothermal method can avoid the damage to the structure of the adsorbent itself by high temperature calcination in the conventional impregnation loading method. The structure and pore size of the metal organic framework are maintained, so the adsorbent of this embodiment can show efficient adsorption of methane.
[0094] (2) High efficiency in removing phosphine. The process of removing phosphine is as follows: phosphine first enters the pores of the adsorbent and is adsorbed, and then the adsorbed phosphine reacts chemically with the active components loaded on the adsorbent. In this embodiment, a metal organic framework material is first synthesized, and then electrophilic functional groups such as sulfonic acid group and carboxyl group are introduced to modify the metal organic framework. This process of introducing electrophilic functional groups not only ensures that the pores and structure of the metal organic framework are not changed, but also strengthens the adsorption process of phosphine by the adsorbent. The directly loaded active components or the decomposition products of the metal salt loaded during the hydrothermal process can react chemically with the adsorbed phosphine. The combination of efficient adsorption and chemical reaction in this embodiment can fully improve the removal rate of phosphine.
[0095] (3) Good loading effect of active components. The hydrothermal method can load the active components more evenly on the metal organic framework to avoid the agglomeration of active components caused by conventional impregnation methods. In addition, the active components have small particle size and do not block the pore structure of the metal organic framework material.
[0096] Example 5
[0097] The steps for preparing the adsorbent in Example 5 are the same as those in Example 2, except that the metal salt in step (1) is replaced with chromium chloride hexahydrate. The obtained adsorbent product is recorded as MIL-4.
[0098] Compared with the prior art, the modified organic metal ligand and the preparation method thereof in this embodiment, the adsorbent for removing methane and phosphine from circulating hydrogen and the preparation method thereof have the following beneficial effects:
[0099] (1) The material structure is maintained and the methane adsorption effect is good. According to the adsorption requirements, the pore structure and other characteristics of the metal organic framework can be controlled by the solvent ratio during the synthesis process, and the metal salt loading by the hydrothermal method can avoid the damage to the structure of the adsorbent itself by high temperature calcination in the conventional impregnation loading method. The structure and pore size of the metal organic framework are maintained, so the adsorbent of this embodiment can show efficient adsorption of methane.
[0100] (2) High efficiency in removing phosphine. The process of removing phosphine is as follows: phosphine first enters the pores of the adsorbent and is adsorbed, and then the adsorbed phosphine reacts chemically with the active components loaded on the adsorbent. In this embodiment, a metal organic framework material is first synthesized, and then electrophilic functional groups such as sulfonic acid group and carboxyl group are introduced to modify the metal organic framework. This process of introducing electrophilic functional groups not only ensures that the pores and structure of the metal organic framework are not changed, but also strengthens the adsorption process of phosphine by the adsorbent. The directly loaded active components or the decomposition products of the metal salt loaded during the hydrothermal process can react chemically with the adsorbed phosphine. The combination of efficient adsorption and chemical reaction in this embodiment can fully improve the removal rate of phosphine.
[0101] (3) Good loading effect of active components. The hydrothermal method can load the active components more evenly on the metal organic framework to avoid the agglomeration of active components caused by conventional impregnation methods. In addition, the active components have small particle size and do not block the pore structure of the metal organic framework material.
[0102] Example 6
[0103] The preparation steps of the adsorbent in Example 6 are the same as those in Example 2, except that the solvent in step (1) is replaced with a mixture of DMF and water in a volume ratio of 10:1. The obtained adsorbent product is recorded as MIL-5.
[0104] Compared with the prior art, the modified organic metal ligand and the preparation method thereof in this embodiment, the adsorbent for removing methane and phosphine from circulating hydrogen and the preparation method thereof have the following beneficial effects:
[0105] (1) The material structure is maintained and the methane adsorption effect is good. According to the adsorption requirements, the pore structure and other characteristics of the metal organic framework can be controlled by the solvent ratio during the synthesis process, and the metal salt loading by the hydrothermal method can avoid the damage to the structure of the adsorbent itself by high temperature calcination in the conventional impregnation loading method. The structure and pore size of the metal organic framework are maintained, so the adsorbent of this embodiment can show efficient adsorption of methane.
[0106] (2) High efficiency in removing phosphine. The process of removing phosphine is as follows: phosphine first enters the pores of the adsorbent and is adsorbed, and then the adsorbed phosphine reacts chemically with the active components loaded on the adsorbent. In this embodiment, a metal organic framework material is first synthesized, and then electrophilic functional groups such as sulfonic acid group and carboxyl group are introduced to modify the metal organic framework. This process of introducing electrophilic functional groups not only ensures that the pores and structure of the metal organic framework are not changed, but also strengthens the adsorption process of phosphine by the adsorbent. The directly loaded active components or the decomposition products of the metal salt loaded during the hydrothermal process can react chemically with the adsorbed phosphine. The combination of efficient adsorption and chemical reaction in this embodiment can fully improve the removal rate of phosphine.
[0107] (3) Good loading effect of active components. The hydrothermal method can load the active components more evenly on the metal organic framework to avoid the agglomeration of active components caused by conventional impregnation methods. In addition, the active components have small particle size and do not block the pore structure of the metal organic framework material.
[0108] Example 7
[0109] The preparation steps of the adsorbent in Example 7 are the same as those in Example 2, except that the concentration of the 2-sulfonato monosodium terephthalate DMF solution in step (2) is changed to 2.5 g / L, and the obtained adsorbent product is MIL-6.
[0110] Compared with the prior art, the modified organic metal ligand and the preparation method thereof in this embodiment, the adsorbent for removing methane and phosphine from circulating hydrogen and the preparation method thereof have the following beneficial effects:
[0111] (1) The material structure is maintained and the methane adsorption effect is good. According to the adsorption requirements, the pore structure and other characteristics of the metal organic framework can be controlled by the solvent ratio during the synthesis process, and the metal salt loading by the hydrothermal method can avoid the damage to the structure of the adsorbent itself by high temperature calcination in the conventional impregnation loading method. The structure and pore size of the metal organic framework are maintained, so the adsorbent of this embodiment can show efficient adsorption of methane.
[0112] (2) High efficiency in removing phosphine. The process of removing phosphine is as follows: phosphine first enters the pores of the adsorbent and is adsorbed, and then the adsorbed phosphine reacts chemically with the active components loaded on the adsorbent. In this embodiment, a metal organic framework material is first synthesized, and then electrophilic functional groups such as sulfonic acid group and carboxyl group are introduced to modify the metal organic framework. This process of introducing electrophilic functional groups not only ensures that the pores and structure of the metal organic framework are not changed, but also strengthens the adsorption process of phosphine by the adsorbent. The directly loaded active components or the decomposition products of the metal salt loaded during the hydrothermal process can react chemically with the adsorbed phosphine. The combination of efficient adsorption and chemical reaction in this embodiment can fully improve the removal rate of phosphine.
[0113] (3) Good loading effect of active components. The hydrothermal method can load the active components more evenly on the metal organic framework to avoid the agglomeration of active components caused by conventional impregnation methods. In addition, the active components have small particle size and do not block the pore structure of the metal organic framework material.
[0114] Example 8
[0115] The preparation steps of the adsorbent in Example 8 are the same as those in Example 2, except that the concentration of the hydrochloric acid solution in step (2) is changed to 1.7 mol / L, and the obtained adsorbent product is recorded as MIL-7.
[0116] Compared with the prior art, the modified organic metal ligand and the preparation method thereof in this embodiment, the adsorbent for removing methane and phosphine from circulating hydrogen and the preparation method thereof have the following beneficial effects:
[0117] (1) The material structure is maintained and the methane adsorption effect is good. According to the adsorption requirements, the pore structure and other characteristics of the metal organic framework can be controlled by the solvent ratio during the synthesis process, and the metal salt loading by the hydrothermal method can avoid the damage to the structure of the adsorbent itself by high temperature calcination in the conventional impregnation loading method. The structure and pore size of the metal organic framework are maintained, so the adsorbent of this embodiment can show efficient adsorption of methane.
[0118] (2) High efficiency in removing phosphine. The process of removing phosphine is as follows: phosphine first enters the pores of the adsorbent and is adsorbed, and then the adsorbed phosphine reacts chemically with the active components loaded on the adsorbent. In this embodiment, a metal organic framework material is first synthesized, and then electrophilic functional groups such as sulfonic acid group and carboxyl group are introduced to modify the metal organic framework. This process of introducing electrophilic functional groups not only ensures that the pores and structure of the metal organic framework are not changed, but also strengthens the adsorption process of phosphine by the adsorbent. The directly loaded active components or the decomposition products of the metal salt loaded during the hydrothermal process can react chemically with the adsorbed phosphine. The combination of efficient adsorption and chemical reaction in this embodiment can fully improve the removal rate of phosphine.
[0119] (3) Good loading effect of active components. The hydrothermal method can load the active components more evenly on the metal organic framework to avoid the agglomeration of active components caused by conventional impregnation methods. In addition, the active components have small particle size and do not block the pore structure of the metal organic framework material.
[0120] Example 9
[0121] The preparation steps of the adsorbent in Example 9 are the same as those in Example 2, except that the solvent in step (3) is replaced with a mixed solution of water and ethanol in a volume ratio of 10:1. The obtained adsorbent product is recorded as MIL-8.
[0122] Compared with the prior art, the modified organic metal ligand and the preparation method thereof in this embodiment, the adsorbent for removing methane and phosphine from circulating hydrogen and the preparation method thereof have the following beneficial effects:
[0123] (1) The material structure is maintained and the methane adsorption effect is good. According to the adsorption requirements, the pore structure and other characteristics of the metal organic framework can be controlled by the solvent ratio during the synthesis process, and the metal salt loading by the hydrothermal method can avoid the damage to the structure of the adsorbent itself by high temperature calcination in the conventional impregnation loading method. The structure and pore size of the metal organic framework are maintained, so the adsorbent of this embodiment can show efficient adsorption of methane.
[0124] (2) High efficiency in removing phosphine. The process of removing phosphine is as follows: phosphine first enters the pores of the adsorbent and is adsorbed, and then the adsorbed phosphine reacts chemically with the active components loaded on the adsorbent. In this embodiment, a metal organic framework material is first synthesized, and then electrophilic functional groups such as sulfonic acid group and carboxyl group are introduced to modify the metal organic framework. This process of introducing electrophilic functional groups not only ensures that the pores and structure of the metal organic framework are not changed, but also strengthens the adsorption process of phosphine by the adsorbent. The directly loaded active components or the decomposition products of the metal salt loaded during the hydrothermal process can react chemically with the adsorbed phosphine. The combination of efficient adsorption and chemical reaction in this embodiment can fully improve the removal rate of phosphine.
[0125] (3) Good loading effect of active components. The hydrothermal method can load the active components more evenly on the metal organic framework to avoid the agglomeration of active components caused by conventional impregnation methods. In addition, the active components have small particle size and do not block the pore structure of the metal organic framework material.
[0126] Example 10
[0127] The preparation steps of the adsorbent in Example 10 are the same as those in Example 2, except that the mass fraction of the active component in step (3) is changed to 12%. The obtained adsorbent product is recorded as MIL-9.
[0128] Compared with the prior art, the modified organic metal ligand and the preparation method thereof in this embodiment, the adsorbent for removing methane and phosphine from circulating hydrogen and the preparation method thereof have the following beneficial effects:
[0129] (1) The material structure is maintained and the methane adsorption effect is good. According to the adsorption requirements, the pore structure and other characteristics of the metal organic framework can be controlled by the solvent ratio during the synthesis process, and the metal salt loading by the hydrothermal method can avoid the damage to the structure of the adsorbent itself by high temperature calcination in the conventional impregnation loading method. The structure and pore size of the metal organic framework are maintained, so the adsorbent of this embodiment can show efficient adsorption of methane.
[0130] (2) High efficiency in removing phosphine. The process of removing phosphine is as follows: phosphine first enters the pores of the adsorbent and is adsorbed, and then the adsorbed phosphine reacts chemically with the active components loaded on the adsorbent. In this embodiment, a metal organic framework material is first synthesized, and then electrophilic functional groups such as sulfonic acid group and carboxyl group are introduced to modify the metal organic framework. This process of introducing electrophilic functional groups not only ensures that the pores and structure of the metal organic framework are not changed, but also strengthens the adsorption process of phosphine by the adsorbent. The directly loaded active components or the decomposition products of the metal salt loaded during the hydrothermal process can react chemically with the adsorbed phosphine. The combination of efficient adsorption and chemical reaction in this embodiment can fully improve the removal rate of phosphine.
[0131] (3) Good loading effect of active components. The hydrothermal method can load the active components more evenly on the metal organic framework to avoid the agglomeration of active components caused by conventional impregnation methods. In addition, the active components have small particle size and do not block the pore structure of the metal organic framework material.
[0132] Embodiment 11
[0133] The steps for preparing the adsorbent in Example 11 are the same as those in Example 2, except that the reaction temperature in step (3) is changed to 250° C. The obtained adsorbent product is recorded as MIL-10.
[0134] Compared with the prior art, the modified organic metal ligand and the preparation method thereof in this embodiment, the adsorbent for removing methane and phosphine from circulating hydrogen and the preparation method thereof have the following beneficial effects:
[0135] (1) The material structure is maintained and the methane adsorption effect is good. According to the adsorption requirements, the pore structure and other characteristics of the metal organic framework can be controlled by the solvent ratio during the synthesis process, and the metal salt loading by the hydrothermal method can avoid the damage to the structure of the adsorbent itself by high temperature calcination in the conventional impregnation loading method. The structure and pore size of the metal organic framework are maintained, so the adsorbent of this embodiment can show efficient adsorption of methane.
[0136] (2) High efficiency in removing phosphine. The process of removing phosphine is as follows: phosphine first enters the pores of the adsorbent and is adsorbed, and then the adsorbed phosphine reacts chemically with the active components loaded on the adsorbent. In this embodiment, a metal organic framework material is first synthesized, and then electrophilic functional groups such as sulfonic acid group and carboxyl group are introduced to modify the metal organic framework. This process of introducing electrophilic functional groups not only ensures that the pores and structure of the metal organic framework are not changed, but also strengthens the adsorption process of phosphine by the adsorbent. The directly loaded active components or the decomposition products of the metal salt loaded during the hydrothermal process can react chemically with the adsorbed phosphine. The combination of efficient adsorption and chemical reaction in this embodiment can fully improve the removal rate of phosphine.
[0137] (3) Good loading effect of active components. The hydrothermal method can load the active components more evenly on the metal organic framework to avoid the agglomeration of active components caused by conventional impregnation methods. In addition, the active components have small particle size and do not block the pore structure of the metal organic framework material.
[0138] Example 12
[0139] The steps for preparing the adsorbent in Example 12 are the same as those in Example 2, except that the reaction temperature in step (1) is changed to 150° C. The obtained adsorbent product is recorded as MIL-11.
[0140] Compared with the prior art, the modified organic metal ligand and the preparation method thereof in this embodiment, the adsorbent for removing methane and phosphine from circulating hydrogen and the preparation method thereof have the following beneficial effects:
[0141] (1) The material structure is maintained and the methane adsorption effect is good. According to the adsorption requirements, the pore structure and other characteristics of the metal organic framework can be controlled by the solvent ratio during the synthesis process, and the metal salt loading by the hydrothermal method can avoid the damage to the structure of the adsorbent itself by high temperature calcination in the conventional impregnation loading method. The structure and pore size of the metal organic framework are maintained, so the adsorbent of this embodiment can show efficient adsorption of methane.
[0142] (2) High efficiency in removing phosphine. The process of removing phosphine is as follows: phosphine first enters the pores of the adsorbent and is adsorbed, and then the adsorbed phosphine reacts chemically with the active components loaded on the adsorbent. In this embodiment, a metal organic framework material is first synthesized, and then electrophilic functional groups such as sulfonic acid group and carboxyl group are introduced to modify the metal organic framework. This process of introducing electrophilic functional groups not only ensures that the pores and structure of the metal organic framework are not changed, but also strengthens the adsorption process of phosphine by the adsorbent. The directly loaded active components or the decomposition products of the metal salt loaded during the hydrothermal process can react chemically with the adsorbed phosphine. The combination of efficient adsorption and chemical reaction in this embodiment can fully improve the removal rate of phosphine.
[0143] (3) Good loading effect of active components. The hydrothermal method can load the active components more evenly on the metal organic framework to avoid the agglomeration of active components caused by conventional impregnation methods. In addition, the active components have small particle size and do not block the pore structure of the metal organic framework material.
[0144] Embodiment 13
[0145] The preparation steps of the adsorbent in Example 13 are the same as those in Example 2, except that the active component in step (3) is replaced by cupric chloride. The obtained adsorbent product is recorded as MIL-12.
[0146] Compared with the prior art, the modified organic metal ligand and the preparation method thereof in this embodiment, the adsorbent for removing methane and phosphine from circulating hydrogen and the preparation method thereof have the following beneficial effects:
[0147] (1) The material structure is maintained and the methane adsorption effect is good. According to the adsorption requirements, the pore structure and other characteristics of the metal organic framework can be controlled by the solvent ratio during the synthesis process, and the metal salt loading by the hydrothermal method can avoid the damage to the structure of the adsorbent itself by high temperature calcination in the conventional impregnation loading method. The structure and pore size of the metal organic framework are maintained, so the adsorbent of this embodiment can show efficient adsorption of methane.
[0148] (2) High efficiency in removing phosphine. The process of removing phosphine is as follows: phosphine first enters the pores of the adsorbent and is adsorbed, and then the adsorbed phosphine reacts chemically with the active components loaded on the adsorbent. In this embodiment, a metal organic framework material is first synthesized, and then electrophilic functional groups such as sulfonic acid group and carboxyl group are introduced to modify the metal organic framework. This process of introducing electrophilic functional groups not only ensures that the pores and structure of the metal organic framework are not changed, but also strengthens the adsorption process of phosphine by the adsorbent. The directly loaded active components or the decomposition products of the metal salt loaded during the hydrothermal process can react chemically with the adsorbed phosphine. The combination of efficient adsorption and chemical reaction in this embodiment can fully improve the removal rate of phosphine.
[0149] (3) Good loading effect of active components. The hydrothermal method can load the active components more evenly on the metal organic framework to avoid the agglomeration of active components caused by conventional impregnation methods. In addition, the active components have small particle size and do not block the pore structure of the metal organic framework material.
[0150] Embodiment 14
[0151] The adsorbent preparation steps of Example 14 are the same as those of Example 2, except that the reaction time in step (2) is changed to 7 hours. The obtained adsorbent product is recorded as MIL-13.
[0152] Compared with the prior art, the modified organic metal ligand and the preparation method thereof in this embodiment, the adsorbent for removing methane and phosphine from circulating hydrogen and the preparation method thereof have the following beneficial effects:
[0153] (1) The material structure is maintained and the methane adsorption effect is good. According to the adsorption requirements, the pore structure and other characteristics of the metal organic framework can be controlled by the solvent ratio during the synthesis process, and the metal salt loading by the hydrothermal method can avoid the damage to the structure of the adsorbent itself by high temperature calcination in the conventional impregnation loading method. The structure and pore size of the metal organic framework are maintained, so the adsorbent of this embodiment can show efficient adsorption of methane.
[0154] (2) High efficiency in removing phosphine. The process of removing phosphine is as follows: phosphine first enters the pores of the adsorbent and is adsorbed, and then the adsorbed phosphine reacts chemically with the active components loaded on the adsorbent. In this embodiment, a metal organic framework material is first synthesized, and then electrophilic functional groups such as sulfonic acid group and carboxyl group are introduced to modify the metal organic framework. This process of introducing electrophilic functional groups not only ensures that the pores and structure of the metal organic framework are not changed, but also strengthens the adsorption process of phosphine by the adsorbent. The directly loaded active components or the decomposition products of the metal salt loaded during the hydrothermal process can react chemically with the adsorbed phosphine. The combination of efficient adsorption and chemical reaction in this embodiment can fully improve the removal rate of phosphine.
[0155] (3) Good loading effect of active components. The hydrothermal method can load the active components more evenly on the metal organic framework to avoid the agglomeration of active components caused by conventional impregnation methods. In addition, the active components have small particle size and do not block the pore structure of the metal organic framework material.
[0156] Embodiment 15
[0157] This embodiment provides a method for preparing a modified organometallic ligand, comprising the following steps:
[0158] (1) Aluminum nitrate and terephthalic acid, reactants in a molar ratio of 1:1, were added to deionized water and mixed, the mixture was ultrasonically dispersed, stirred at room temperature until uniformly mixed, and then transferred to a reactor, heated to 100° C. at 10° C. / min and reacted for 12 h to generate an organometallic ligand MOF;
[0159] (2) After the reaction is completed, the temperature is lowered to 60°C, the organic metal ligand MOF is filtered and placed in a reactor, and a DMF solution of 2-sulfonato terephthalate monosodium with a concentration of 5 g / L is added to the reactor, and the mixture is stirred evenly and then reacted at 70°C for 10 h to generate an organic metal ligand MOF modified with 2-sulfonato terephthalic acid carboxyl. After the reaction is completed, the mixture is cooled to room temperature and filtered, and then soaked in 2 mol / L hydrochloric acid for 30 min. After soaking, the mixture is washed with deionized water until neutral, and then washed with DMF and ethanol for 6 times in sequence, and finally dried under vacuum at 60°C for 8 h to obtain an organic metal ligand MOF modified with 2-sulfonato terephthalic acid carboxyl, which is an adsorbent carrier.
[0160] This embodiment provides a modified organic metal ligand, which is prepared by the above method.
[0161] This embodiment provides a method for preparing an adsorbent for removing methane and phosphine from circulating hydrogen, comprising the following steps:
[0162] (a) The active components of copper nitrate and copper sulfate (mass ratio of 1:2) are placed in ethylene glycol and stirred until completely dissolved, and then the adsorbent carrier obtained in step (2) is placed in the solution, and the copper acetate mass fraction is 5% based on copper. After stirring and mixing at room temperature, the mixture is placed in a reactor for reaction, and the temperature is increased to 100° C. at 10° C. / min and reacted for 4 hours. After the reaction is completed, the mixture is cooled to room temperature, washed with deionized water, filtered, and then the product is vacuum dried at 60° C. for 4 hours to obtain an adsorbent product. The obtained adsorbent product is recorded as MIL-14.
[0163] This embodiment also provides an adsorbent for removing methane and phosphine from circulating hydrogen, which is prepared by the above method.
[0164] Compared with the prior art, the modified organic metal ligand and the preparation method thereof in this embodiment, the adsorbent for removing methane and phosphine from circulating hydrogen and the preparation method thereof have the following beneficial effects:
[0165] (1) The material structure is maintained and the methane adsorption effect is good. According to the adsorption requirements, the pore structure and other characteristics of the metal organic framework can be controlled by the solvent ratio during the synthesis process, and the metal salt loading by the hydrothermal method can avoid the damage to the structure of the adsorbent itself by high temperature calcination in the conventional impregnation loading method. The structure and pore size of the metal organic framework are maintained, so the adsorbent of this embodiment can show efficient adsorption of methane.
[0166] (2) High efficiency in removing phosphine. The process of removing phosphine is as follows: phosphine first enters the pores of the adsorbent and is adsorbed, and then the adsorbed phosphine reacts chemically with the active components loaded on the adsorbent. In this embodiment, a metal organic framework material is first synthesized, and then electrophilic functional groups such as sulfonic acid group and carboxyl group are introduced to modify the metal organic framework. This process of introducing electrophilic functional groups not only ensures that the pores and structure of the metal organic framework are not changed, but also strengthens the adsorption process of phosphine by the adsorbent. The directly loaded active components or the decomposition products of the metal salt loaded during the hydrothermal process can react chemically with the adsorbed phosphine. The combination of efficient adsorption and chemical reaction in this embodiment can fully improve the removal rate of phosphine.
[0167] (3) Good loading effect of active components. The hydrothermal method can load the active components more evenly on the metal organic framework to avoid the agglomeration of active components caused by conventional impregnation methods. In addition, the active components have small particle size and do not block the pore structure of the metal organic framework material.
[0168] Example 16
[0169] This embodiment provides a method for preparing a modified organometallic ligand, comprising the following steps:
[0170] (1) adding reactants of ferric nitrate, chromium nitrate (mass ratio of 1:1) and terephthalic acid into hydrofluoric acid and mixing them, wherein the molar ratio of the mixture of ferric nitrate and chromium nitrate to the molar ratio of terephthalic acid is 5:1, ultrasonically dispersing the mixture, stirring at room temperature until the mixture is uniformly mixed, and then transferring the mixture to a reactor, heating the mixture to 250° C. at a rate of 0.5° C. / min and reacting the mixture for 10 h to generate an organometallic ligand MOF;
[0171] (2) After the reaction is completed, the temperature is lowered to 60°C, the organic metal ligand MOF is filtered and placed in a reactor, and a DMF solution of 2-sulfonato terephthalate monosodium with a concentration of 1g / L is added to the reactor, and the mixture is stirred evenly and then reacted at 80°C for 4h to generate an organic metal ligand MOF modified with 2-sulfonato terephthalic acid carboxyl. After the reaction is completed, the mixture is cooled to room temperature and filtered, and then soaked in 4mol / L hydrochloric acid for 20min. After soaking, the mixture is washed with deionized water until neutral, and then washed with DMF and ethanol for 10 times in sequence, and finally dried under vacuum at 120°C for 4h to obtain an organic metal ligand MOF modified with 2-sulfonato terephthalic acid carboxyl, which is an adsorbent carrier.
[0172] This embodiment provides a modified organic metal ligand, which is prepared by the above method.
[0173] This embodiment provides a method for preparing an adsorbent for removing methane and phosphine from circulating hydrogen, comprising the following steps:
[0174] (a) The active component copper carbonate is placed in a mixed solvent of methanol and water (mass ratio of 3:1) and stirred until completely dissolved, and then the adsorbent carrier obtained in step (2) is placed in the solution, and the mass fraction of copper acetate is 15% based on copper. After stirring and mixing at room temperature, the mixture is placed in a reactor for reaction, and the temperature is increased to 250° C. at 0.5° C. / min for reaction for 8 h. After the reaction is completed, the mixture is cooled to room temperature, washed with deionized water, filtered, and then the product is vacuum dried at 80° C. for 8 h to obtain an adsorbent product, which is recorded as MIL-15.
[0175] This embodiment also provides an adsorbent for removing methane and phosphine from circulating hydrogen, which is prepared by the above method.
[0176] Compared with the prior art, the modified organic metal ligand and the preparation method thereof in this embodiment, the adsorbent for removing methane and phosphine from circulating hydrogen and the preparation method thereof have the following beneficial effects:
[0177] (1) The material structure is maintained and the methane adsorption effect is good. According to the adsorption requirements, the pore structure and other characteristics of the metal organic framework can be controlled by the solvent ratio during the synthesis process, and the metal salt loading by the hydrothermal method can avoid the damage to the structure of the adsorbent itself by high temperature calcination in the conventional impregnation loading method. The structure and pore size of the metal organic framework are maintained, so the adsorbent of this embodiment can show efficient adsorption of methane.
[0178] (2) High efficiency in removing phosphine. The process of removing phosphine is as follows: phosphine first enters the pores of the adsorbent and is adsorbed, and then the adsorbed phosphine reacts chemically with the active components loaded on the adsorbent. In this embodiment, a metal organic framework material is first synthesized, and then electrophilic functional groups such as sulfonic acid group and carboxyl group are introduced to modify the metal organic framework. This process of introducing electrophilic functional groups not only ensures that the pores and structure of the metal organic framework are not changed, but also strengthens the adsorption process of phosphine by the adsorbent. The directly loaded active components or the decomposition products of the metal salt loaded during the hydrothermal process can react chemically with the adsorbed phosphine. The combination of efficient adsorption and chemical reaction in this embodiment can fully improve the removal rate of phosphine.
[0179] (3) Good loading effect of active components. The hydrothermal method can load the active components more evenly on the metal organic framework to avoid the agglomeration of active components caused by conventional impregnation methods. In addition, the active components have small particle size and do not block the pore structure of the metal organic framework material.
[0180] Embodiment 17
[0181] This embodiment provides a method for preparing a modified organometallic ligand, comprising the following steps:
[0182] (1) Adding reactants of ferric nitrate and terephthalic acid in a molar ratio of 2:1 into DMF and mixing, ultrasonically dispersing the mixture, stirring at room temperature until the mixture is uniformly mixed, transferring the mixture to a reactor, heating the mixture to 180°C at a rate of 15°C / min and reacting for 1 hour to generate an organometallic ligand MOF;
[0183] (2) After the reaction is completed, the temperature is lowered to 60°C, the organic metal ligand MOF is filtered and placed in a reactor, and a DMF solution of 2-sulfonato terephthalate monosodium with a concentration of 3g / L is added to the reactor, and the mixture is stirred evenly and then reacted at 65°C for 12h to generate an organic metal ligand MOF modified with 2-sulfonato terephthalic acid carboxyl. After the reaction is completed, the mixture is cooled to room temperature and filtered, and then soaked in 2.5mol / L hydrochloric acid for 40min. After soaking, the mixture is washed with deionized water until neutral, and then washed with DMF and ethanol for 8 times in sequence, and finally dried under vacuum at 80°C for 12h to obtain an organic metal ligand MOF modified with 2-sulfonato terephthalic acid carboxyl, which is an adsorbent carrier.
[0184] This embodiment provides a modified organic metal ligand, which is prepared by the above method.
[0185] This embodiment provides a method for preparing an adsorbent for removing methane and phosphine from circulating hydrogen, comprising the following steps:
[0186] (a) The active component copper acetate is placed in ethanol and stirred until completely dissolved, and then the adsorbent carrier obtained in step (2) is placed in the solution, the mass fraction of copper acetate is 11% based on copper, and after stirring and mixing at room temperature, the mixture is placed in a reactor for reaction, and the temperature is increased to 220° C. at a rate of 15° C. / min and reacted for 12 h. After the reaction is completed, the mixture is cooled to room temperature, washed with deionized water, filtered, and then the product is vacuum dried at 120° C. for 12 h to obtain an adsorbent product, which is recorded as MIL-16.
[0187] This embodiment also provides an adsorbent for removing methane and phosphine from circulating hydrogen, which is prepared by the above method.
[0188] Compared with the prior art, the modified organic metal ligand and the preparation method thereof in this embodiment, the adsorbent for removing methane and phosphine from circulating hydrogen and the preparation method thereof have the following beneficial effects:
[0189] (1) The material structure is maintained and the methane adsorption effect is good. According to the adsorption requirements, the pore structure and other characteristics of the metal organic framework can be controlled by the solvent ratio during the synthesis process, and the metal salt loading by the hydrothermal method can avoid the damage to the structure of the adsorbent itself by high temperature calcination in the conventional impregnation loading method. The structure and pore size of the metal organic framework are maintained, so the adsorbent of this embodiment can show efficient adsorption of methane.
[0190] (2) High efficiency in removing phosphine. The process of removing phosphine is as follows: phosphine first enters the pores of the adsorbent and is adsorbed, and then the adsorbed phosphine reacts chemically with the active components loaded on the adsorbent. In this embodiment, a metal organic framework material is first synthesized, and then electrophilic functional groups such as sulfonic acid group and carboxyl group are introduced to modify the metal organic framework. This process of introducing electrophilic functional groups not only ensures that the pores and structure of the metal organic framework are not changed, but also strengthens the adsorption process of phosphine by the adsorbent. The directly loaded active components or the decomposition products of the metal salt loaded during the hydrothermal process can react chemically with the adsorbed phosphine. The combination of efficient adsorption and chemical reaction in this embodiment can fully improve the removal rate of phosphine.
[0191] (3) Good loading effect of active components. The hydrothermal method can load the active components more evenly on the metal organic framework to avoid the agglomeration of active components caused by conventional impregnation methods. In addition, the active components have small particle size and do not block the pore structure of the metal organic framework material.
[0192] Comparative Example 1
[0193] The preparation of the adsorbent carrier in Comparative Example 1 is the same as steps (1) and (2) in Example 2, but step (3) uses an impregnation and calcination method: the adsorbent carrier is immersed in a copper acetate solution for 6 hours and then calcined in a muffle furnace at 200° C. for 6 hours to obtain an adsorbent product, which is recorded as MIL-18. Comparative Example 1 is used to illustrate that the method of hydrothermal loading of active components in Example 2 can ensure that the characteristics of the metal organic framework structure and the like are maintained, thereby having a higher adsorption effect on methane and phosphine.
[0194] Comparative Example 2
[0195] The preparation steps of the adsorbent carrier in Comparative Example 2 are the same as steps (1) and (3) in Example 2, but the steps of preparing the solution, reacting, and soaking in hydrochloric acid in step (2) are omitted, and the adsorbent carrier is directly washed with deionized water, DMF, and ethanol, filtered and dried to obtain the adsorbent carrier, and then step (3) is performed. The adsorbent product obtained in Comparative Example 2 is recorded as MIL-19. Comparative Example 2 is used to illustrate that the electrophilic group introduced in step (2) in Example 2 can improve the adsorption effect of phosphine.
[0196] Comparative Example 3
[0197] The active component loading of the adsorbent in Comparative Example 3 is the same as step (3) in Example 2, but a commercial activated carbon of a certain brand is used instead of the metal organic framework as the adsorbent carrier, and the obtained adsorbent product is recorded as AC-1. Comparative Example 3 is used to illustrate that the adsorbent synthesized in Example 2 has a high adsorption and removal effect on methane and phosphine.
[0198] The adsorbents in Examples 2 to 17 were analyzed using Fourier transform infrared spectroscopy. -1 1050cm -1 The absorption vibration peak of the sulfur-oxygen double bond was analyzed, and the sulfonic acid group was successfully modified onto the metal organic framework adsorbent.
[0199] The adsorption experiments of the above embodiments and comparative examples were all carried out under the following conditions:
[0200] The adsorbent is 1g, the phosphine concentration at the adsorption column inlet is 50ppm, the methane concentration is 50ppm, nitrogen is the carrier gas, the adsorption temperature is 25-30℃, the operating pressure is normal pressure, and the mixed gas flow rate is 50ml / min.
[0201] The removal data of methane and phosphine by different adsorbent materials are shown in the following table:
[0202]
[0203]
[0204]
[0205] It is to be understood that the above embodiments are merely exemplary embodiments used to illustrate the principles of the present invention, but the present invention is not limited thereto. For those of ordinary skill in the art, various modifications and improvements can be made without departing from the spirit and essence of the present invention, and these modifications and improvements are also considered to be within the scope of protection of the present invention.
Claims
1. A method for preparing a modified organometallic ligand, It is characterized in that The following steps are involved: 1) adding a first metal salt and terephthalic acid into a first solvent, heating and reacting to generate an organic metal ligand MOF; 2) Separating the organic metal ligand MOF, mixing it with the N,N-dimethylformamide solution of 2-sulfonato terephthalic acid monosodium, and reacting it to generate the organic metal ligand MOF modified with 2-sulfonato terephthalic acid carboxyl group.
2. The method for preparing the modified organometallic ligand according to claim 1, It is characterized in that The first metal salt in step 1) is one or more of aluminum nitrate, aluminum chloride, ferric nitrate, ferric chloride, chromium nitrate and chromium chloride.
3. The method for preparing the modified organometallic ligand according to claim 1, It is characterized in that The molar ratio of the first metal salt to terephthalic acid in step 1) is (1-5):
1.
4. The method for preparing the modified organometallic ligand according to claim 1, It is characterized in that The first solvent in step 1) is one or more of water, hydrofluoric acid, and N,N-dimethylformamide.
5. The method for preparing the modified organometallic ligand according to claim 1, It is characterized in that The heating temperature in step 1) is 100-250° C., and the heating time is 1-12 hours.
6. The method for preparing the modified organometallic ligand according to claim 1, It is characterized in that The concentration of the N,N-dimethylformamide solution of monosodium 2-sulfonate terephthalate in step 2) is 1 to 5 g / L.
7. The method for preparing the modified organometallic ligand according to claim 1, It is characterized in that The reaction temperature in step 2) is 60-80° C., and the reaction time is 4-12 hours.
8. A modified organometallic ligand, It is characterized in that It is prepared by the method described in any one of claims 1 to 7.
9. A method for preparing an adsorbent for removing methane and phosphine from circulating hydrogen. It is characterized in that The following steps are involved: a) adding a second metal salt and the modified organometallic ligand MOF prepared by the method according to any one of claims 1 to 7 into a second solvent, heating the mixture for reaction, and generating an adsorbent for removing methane and phosphine from circulating hydrogen.
10. The method for preparing an adsorbent for removing methane and phosphine from circulating hydrogen according to claim 9, It is characterized in that The second metal salt is a copper metal salt, and the copper metal salt is one or more of copper acetate, copper nitrate, copper chloride, copper sulfate, and copper carbonate.
11. The method for preparing an adsorbent for removing methane and phosphine from circulating hydrogen according to claim 9, It is characterized in that In the step a), the concentration of the metal element in the second metal salt in the solution is 5% to 15% based on the mass fraction of the metal element.
12. The method for preparing an adsorbent for removing methane and phosphine from circulating hydrogen according to claim 9, It is characterized in that The second solvent is one or more of water, methanol, ethanol and ethylene glycol.
13. The method for preparing an adsorbent for removing methane and phosphine from circulating hydrogen according to claim 9, It is characterized in that The reaction in step a) is a hydrothermal reaction, the heating temperature is 100-250° C., and the heating time is 4-12 hours.
14. An adsorbent for removing methane and phosphine from circulating hydrogen. It is characterized in that It is prepared by the method according to any one of claims 9 to 13.