CN115155533A - Application of hydrophobic long-chain vapor deposition modified MOFs adsorbent in separation of methane and nitrogen - Google Patents
Application of hydrophobic long-chain vapor deposition modified MOFs adsorbent in separation of methane and nitrogen Download PDFInfo
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Abstract
The invention discloses an application of a hydrophobic long-chain vapor deposition modified MOFs adsorbent in methane and nitrogen separation. The method is characterized in that hydrophobic modified MOFs prepared by depositing hydrophobic organic long-chain molecules on the surface of the MOFs through a vapor deposition method is used as an adsorbent, and methane and nitrogen are adsorbed and separated. According to the invention, the adsorbent is modified by adopting a vapor deposition method, the pore structure and the crystal morphology of MOFs are not changed, the gas separation performance is not reduced under a drying condition, meanwhile, the MOFs structure is wrapped by rich hydrophobic methyl groups on a long chain, the adsorption separation performance and the water vapor stability of the adsorbent material to methane under the water vapor working condition are improved, and the cyclic use in practical engineering application is facilitated.
Description
Technical Field
The invention belongs to the technical field of methane and nitrogen adsorption separation, and particularly relates to an application of a hydrophobic long-chain vapor deposition modified MOFs adsorbent in methane and nitrogen separation.
Background
Methane (CH) 4 ) As the main component (75-90%) of natural gas, has rich natural resources and environmental friendliness, and is a promising substitute for traditional fossil fuelClean energy. However, natural gas collected naturally contains a small amount of components such as ethane (9%), propane (3%), nitrogen (2%), butane and the like, and the single-component light hydrocarbon also plays an important role in industrial production. Therefore, in order to solve the problem of low energy utilization rate, methane needs to be purified and recovered from methane storage bodies such as natural gas, and the like, which brings great economic and environmental benefits.
CH reported so far 4 /N 2 The adsorbent for separating MOFs has high specific surface area and good selectivity, such as AHC-Cu to CH 4 The adsorption capacity is 64.96cm 3 G, to CH 4 /N 2 The separation selectivity is about 9.7. Charlie et al developed a metal organic framework material with a 3D structure having 1168m 2 Specific surface area per gram and 0.807cm 3 A pore volume of 1.76mmol/g and an adsorption capacity of 0.47mmol/g for methane nitrogen gas at 298K and 100kPa, respectively, and a selectivity of 7.0 (KIVI C E, GELFAND B S, DURECKOVA H, et al.3D pore metal-organic frame for selective adsorption of methane over inhibitor unit atmospheric pressure [ J]Chem Commun (Camb), 2018,54 (100): 14104-7). Miao reports that Al-CDC material can efficiently separate CH 4 /N 2 But under the water vapor condition, H 2 O molecule and CH 4 Molecules generate competitive adsorption at adsorption sites, so that the separation performance of the material under the water vapor working condition is reduced (Chang M, ZHAO Y, LIU D, et al. Methane-bridging metal-organic frames with an ionic ligand for an adsorbent CH) 4 /N 2 separation[J].Sustainable Energy&Fuels,2020,4 (1): 138-42.). Meanwhile, the MOFs material generally has the defect of poor water vapor stability, and is difficult to realize industrialization. Therefore, how to realize the industrialization of methane/nitrogen separation still remains to be solved.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide the application of the hydrophobic long-chain vapor deposition modified MOFs adsorbent in the separation of methane and nitrogen.
According to the invention, the MOFs is subjected to hydrophobic modification by adopting organic long-chain molecules through a vapor deposition method, the prepared hydrophobic modified MOFs adsorbent is used for improving the separation performance of methane and nitrogen under the water vapor working condition, the pore structure and the crystal morphology of the MOFs are not changed by the vapor deposition modified hydrophobic adsorbent, the gas separation performance is not reduced under the dry condition, the adsorption separation performance and the water vapor stability of the adsorbent material under the water vapor working condition are improved, and the cyclic use in the practical engineering application is facilitated.
The purpose of the invention is realized by the following technical scheme:
the application of the hydrophobic long-chain vapor deposition modified MOFs adsorbent in methane and nitrogen separation is characterized in that the hydrophobic long-chain vapor deposition modified MOFs adsorbent is prepared by depositing hydrophobic organic long-chain molecules on the surface of MOFs through a vapor deposition method;
the hydrophobic organic long-chain molecule is at least one of Polydimethylsiloxane (PDMS), polymethyl triethoxysilane, cyclomethicone, amino modified polysiloxane, polymethylphenylsiloxane and polyether polysiloxane; more preferably.
Preferably, the mass ratio of the hydrophobic organic long-chain molecules to the MOFs is (0.01-0.1): 1.
preferably, the deposition temperature is 150-250 ℃ and the deposition time is 30-60 min.
Preferably, the temperature programming rate of the vapor deposition method is 1 to 10 ℃/min.
Preferably, the MOFs are prepared by the following method:
metal salt, trans-cyclohexane dicarboxylic acid (H) 2 CDC), N-Dimethylformamide (DMF) and water are subjected to a co-thermal reaction, and then channel activation is carried out in an organic solvent and drying is carried out to obtain the MOFs.
Further preferably, the metal salt is reacted with H 2 CDC in a molar ratio of (0.8-1.2): 1. the metal salt is AlCl 3 ·6H 2 O、FeCl 3 ·6H 2 O and Cr (NO) 3 ) 3 At least one of; more preferably AlCl 3 ·6H 2 O and FeCl 3 ·6H 2 At least one of O.
Further preferably, the volume ratio of DMF to water is (3-5): 1.
further preferably, said H 2 Molar mass of CDC and volume ratio of DMF 6mmol:24 to 40mL.
Further preferably, the temperature of the co-heating reaction is 100-150 ℃ and the time is 5-60 min.
Further preferably, the organic solvent is at least one of acetone, methanol, ethanol and dichloromethane and N, N-Dimethylformamide (DMF), and the organic solvent is washed with the N, N-Dimethylformamide (DMF) and then washed with at least one of acetone, methanol, ethanol and dichloromethane.
Further preferably, the drying temperature is 100-150 ℃ and the drying time is 3-24 h.
Preferably, the application is: hydrophobic long-chain vapor deposition modified MOFs adsorbent for CH under water vapor working condition 4 /N 2 And (5) carrying out adsorption separation.
Further preferably, the moisture condition refers to RH0.1% to 95%.
Further preferably, the CH 4 And N 2 Is 99:1 to 1:99.
further preferably, the adsorption separation process is performed on CH 4 /N 2 The gas flow rate of (2) to (10) ml/min.
Compared with the prior art, the invention has the following advantages and beneficial effects:
according to the hydrophobic long-chain vapor deposition modified hydrophobic adsorbent, the MOFs structure is wrapped by abundant hydrophobic methyl groups contained in PDMS, polymethyl triethoxy silane, cyclomethicone, amino modified polysiloxane, polymethyl phenyl siloxane or polyether polysiloxane, so that the methane permeation time of the adsorbent material under the water vapor working condition is prolonged, the methane/nitrogen adsorption separation performance and the water vapor stability of the adsorbent material are improved, the gas separation performance is not reduced under the dry condition, and the hydrophobic adsorbent is favorable for recycling in practical engineering application.
Drawings
FIG. 1 is an XRD spectrum of adsorbents obtained in examples 1 to 3 and comparative examples 1 to 5.
FIG. 2 shows CH at 20% RH for MOFs adsorbents obtained in example 1, comparative example 1 and comparative example 4 4 /N 2 Fixed bed permeation profile of the gas mixture.
FIG. 3 shows CH at 20% RH for MOFs adsorbents obtained in example 2, comparative example 2 and comparative example 5 4 /N 2 Fixed bed permeation profile of the gas mixture.
FIG. 4 shows CH at RH20% for MOFs adsorbents obtained in example 3 and comparative example 3 4 /N 2 Fixed bed permeation profile of the gas mixture.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Those who do not specify specific conditions in the examples of the present invention follow conventional conditions or conditions recommended by the manufacturer. The raw materials, reagents and the like which are not indicated for manufacturers are all conventional products which can be obtained by commercial purchase.
Example 1
Mixing AlCl 3 ·6H 2 O(1.448g，6mmol)、H 2 CDC (1.002g, 6 mmol), DMF (32 mL) and H 2 O (8 mL) is placed in a blue-cap bottle and heated in an oil bath at 130 ℃ for 30min to obtain Al-CDC crystals. The Al-CDC material is washed by DMF and acetone in sequence, and then is dried in vacuum at 130 ℃ for 12h. The dried Al-CDC was uniformly dispersed in a weighing dish, a glass crucible containing polydimethylsiloxane (PDMS, mecanne, CAS 9006-65-9, molecular weight 1000) was placed in the center, and after covering, the crucible was heated to 180 ℃ in an oven at a temperature programmed at 10 ℃/min for 30min to obtain the product labeled as example 1.
Example 2
FeCl 3 ·6H 2 O(1.297g，4.8mmol)、H 2 CDC (1.002g, 6 mmol), DMF (24 mL) and H 2 O (8 mL) was added to a blue-capped bottle and heated at 100 ℃ for 60min to obtain Fe-CDC crystals. The Fe-CDC material was washed with DMF, then methanol, and then dried under vacuum at 100 ℃ for 3h. The Fe-CDC was uniformly dispersed in the weighing dish, the glass crucible with Polydimethylsiloxane (PDMS) was placed in the center, covered and heated to 150 ℃ in an oven at a temperature program of 10 ℃/min for 45min to obtain the product and labeled as example 2.
Example 3
Mixing Cr (NO) 3 ) 3 (1.714g，7.2mmol)、H 2 CDC (1.002g, 6 mmol), DMF (40 mL) and H 2 O (8 mL) is put in a blue-cap bottle and mixed evenly, and Cr-CDC crystals are obtained by heating for 5min at 150 ℃. The Cr-CDC material is washed by DMF and acetone in sequence, and then is dried in vacuum for 24 hours at 150 ℃. The Cr-CDC was uniformly dispersed in a weighing dish, a glass crucible containing polymethyltriethoxysilane was placed in the center, covered and heated in an oven to 250 ℃ at 1 ℃/min program for 30min to give the product and labeled as example 3.
Comparative example 1
Mixing AlCl 3 ·6H 2 O(1.448g，6mmol)、H 2 CDC (1.002g, 6 mmol), DMF (32 mL) and H 2 O (8 mL) is placed in a blue-capped bottle and heated in an oil bath at 130 ℃ for 30min to obtain Al-CDC crystals. The Al-CDC material is washed by DMF and acetone in sequence and then dried for 12h under vacuum at 130 ℃. The product was obtained and labeled comparative example 1.
Comparative example 2
FeCl is added 3 ·6H 2 O(1.297g，4.8mmol)、H 2 CDC (1.002g, 6 mmol), DMF (24 mL) and H 2 O (8 mL) was added to a blue-capped bottle and heated at 100 ℃ for 60min to obtain Fe-CDC crystals. The Fe-CDC material is washed by DMF and acetone in sequence and then dried for 3h under vacuum at 100 ℃. The product was obtained and labeled comparative example 2.
Comparative example 3
Mixing Cr (NO) 3 ) 3 (1.714g，7.2mmol)、H 2 CDC (1.002g, 6 mmol), DMF (40 mL) and H 2 Placing O (8 mL) in a blue-cap bottle, uniformly mixing, and heating at 150 ℃ for 5min to obtain Cr-CDC crystals. The Cr-CDC material is washed by DMF and acetone in sequence and then dried for 24 hours in vacuum at 150 ℃. The product was obtained and labeled comparative example 3.
Comparative example 4
Mixing AlCl 3 ·6H 2 O(1.448g，6mmol)、H 2 CDC (1.002g, 6 mmol), DMF (32 mL) and H 2 O (8 mL) is placed in a blue-capped bottle and heated in an oil bath at 130 ℃ for 30min to obtain Al-CDC crystals. The Al-CDC material is washed by DMF and acetone in sequence, and then is dried in vacuum at 130 ℃ for 12h.The dried Al-CDC was uniformly dispersed in a weighing dish, a glass crucible containing octamethylcyclotetrasiloxane (monomer of polydimethylsiloxane) was placed in the center, and after covering, the glass crucible was heated to 180 ℃ in an oven at a temperature program of 10 ℃/min for 30min to obtain a product and labeled as comparative example 4.
Comparative example 5
FeCl 3 ·6H 2 O(1.297g，4.8mmol)、H 2 CDC (1.002g, 6 mmol), DMF (24 mL) and H 2 O (8 mL) was added to a blue-capped bottle and heated at 100 ℃ for 60min to obtain Fe-CDC crystals. The Fe-CDC material was washed with DMF, then methanol, and then dried under vacuum at 100 ℃ for 3h. And uniformly dispersing Fe-CDC in a weighing dish, placing a glass crucible filled with octamethylcyclotetrasiloxane at the center, covering the glass crucible, heating to 150 ℃ in an oven at the temperature programming of 10 ℃/min, and heating for 45min to obtain a product, wherein the product is marked as comparative example 5.
Structural characteristics of the adsorption materials prepared for examples 1 to 3 and comparative examples 1 to 5 and for CH 4 /N 2 The results of the separation performance test under dry and water vapor conditions are as follows:
fig. 1 shows XRD patterns of examples 1-3 and comparative examples 1-5. The sharp characteristic peaks in the figure indicate that the hydrophobic adsorbent prepared in the example inherits the crystal structure of the original material.
FIGS. 2, 3 and 4 are graphs of the RH at 20% and the gas flow rate at 2ml/min for CH in comparative examples 1 and 4 and example 1, comparative examples 2 and 5 and example 2, comparative example 3 and example 3, respectively 4 /N 2 (volume ratio 1: the methane/nitrogen gas mixture is passed through a bubbling bottle filled with saturated potassium acetate solution, so that the mixture is mixed with water vapor and has a humidity of RH20%, the methane/nitrogen gas/water gas mixture is passed through a fixed bed filled with an adsorbent material, and the gas chromatography of a TCD detector is adopted to analyze the gas flowing out of the fixed bed. The adsorbent does not adsorb nitrogen, so that nitrogen can be detected firstly, and methane can be detected after the adsorbent is saturated in methane adsorption for a period of time.
It is evident from the figure that examples 1, 2 and 3 all extended the time for methane to pass through under water vapor, indicating that the material promoted the materialCH of material under water vapor working condition 4 /N 2 The adsorption and separation performance is good, and the water vapor stability is good. By adopting the vapor deposition of the small molecular monomer, the small molecules can partially enter the pore channel to be blocked, so that the separation performance is reduced, and the long polymer chain is only deposited on the surface of the MOFs and the performance is improved by hydrophobic property. Therefore, the vapor deposition modified hydrophobic adsorbent provided by the invention can be used for treating CH under the water vapor working condition 4 /N 2 The separation has good application prospect.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such modifications are intended to be included in the scope of the present invention.
Claims (10)
1. The application of the hydrophobic long-chain vapor deposition modified MOFs adsorbent in methane and nitrogen separation is characterized in that the hydrophobic long-chain vapor deposition modified MOFs adsorbent is prepared by depositing hydrophobic organic long-chain molecules on the surface of MOFs through a vapor deposition method;
the hydrophobic organic long-chain molecule is at least one of polydimethylsiloxane, polymethyltriethoxysilane, cyclomethicone, amino modified polysiloxane, polymethylphenylsiloxane and polyether polysiloxane.
2. The application of the hydrophobic long-chain vapor deposition modified MOFs adsorbent in the separation of methane and nitrogen according to claim 1, wherein the mass ratio of the hydrophobic organic long-chain molecules to the MOFs is (0.01-0.1): 1.
3. the use of hydrophobic long-chain vapor deposition modified MOFs adsorbents in the separation of methane and nitrogen according to claim 1, wherein the deposition temperature is 150-250 ℃ and the deposition time is 30-60 min.
4. The use of hydrophobic long-chain vapor deposition modified MOFs adsorbents for methane and nitrogen separation according to claim 1, wherein said MOFs are prepared by the following method:
the metal salt, trans-cyclohexane dicarboxylic acid, N-dimethylformamide and water are subjected to a co-thermal reaction for 5-60 min at 100-150 ℃, and then subjected to channel activation in an organic solvent and then dried to obtain the MOFs.
5. The use of hydrophobic long-chain vapor deposition modified MOFs adsorbent according to claim 4, wherein the molar ratio of said metal salt to trans-cyclohexanedicarboxylic acid is (0.8-1.2): 1; the metal salt is AlCl 3 ·6H 2 O、FeCl 3 ·6H 2 O and Cr (NO) 3 ) 3 At least one of (1).
6. The use of the hydrophobic long-chain vapor deposition modified MOFs adsorbent according to claim 4, wherein the volume ratio of N, N-dimethylformamide to water is (3-5): 1; the molar amount of the trans-cyclohexane dicarboxylic acid and the volume ratio of the N, N-dimethylformamide are 6mmol:24 to 40mL.
7. The use of hydrophobic long-chain vapor deposition modified MOFs adsorbents in the separation of methane and nitrogen according to claim 1, wherein a temperature programming rate of said vapor deposition process is 1-10 ℃/min.
8. The application of the hydrophobic long-chain vapor deposition modified MOFs adsorbent according to claim 1, wherein said application is characterized in that: hydrophobic long-chain vapor deposition modified MOFs adsorbent is used for treating CH under water vapor working condition 4 /N 2 And (5) carrying out adsorption separation.
9. The use of the hydrophobic long-chain vapor deposition modified MOFs adsorbents in the separation of methane and nitrogen according to claim 8, wherein said water vapor condition refers to RH0.1% -95%; the CH 4 And N 2 Is 99:1 to 1:99; CH in the adsorption separation process 4 /N 2 The gas flow rate of (2) to (10) ml/min.
10. The use of hydrophobic long-chain vapor deposition modified MOFs adsorbent according to claim 4, wherein said organic solvent is at least one of acetone, methanol, ethanol and dichloromethane and N, N-dimethylformamide, and is washed with N, N-dimethylformamide and then with at least one of acetone, methanol, ethanol and dichloromethane; the drying temperature is 100-150 ℃, and the drying time is 3-24 h.
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| CN115595040A (en) * | 2022-10-24 | 2023-01-13 | 上海正欧实业有限公司（Cn） | Epoxy floor paint and preparation method thereof |
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