Preparation method of metal-organic framework material for adsorbing separation of carbon dioxide/ methane

Abstract

The invention discloses a preparation method of a metal-organic framework material for adsorbing separation of carbon dioxide / methane. The preparation method comprises the following steps of: (1) mixing 0.46-1.16mol / L cupric nitrate water solution and 0.23-0.58mol / L trimesic acid ethanol solution, fully stirring, then adding into a stainless steel reaction kettle provided with a polytetrafluoroethylene inner liner for sealing, and carrying out solvent thermal reaction while controlling the crystallization temperature to be 60-150 DEG C and the crystallization time at 12-24h; (2) opening the stainless steel reaction kettle, filtering, sequentially washing by methyl alcohol and deionized water, and drying at the temperature of 80-105 DEG C to obtain blue crystal; and (3) vacuumizing the blue crystal at the temperature of 150-200 DEG C to obtain the Cu-containing metal-organic framework material.

Description

technical field

[0001] The invention belongs to the technical field of environmental protection, and in particular relates to a preparation method of a metal organic framework material for absorbing and separating carbon dioxide / methane. Background technique

[0002] Carbon dioxide is the highest content component in biogas landfill gas except methane, accounting for 30%~40% of biogas components. The presence of carbon dioxide in biogas greatly reduces the calorific value of biogas combustion, reducing its energy utilization efficiency. Therefore, in the biogas purification technology, the separation of methane and carbon dioxide to obtain high-purity methane is required to improve energy utilization efficiency, produce high-grade products, and increase the economic value of biogas.

[0003] In recent years, some researchers have conducted research on biogas removal, purification and high-value utilization technologies, and have achieved many meaningful results in the devel...

Examples

preparation example Construction

[0023] The present invention provides a method for preparing a metal-organic framework material that absorbs and separates carbon dioxide / methane, and in one embodiment, includes the following steps:

[0024] (1) Mix 0.46~1.16 mol / L copper nitrate aqueous solution and 0.23~0.58 mol / L trimesenetricarboxylic acid (1,3,5-Benzenetricarboxylic Acid, C 9 h 6 o 6 , abbreviated as H 3 btc) ethanol solution is mixed, fully stirred and then added to a stainless steel reactor with a polytetrafluoroethylene liner to seal, and the crystallization temperature is controlled at 60~150°C and the crystallization time is 12~24 hours for solvothermal reaction;

[0025] (2) Open the stainless steel reaction kettle, filter, wash with methanol and deionized water in sequence, and dry at 80~105°C to obtain blue crystals;

[0026] (3) Vacuumizing the blue crystal at 150-200° C. to obtain a copper-containing metal-organic framework material.

[0027] Preferably, the temperature in the step (3) ...

Embodiment 1

[0033] Weigh a certain amount of Cu(NO 3 ) 2 ·3H 2 O, dissolved in a certain amount of deionized water, prepared 25ml Cu(NO 3 ) 2 ·3H 2 O aqueous solution, marked as solution Ⅰ; prepare 25ml of H with a concentration of 0.58 mol / L 3 The ethanol solution of btc is marked as solution Ⅱ; mix solution Ⅰ and solution Ⅱ, stir well, put it into a 100ml stainless steel reaction kettle with polytetrafluoroethylene lining, crystallize at 95°C for 15 hours, filter and then Wash three times with methanol and deionized water, 50ml each time, stir thoroughly for 10min, and dry at 105°C for 10 hours to obtain blue crystals. The obtained blue crystals were vacuumized at 175°C for 10 hours, and the measured specific surface area was 1136m 2 / g, X-ray diffraction pattern (XRD) such as figure 1 As shown, characteristic peaks appear at 2θ angles of 6.72°, 9.56°, 11.70°, 13.48°, 14.70°, 16.5°, and 17.54° in the figure, indicating that the material has a typical metal-organic framework mater...

Embodiment 2

[0035] The difference from Example 1 is: crystallize at 60°C for 15 hours in a stainless steel reaction kettle lined with polytetrafluoroethylene, filter and wash with methanol and deionized water three times in sequence, 50ml each time, and fully stir for 10min , dried at 80°C for 2 hours to obtain blue crystals. The obtained blue crystals were subjected to vacuum treatment at 150°C for 3 hours, and the measured specific surface area was 539m 2 / g.

technical field

[0001] The invention belongs to the technical field of environmental protection, and in particular relates to a preparation method of a metal organic framework material for absorbing and separating carbon dioxide / methane. Background technique

[0002] Carbon dioxide is the highest content component in biogas landfill gas except methane, accounting for 30%~40% of biogas components. The presence of carbon dioxide in biogas greatly reduces the calorific value of biogas combustion, reducing its energy utilization efficiency. Therefore, in the biogas purification technology, the separation of methane and carbon dioxide to obtain high-purity methane is required to improve energy utilization efficiency, produce high-grade products, and increase the economic value of biogas.

[0003] In recent years, some researchers have conducted research on biogas removal, purification and high-value utilization technologies, and have achieved many meaningful results in the devel...

Examples

preparation example Construction

[0023] The present invention provides a method for preparing a metal-organic framework material that absorbs and separates carbon dioxide / methane, and in one embodiment, includes the following steps:

[0024] (1) Mix 0.46~1.16 mol / L copper nitrate aqueous solution and 0.23~0.58 mol / L trimesenetricarboxylic acid (1,3,5-Benzenetricarboxylic Acid, C 9 h 6 o 6 , abbreviated as H 3 btc) ethanol solution is mixed, fully stirred and then added to a stainless steel reactor with a polytetrafluoroethylene liner to seal, and the crystallization temperature is controlled at 60~150°C and the crystallization time is 12~24 hours for solvothermal reaction;

[0025] (2) Open the stainless steel reaction kettle, filter, wash with methanol and deionized water in sequence, and dry at 80~105°C to obtain blue crystals;

[0026] (3) Vacuumizing the blue crystal at 150-200° C. to obtain a copper-containing metal-organic framework material.

[0027] Preferably, the temperature in the step (3) ...

Embodiment 1

[0033] Weigh a certain amount of Cu(NO 3 ) 2 ·3H 2 O, dissolved in a certain amount of deionized water, prepared 25ml Cu(NO 3 ) 2 ·3H 2 O aqueous solution, marked as solution Ⅰ; prepare 25ml of H with a concentration of 0.58 mol / L 3 The ethanol solution of btc is marked as solution Ⅱ; mix solution Ⅰ and solution Ⅱ, stir well, put it into a 100ml stainless steel reaction kettle with polytetrafluoroethylene lining, crystallize at 95°C for 15 hours, filter and then Wash three times with methanol and deionized water, 50ml each time, stir thoroughly for 10min, and dry at 105°C for 10 hours to obtain blue crystals. The obtained blue crystals were vacuumized at 175°C for 10 hours, and the measured specific surface area was 1136m 2 / g, X-ray diffraction pattern (XRD) such as figure 1 As shown, characteristic peaks appear at 2θ angles of 6.72°, 9.56°, 11.70°, 13.48°, 14.70°, 16.5°, and 17.54° in the figure, indicating that the material has a typical metal-organic framework mater...

Embodiment 2

[0035] The difference from Example 1 is: crystallize at 60°C for 15 hours in a stainless steel reaction kettle lined with polytetrafluoroethylene, filter and wash with methanol and deionized water three times in sequence, 50ml each time, and fully stir for 10min , dried at 80°C for 2 hours to obtain blue crystals. The obtained blue crystals were subjected to vacuum treatment at 150°C for 3 hours, and the measured specific surface area was 539m 2 / g.

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