CN115591526A - Porous composite material, preparation method and application in hydrogen purification - Google Patents
Porous composite material, preparation method and application in hydrogen purification Download PDFInfo
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- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
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- C01B2203/047—Composition of the impurity the impurity being carbon monoxide
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- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
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- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Abstract
The invention discloses a porous composite material, a preparation method and application thereof in hydrogen purification, belonging to the technical field of advanced functional materials 4 The MOF material has a designable space structure and active sites, and has high adsorption selectivity to gas. The high-performance porous composite material adsorbent is prepared by adjusting the proportion of the three porous materials, can overcome the defects of poor adsorption selectivity and high price of the traditional adsorption material, and is used for deeply removing impurity gas in industrial byproduct hydrogenThe whole preparation process is simple, the adsorption efficiency is high, the energy consumption is low, the adsorbent is non-toxic and can be recycled, and the industrial large-scale production and use of the adsorbent are facilitated.
Description
Technical Field
The invention belongs to the technical field of advanced functional materials, and particularly relates to a porous composite material, a preparation method and application thereof in hydrogen purification.
Background
With the increase of human energy demand and use, non-renewable energy sources such as traditional fossil fuels (coal, petroleum and natural gas) are increasingly exhausted.The hydrogen energy has the characteristics of rich sources, environmental friendliness, renewability, high energy density and the like, is considered as an important secondary energy in the new century, and is the only new energy which can simultaneously meet the requirements of resources, environment and sustainable development. From a source perspective, there are three main ways of hydrogen production: (1) preparing hydrogen from coal and natural gas; (2) electrolyzing water to prepare hydrogen; and (3) collecting rich hydrogen production of the chemical plant. The scale of hydrogen production by water electrolysis is very small, and the current large-scale hydrogen production still cannot be realized by fossil fuels, but the environmental problems such as greenhouse effect and the like are brought. In comparison, the collection of rich hydrogen produced in a chemical plant is a main hydrogen production mode in the future, and is environment-friendly, efficient and safe. The problem of purifying industrial hydrogen is always one of the serious problems in the world, and CO, ar and CH often exist in industrial by-product hydrogen 4 And the byproducts are usually removed by energy-consuming separation means such as low-temperature rectification, and the like, and the membrane separation method has high cost and large equipment investment, so that the development of the pressure swing adsorption separation technology based on the advanced composite material is one of effective ways for reducing energy consumption and recovering hydrogen.
Currently, there are many researches on how to adsorb and separate hydrogen, but the conventional porous materials for hydrogen adsorption separation have the following defects: firstly, the difference of the adsorption capacity of the porous material to various components is obvious, and it is difficult to find a material for effectively adsorbing and separating all byproducts; secondly, the porous material has poor adsorption selectivity for multiple components, and has low adsorption selectivity for CO, ar and the like, so that the aim of separation and recovery cannot be achieved; and thirdly, the cost of the high-efficiency porous adsorption material such as MOF is high, and the background of large-scale industrial application is not met. Therefore, the development of the high-efficiency hydrogen purification composite porous material has important significance for industrial hydrogen purification.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a porous composite material, a preparation method and application in hydrogen purification, and solves the technical problem that the traditional porous material has poor adsorption selectivity on multi-component byproducts.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a preparation method of a porous composite material, which comprises the following steps:
fully and uniformly mixing the molecular sieve, the activated carbon and the MOF material, and heating and activating the mixture in an inert atmosphere to obtain a porous composite material;
the molecular sieve is as follows: activated carbon: the mass ratio of MOF material was 70.
Preferably, the temperature for heating and activating under the inert atmosphere is 100-140 ℃ and the time is 1-3 h.
Further preferably, the inert gas is He gas.
Still more preferably, the flow rate of the He gas is 30mL/min, and the flowing time is 2h.
Preferably, the MOF material is made by the following method:
and adding metal salt and an organic ligand into an organic solvent, and drying the material for later use through solvent exchange after hydrothermal reaction to obtain the MOF material.
Further preferably, the metal salt is Cu (NO) 3 ) 2 ·3H 2 O、Ni(NO 3 ) 2 ·6H 2 O and Cr (NO) 3 ) 3 ·9H 2 And O is any one of the above.
Further preferably, the organic ligand is any one of trimesic acid, 2, 5-dihydroxy-p-dibenzoic acid and p-dibenzoic acid.
Further preferably, the temperature of the hydrothermal reaction is 80-200 ℃; the time of the hydrothermal reaction is as follows: 8-72 h.
The invention also discloses the porous composite material prepared by the preparation method.
The invention also discloses application of the porous composite material in a hydrogen purification material.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a porous composite material, which selects a molecular sieve, active carbon and an MOF material as raw materials, on one hand, the MOF material has designable space structure and active sitesThe adsorption selectivity for gas is high, a proper adsorption site can be provided, and the gas which is difficult to adsorb by the molecular sieve and the activated carbon can be preferentially captured through the open metal site and the matched pore structure; on the other hand, the molecular sieve and the activated carbon have good chemical stability and mechanical stability, and are low in cost and suitable for CO and CH 4 The gas has higher adsorption capacity, stable structure and high mechanical strength, can be well suitable for adsorption separation of individual components, realizes primary purification of some moisture and easily-adsorbed gas in industrial byproduct hydrogen, and provides a good adsorption matrix for the porous composite material. Therefore, the molecular sieve, the activated carbon and the prepared MOF material are mixed and reacted, and the three materials are combined and adsorbed cooperatively, so that the prepared porous composite material overcomes the defect of poor adsorption selectivity of the traditional adsorption material, greatly improves the adsorption quantity and the adsorption selectivity of other impurity gases in the industrial byproduct hydrogen gas, realizes the efficient purification of the industrial byproduct hydrogen, and further obtains the hydrogen with high purity. In addition, the whole operation process of the method is simple, pollution-free and high in adsorption efficiency, the reaction solution in the whole process can be recycled, raw materials in the preparation process are saved, the reaction energy consumption is low, the synthesis of the MOF material can be realized in a simple industrial reaction kettle, the operation is simple, and the industrial production is easy.
The porous composite material disclosed by the invention is of a three-section structure, wherein the first section is activated carbon, the second section is a molecular sieve, and the third section is an MOF material, so that different types of impurity gases can be adsorbed, hydrogen can be easily purified at normal temperature and normal pressure, and the porous composite material has the characteristics of low cost, no toxicity, no harm, high adsorption performance and cyclic utilization; the porous composite material can ensure the mechanical property, the adsorption property and the cycle property of the material, has wide application range, makes up the defect of poor adsorption property of a single material, and can solve the problem of higher cost of the pure MOF material.
When the porous composite material disclosed by the invention is applied to hydrogen purification, impurity gases such as CO and H in the hydrogen purification process 2 S、Ar、N 2 And CH 4 And the like have higher selectivity and adsorption capacity.
Drawings
FIG. 1 is a powder diffraction (PXRD) pattern of HKUST-1 prepared in example 1 of the present invention;
FIG. 2 is a PXRD pattern of Ni-MOF-74 prepared in example 2 of the present invention;
FIG. 3 is a PXRD pattern of MIL-101 prepared in example 3 of the present invention;
FIG. 4 shows HKUST-1 composite material pair CH prepared in example 1 of the present invention 4 、CO、Ar、H 2 The room temperature breakthrough curve of (1);
FIG. 5 shows the Ni-MOF-74 composite material pair CH prepared in example 2 of the present invention 4 、CO、Ar、H 2 The room temperature breakthrough curve of (1);
FIG. 6 shows MIL-101 composite Pair CH prepared in example 3 of the present invention 4 、CO、Ar、H 2 The room temperature breakthrough curve of (1);
FIG. 7 is a schematic view of the packing of the composite material of the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the accompanying drawings:
a preparation method of a porous composite material comprises the following steps:
1) Preparation of metal-organic framework (MOFs) materials: firstly, synthesizing three different MOF materials, adding different metal salts and different organic ligands with different molar numbers into different solvents, then placing the materials into a hydrothermal reaction kettle, reacting for 8-72h at 80-200 ℃, then fully exchanging the obtained materials with solvents such as MeOH/EtOH and the like for 3 days, replacing fresh solvents every day, then placing the obtained materials into a vacuum oven, and drying for later use to obtain the MOF materials.
2) Preparing a composite material: mixing a commercially available 5A molecular sieve, activated carbon and MOF material prepared in the step 1) according to a mass ratio of 70:15:15 to obtain three different MOF composite materials, namely an HKUST-1 composite material, a Ni-MOF-74 composite material and an MIL-101 composite material. Wherein the 5A molecular sieve was purchased from alatin biochemical technologies, inc: 69912-79-4; the components: si, al, ca and O;20-40 mesh with pore diameter of
Activated carbon was purchased from alatin biochemical technologies, inc: 7440-44-0, component: carbon, molecular weight: 12.01.
3) Activation of the composite material: and (3) placing the composite material prepared in the step 2) at 120 ℃, purging under the atmosphere of He gas at the flow rate of 30mL/min, and heating and activating the composite material for 2 hours to obtain the activated composite material.
Example 1
A preparation method of a porous HKUST-1 composite material comprises the following steps:
1) Preparation of HKUST-1: adding Cu (NO) 3 ) 2 ·3H 2 O (6.25 g) was dissolved in a beaker containing 75mL of water; trimesic acid (1.7g, BTC) was dissolved in a beaker containing 75mL of ethanolPerforming the following steps; adding Cu (NO) under magnetic stirring 3 ) 2 Slowly adding the aqueous solution into the BTC solution, and then adding 4mL of N, N-Dimethylformamide (DMF); transferring the obtained mixed solution into a 250mL glass bottle, and reacting for 20h at 80 ℃; after the reaction is finished, the mixture is naturally cooled to room temperature, washed by ethanol for a plurality of times, and dried in vacuum at 60 ℃ overnight to obtain blue powder. The experiment gave 2.187g of HKUST-1 in 83% yield.
2) Combination of composite materials: commercially purchased 5A molecular sieve, activated carbon and HKUST-1 prepared in step 1) were mixed in a mass ratio of 70:15:15, to obtain the HKUST-1 composite material.
3) Activation of the composite material: and (3) placing the HKUST-1 composite material combined in the step 2) at 120 ℃, purging under the atmosphere of He gas with the flow rate of 30mL/min, and heating and activating the composite material for 2h to obtain the activated HKUST-1 composite material.
Referring to FIG. 1, which is a PXRD pattern of HKUST-1 prepared in example 1 of the present invention, and a red line is the HKUST-1 prepared in example 1, it can be seen that the synthesized HKUST-1 sample has high purity and no impurity peak. Referring to FIG. 4, HKUST-1 composite material pair CH prepared in example 1 of the present invention 4 、CO、Ar、H 2 The room temperature breakthrough curve shows that the HKUST-1 composite material has good adsorption performance on impurity gas in industrial byproduct hydrogen.
Example 2
A preparation method of a porous Ni-MOF-74 composite material comprises the following steps:
1) Preparation of Ni-MOF-74: 0.908g of Ni (NO) 3 ) 2 ·6H 2 O was dissolved in a beaker containing 12.5mL of water, and 0.991g of 2, 5-dihydroxy-p-dibenzoic acid was dissolved in a beaker containing 112.5mL of DMF and then mixed in a 250mL glass bottle and reacted at 100 ℃ for 72 hours. After the reaction is finished, the mixture is naturally cooled to room temperature, washed by water and methanol for a plurality of times, and dried in vacuum at 100 ℃ overnight to obtain brown yellow powder. The experiment yielded 2.187g of Ni-MOF-74 in a 95% yield.
2) Combination of composite materials: commercially purchased 5A molecular sieve, activated carbon and HKUST-1 prepared in the step 1) are mixed according to the mass ratio of 70:15:15, to obtain the Ni-MOF-74 composite material.
3) Activation of the composite material: placing the Ni-MOF-74 composite material prepared in the step 2) at 120 ℃, blowing the composite material under the atmosphere of He gas, wherein the flow rate of the He gas is 30mL/min, and heating and activating the composite material for 2h to obtain the activated Ni-MOF-74 composite material.
Referring to FIG. 2, which is a PXRD diagram of the Ni-MOF-74 prepared in example 2, and a red line is the Ni-MOF-74 prepared in example 2, it can be seen that the synthesized Ni-MOF-74 sample has high purity and no impurity peak. Referring to FIG. 5, the pair CH of Ni-MOF-74 composite material prepared in example 2 is shown 4 、CO、Ar、H 2 The room temperature breakthrough curve shows that the Ni-MOF-74 composite material has good adsorption performance on impurity gases in industrial byproduct hydrogen.
Example 3
A preparation method of a porous MIL-101 composite material comprises the following steps:
1) Preparation of MIL-101: 2.0g of Cr (NO) 3 ) 3 ·9H 2 Dissolving O and 0.830g of p-dibenzoic acid in 25mL of water, uniformly mixing, transferring into a 50mL reaction kettle, and reacting for 8 hours at 200 ℃; after the reaction is finished, the mixture is naturally cooled to room temperature, and the green precipitate is collected by centrifugation and dried in vacuum at 100 ℃ overnight to obtain green powder. 0.992g of MIL-101 was obtained in 85% yield.
2) Combination of composite materials: mixing commercially available 5A molecular sieve, activated carbon and MIL-101 prepared in the step 1) according to a mass ratio of 70:15:15, to obtain the MIL-101 composite material.
3) Activation of the composite material: placing the MIL-101 composite material prepared in the step 2) at 120 ℃, purging under the atmosphere of He gas with the flow rate of 30mL/min, and heating and activating the composite material for 2h to obtain the activated MIL-101 composite material.
Referring to FIG. 3, which is a PXRD pattern of MIL-101 prepared in example 3, and a red line is Ni-MOF-74 prepared in example 3, it can be seen that the synthesized MIL-101 sample has high purity and no impurity peak. FIG. 6 shows the MIL-101 composite material pair CH prepared in example 3 4 、CO、Ar、H 2 The room temperature breakthrough curve shows that the MIL-101 composite material has good adsorption performance on impurity gases in industrial byproduct hydrogen.
Referring to fig. 7, a filling schematic diagram of the combined material of the invention is shown, a columnar filling mode is adopted, the bottom section is a 5A molecular sieve, the middle section is activated carbon, and the upper section is an MOF material, and as the 5A molecular sieve is stacked to form a gap, the activated carbon and the MOF material can fill the gap at the stacked position, so that the problem of reduced purification efficiency caused by the outflow of the gas to be purified from the side surface is solved.
In summary, porous materials such as molecular sieves and activated carbon, which are widely used in industry, are used for CO and CH 4 The MOF material has designable space structure and active sites, and has high adsorption selectivity to gas. The invention synthesizes three different MOF materials firstly, then combines the three MOF materials with commercially purchased 5A molecular sieve and activated carbon, combines the three porous materials together to form a porous composite material, can efficiently adsorb and separate non-hydrogen gas in the by-product hydrogen, can overcome the defects of poor adsorption selectivity and the like of the traditional adsorption material, and adsorbs impurity gas in the industrial by-product hydrogen at normal temperature and normal pressure, thereby obtaining hydrogen with higher purity. The composite material can be used for treating CO and CH at normal temperature and normal pressure 4 And Ar has good adsorption capacity to H 2 The method has the advantages of small adsorption amount, simple preparation process, good repeatability, mild reaction conditions and controllable product morphology, is suitable for separation and purification of hydrogen in industrial byproduct hydrogen, provides a new solution for industrial separation and purification of hydrogen, and is beneficial to industrial large-scale production and use.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. A method for preparing a porous composite material, comprising the steps of:
fully and uniformly mixing the molecular sieve, the activated carbon and the MOF material, and heating and activating the mixture in an inert atmosphere to obtain a porous composite material;
the molecular sieve is as follows: activated carbon: the mass ratio of the MOF material is 70.
2. The method for preparing the porous composite material according to claim 1, wherein the temperature for heating and activating under the inert atmosphere is 100-140 ℃ for 1-3 h.
3. The method for preparing a porous composite material according to claim 2, wherein the inert gas is He gas.
4. The preparation method of the porous composite material as claimed in claim 3, wherein the flow rate of the He gas is 30mL/min, and the flowing time is 2h.
5. A method of making a porous composite material according to claims 1 to 4 wherein the MOF material is made by:
adding metal salt and an organic ligand into an organic solvent, carrying out hydrothermal reaction, and drying the material for later use through solvent exchange to obtain the MOF material.
6. Process for the preparation of a porous composite material according to claim 5, characterized in that said metal salt is Cu (NO) 3 ) 2 ·3H 2 O、Ni(NO 3 ) 2 ·6H 2 O and Cr (NO) 3 ) 3 ·9H 2 And O is any one of the above.
7. The method for preparing a porous composite material according to claim 5, wherein the organic ligand is any one of trimesic acid, 2, 5-dihydroxy p-dibenzoic acid and p-dibenzoic acid.
8. The method for preparing the porous composite material according to claim 5, wherein the temperature of the hydrothermal reaction is 80-200 ℃; the time of the hydrothermal reaction is as follows: 8-72 h.
9. A porous composite material obtained by the production method according to any one of claims 1 to 8.
10. Use of the porous composite material of claim 9 in a hydrogen purification material for CO, H 2 S、Ar、N 2 And CH 4 Any one or more of the gases has good adsorption performance.
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