CN115869904A - Transition metal doped molecular sieve applied to CO2 capture in humid environment and preparation method and application thereof - Google Patents
Transition metal doped molecular sieve applied to CO2 capture in humid environment and preparation method and application thereof Download PDFInfo
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 6
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 6
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a method for preparing CO in a humid environment 2 The molecular sieve is prepared with trapped transition metal doped molecular sieve in the chemical composition molar ratio of aYO and its preparation process and application 2 ：bZO：cM 2 O, wherein 10 ≦ a ≦ 50,0.1 ≦ b ≦ 1,0 < c ≦ 2.5, Y is a tetravalent element, Z is a divalent transition metal element, M is an H element, and the molecular sieve has a characteristic peak at least within 4 interplanar spacings (d) where the first interplanar spacing d =11.0 ± 0.3, the second interplanar spacing d =9.9 ± 0.2, the third interplanar spacing d =4.3 ± 0.2, and the fourth interplanar spacing d =3.8 ± 0.2, as measured by X-ray diffraction. The molecular sieve framework of the invention is doped with partial transition metal elementsElement, can be in CO 2 ‑N 2 Preferential mass adsorption of CO in separations 2 . When the molecular sieve is applied to the process of adsorbing and treating waste gas in a humid environment, the molecular sieve can maintain more than 90 percent of CO 2 Adsorption capacity.
Description
Technical Field
The invention relates to a transition metal doped molecular sieve, a preparation method and application thereof, belonging to the field of gas separation adsorbents.
Background
CO 2 Is a main product of the combustion of fossil energy and also one of the main sources of greenhouse effect. In many cases, the gas mixture often contains a large amount of N 2 And N is due to molecular size and polarity 2 Should also be taken into account in the separation process. For containing CO 2 The traditional industrialized separation method is to adopt amine solution to separate CO in gas 2 Absorption is carried out and then thermal desorption regeneration is carried out on the amine solution. The method can capture a large amount of CO in the raw material gas such as flue gas 2 However, the high energy consumption of the amine solution regeneration process is the biggest problem. The Pressure Swing Adsorption (PSA) technology can perform gas molecule desorption in a temperature-changing or pressure-reducing mode, and can effectively solve the problem of high energy consumption of the traditional method. Among the currently developed adsorbents, molecular sieves, metal organic framework Materials (MOFs) and carbon materials are the most promising adsorbents.
MOFs are three-dimensional networks of metal nodes and organic ligands cross-linked, typically with uniform pore sizes ranging from 0.3nm to 2nm (Nature, 2003,423,705). MOFs can selectively screen CO from gas mixtures when they have pore sizes similar to the molecular size 2 And the like (Angew. Chem. Int. Ed.,2016,55,10268-10272). However, in many cases, the separated system often contains a certain amount of waterSteam, such as flue gas, contains 5% -10% of water vapor, which easily damages the MOFs structure and affects the separation performance, and if water is removed in advance, the equipment investment is increased.
The carbon molecular sieve is a carbon-based novel adsorbent with certain characteristics of both activated carbon and molecular sieve, and the pore structure of the carbon molecular sieve is mainly microporous, and the pore diameter is distributed between 0.3nm and 1 nm. Carbon molecular sieves have relatively good hydrophobic properties, but are resistant to CO 2 The adsorption capacity of (a) would also be correspondingly lower (ind. Eng. Chem. Res.2008,47,8048). At the same time, the carbon material tends to be more complex in source and less dense in volume, resulting in greater loading in the adsorbent bed and increased production costs.
The zeolite molecular sieve is in CO 2 The most widely used adsorbent in the trapping process has a basic structure of a ring structure in which regular tetrahedrons centered on Si atoms or Al atoms are connected via oxygen bridges. The largest amount of zeolitic molecular sieves currently used in this process are the 5A molecular sieves and the 13X molecular sieves. Its advantage is high effect on CO 2 The adsorption capacity of the catalyst is large and can reach 5mmol/g at normal temperature and normal pressure, but partial alkali metal cations are introduced into the framework, so that the catalyst can adsorb CO 2 Tends to be higher, resulting in higher energy consumption for molecular sieve regeneration (ind. Eng. Chem. Res.2006,45,3248, j.am. Chem. Soc.,2005,127,17998). The MFI molecular sieve is a small-pore molecular sieve, its main channel is formed from ten-membered ring, and its channel size
Mark Davis et al report low concentrations of CO 2 The size of the restricted space in the adsorption is that of CO capture 2 Key, and the MFI is approximately +due to its bore junction size>
Has good CO 2 Adsorption performance (Proc. Natl. Acad. Sci. U.S.A.,2022,119,39, e2211544119), suitable for CO 2 And N 2 The adsorption separation of (3).
Patent CN111977667A reports synthesis of MFI molecular sieves with silicon to heteroatom ratios as low as 5, but such moleculesThe sieve has a skeleton structure which is easy to deform because the silicon content is too low. Patent CN114259837a uses commercial ZSM-5 molecular sieves for flue gas capture by ion exchange, albeit with higher CO 2 However, the absorption rate still needs to be pretreated to remove water in the gas, and the desorption temperature is high, namely, the adsorption step is increased and the desorption energy consumption is high. The problem of high energy consumption for desorption and regeneration of the molecular sieve adsorbent can be effectively solved by improving the silica-alumina ratio of the molecular sieve and reducing alkali metal cations, which is well verified on an SSZ-13 molecular sieve (Langmuir, 2013,29,832-839). However, the higher silicon-aluminum ratio can lead to the introduction of defect sites in the synthesis process of the molecular sieve, and the increase of the water vapor adsorption amount in the gas. Jun Wang et al successfully improved the water resistance of molecular sieves by doping Fe in the channels (Science 373 (2021): 315-320.), and CN109422276A successfully synthesized molecular sieves with H as the equilibrium cation and successfully applied to CO 2 Adsorption of (2), but still in the absence of CO in the wet condition 2 And (4) adsorption application. Therefore, there is a need for a high performance CO with high silicon content and steam resistance 2 Adsorbing the separation material.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a transition metal doped molecular sieve, a preparation method and application thereof, and the transition metal doped and modified MFI molecular sieve adsorbent can efficiently adsorb CO 2 -N 2 CO in the System 2 While efficiently adsorbing CO in a humid environment 2 。
In order to achieve the aim, the invention adopts tetrapropylammonium hydroxide as a template agent of a hydrothermal system, successfully synthesizes the MFI molecular sieve with high silicon-metal ratio by optimizing the components of the initial gel of the molecular sieve synthesis and selecting proper synthesis conditions, and the MFI molecular sieve is used for preferentially adsorbing CO 2 Is very suitable for CO 2 -N 2 The gas system is separated from the adsorbent. In addition, the MFI molecular sieve treated under the water vapor condition can maintain more than 90 percent of CO 2 Capacity, very suitable for CO under humid conditions 2 And (4) adsorbing.
The technical scheme adopted by the invention is as follows:
the molecular sieve doped with transition metal has a chemical composition molar ratio of aYO 2 ：bZO：cM 2 O, wherein 10 ≦ a ≦ 50,0.1 ≦ b ≦ 1,0 < c ≦ 2.5, Y is a tetravalent element, Z is a divalent transition metal element, M is an H element, and the molecular sieve has characteristic peaks at least within the following 4 interplanar spacings (d), the first interplanar spacing d =11.0 ± 0.3, the second interplanar spacing d =9.9 ± 0.2, the third interplanar spacing d =4.3 ± 0.2, and the fourth interplanar spacing d =3.8 ± 0.2, as determined by X-ray diffraction.
Further, the transition metal doped molecular sieve has MFI molecular sieve configuration identified by International molecular sieves Association (IZA); the element composition contains more tetravalent elements Y and less divalent elements Z, and a is more than or equal to 10 and less than or equal to 20,0.05 and less than or equal to b and less than or equal to 0.4,0 and less than or equal to c and less than or equal to 2.5 which are measured by nuclear magnetic resonance spectroscopy and inductively coupled plasma spectroscopy.
Furthermore, the transition metal doped molecular sieve has a chemical composition in which Y is a tetravalent element, and comprises one or more of Si, ge and Sn, preferably Si; z in the chemical composition is a divalent transition metal element, and comprises one or more of Mg, mn, zn, fe and Cu, preferably Cu or Mn, and more preferably Cu.
The preparation method of the transition metal doped molecular sieve comprises the following steps: carrying out hydrothermal synthesis reaction on a mixed aqueous solution at least containing tetrapropylammonium hydroxide, nitrate, acetate or oxalate of divalent transition metal Z and a compound raw material containing a tetravalent element Y to obtain a precursor of the molecular sieve; and then filtering, washing and drying the precursor of the molecular sieve, and placing the precursor in an air atmosphere for high-temperature calcination to obtain the molecular sieve.
The preparation method of the molecular sieve comprises the following specific steps:
(a) Sequentially adding tetrapropylammonium hydroxide and deionized water into a reaction kettle, heating and stirring to fully dissolve and uniformly mix, and then according to (10-50) YO 2 : the oxide molar ratio of ZO is added into two of the molecular sieve compositionsNitrate, acetate or oxalate of valence transition metal Z (such as copper acetate) and compound raw material containing tetravalent element Y (such as TEOS or silica gel), stirring and aging to obtain initial gel solution, transferring the initial gel solution into a closed reaction kettle, and carrying out hydrothermal synthesis reaction to obtain a precursor of the molecular sieve;
(b) Filtering, washing and drying the molecular sieve precursor after the reaction in the step (a), and then placing the molecular sieve precursor in an air atmosphere for calcining and activating to remove organic matters in the molecular sieve precursor, thereby preparing the molecular sieve.
In the chemical composition of the MFI molecular sieve described in step (a), Y is a tetravalent element, including but not limited to one or more of Si, ge, sn, and the like, preferably Si, sn, and more preferably Si, and the corresponding silicon source includes one or a mixture of silica sol, silica gel, active silica, or orthosilicate.
Further, in the step (a), the mass ratio of the deionized water to the tetrapropylammonium hydroxide is 1-12, preferably 3-10; the mass of the tetrapropylammonium hydroxide is 5 to 20 percent of that of the compound raw material containing the tetravalent element Y.
Further, in the step (a), the aging time is selected from 12 to 80 hours, preferably from 24 to 60 hours; the aging temperature is selected from 0-100 deg.C, preferably 10-60 deg.C; the reaction temperature of the hydrothermal synthesis is 90-300 ℃, preferably 120-250 ℃, and more preferably 140-220 ℃; the reaction time is 1-4 h; preferably 2 to 3 hours.
Further, in the step (b), the temperature in the drying process is selected to be 60-200 ℃, preferably 80-100 ℃, the drying time is selected to be 12-36h, preferably 12-24h, the dried molecular sieve precursor needs to be heated and calcined to remove the internal template agent to have the adsorption and catalysis performances, the calcining temperature is selected to be 400-800 ℃, preferably 500-600 ℃, and the constant-temperature calcining time is selected to be 0.5-24h, preferably 1-24h, and more preferably 3-10h.
The MFI molecular sieve can be applied to CO-containing 2 And N 2 CO in the mixed gas 2 And N 2 Can preferentially adsorb CO in large quantities compared with commercial Si-Al molecular sieves 2 。
The MFI molecular sieve adsorptive separation gas may be operated at 273 to 323K, preferably 288 to 308K.
The MFI molecular sieve can be applied to an adsorbent for adsorbing and treating waste gas in a humid environment, and can maintain more than 90% of CO 2 And (4) adsorption removal rate.
Compared with the prior art, the invention has the following technical effects:
(1) The transition metal doped MFI molecular sieve in the invention modulates CO through the pore channel structure 2 -N 2 The system carries out selective adsorption separation, and can avoid the cation pair CO in the framework structure of the traditional low-silica-alumina ratio zeolite molecular sieve 2 The strong adsorption of the molecular sieve reduces the adsorption heat of the molecular sieve, thereby reducing the energy consumption of molecular sieve regeneration.
(2) Compared with the silicon-aluminum MFI molecular sieve, the MFI molecular sieve pore channel structure doped with the transition metal has little change, but the method of doping part of the transition metal in the molecular sieve framework structure can improve the CO content of the molecular sieve without obviously improving the adsorption heat of the molecular sieve 2 Thereby increasing the adsorption separation factor of the molecular sieve.
(3) The transition metal doped MFI molecular sieve can introduce Cu element in the synthesis process, can obtain a high-silicon MFI molecular sieve with high Cu element dispersion, and can maintain more than 90% of CO in a 298K humid environment 2 And (4) adsorption removal rate.
Drawings
FIG. 1 is a graphic representation of the XRD test results for H-MFI-Cu/10 in example 1;
FIG. 2 is a graph showing the XRD test results of H-MFI-Cu/20 in example 2;
FIG. 3 is a graphic representation of the XRD test results for H-MFI-Cu/30 in example 3;
FIG. 4 is a graphic representation of the XRD test results for H-MFI-Cu/40 in example 4;
FIG. 5 is a graphic representation of the XRD test results for H-MFI-Cu/50 in example 5;
FIG. 6 is a graphic representation of the XRD test results for H-MFI-Mn/10 in example 6;
FIG. 7 is a graphic representation of the XRD test results for H-MFI-Mn/20 in example 7;
FIG. 8 is a graphic representation of the XRD test results for H-MFI-Mn/30 in example 8;
FIG. 9 is a graphic representation of the XRD test results for H-MFI-Mn/40 in example 9;
FIG. 10 is a graphic representation of the XRD test results for H-MFI-Mn/50 in example 10;
FIG. 11 is a TEM and Mapping of H-MFI-Cu/40 in example 11;
FIG. 12 is a TEM and Mapping of H-MFI-Mn/30 in example 12.
Detailed Description
The invention is further illustrated with reference to the following specific examples, without limiting the scope of the invention thereto.
[ Instrument characterization ]
< X-ray diffraction measurement >
The X-ray diffraction measuring instrument is Panalytical X' Pert PRO, a detection light source Cu K alpha, tube voltage of 40kV, tube current of 40mA, a detection angle range of 5-50 degrees and detection time of 10min. The phase structure of the synthesized molecular sieve is determined by X-ray diffraction, ground sample powder is added into a square hole on a glass plate, then the glass plate is inserted into the axial position of an angle measuring instrument, and a probe rotates at the speed of 2 theta/min under the irradiation of a Cu Kalpha light source. Further, the light source is not limited to Cu K α, and Co K α, mo K α, and Ag K α can be used as a light source for phase analysis. The starting material morphology tested may be powder, emulsion or solid particles.
< inductively coupled plasma Spectroscopy >
Inductively coupled plasma spectroscopy (ICP) was performed using a PerkinElmer Optima8x00. The invention determines the contents of tetravalent element Y and divalent element Z in the synthesized molecular sieve by inductively coupled plasma spectroscopy. The concentration gradient absorption curve is made after the standard sample is diluted. The sample is dissolved by hydrofluoric acid, diluted by water and then the concentration of each element in the sample is determined by the absorption peak intensity.
< measurement of pore parameters >
The pore parameters are measured by Quantachrome Autosorb-iQ2. The specific surface area and the pore channel parameters of the zeolite molecular sieve are calculated by an Ar adsorption isotherm under 87K. Taking 50mg of sample, placing the sample into a sample tube, and then placing the sample into 87K solution Ar, wherein the adsorption pressure is 0-760mmHg. All samples were activated at 350 ℃ for more than 6h before adsorption.
< measurement of gas adsorption >
The gas adsorption assay employs Quantachrome Autosorb-iQ2. The present invention tests gas adsorption selectivity by gas adsorption assay. CO2 2 -N 2 And (3) measuring the adsorption isotherm at 288-308K, putting 1000mg of a sample into a sample tube, and then putting the sample into a 288-308K thermostatic water bath, wherein the adsorption pressure is 0-1bar. All samples were activated at 350 ℃ for more than 6h before adsorption. The adsorption heat of the zeolite molecular sieve to different gases is calculated by the Clapperon-Clausius equation according to adsorption isotherm data at different temperatures.
< high-resolution Transmission Electron microscopy measurement >
The shape measurement adopts high resolution Tecnai G2F 30 model
And the transmission electron microscope has the test voltage of 300kV.
< evaluation of Water resistance of molecular Sieve >
Treating the prepared zeolite molecular sieve in 40 deg.C saturated steam atmosphere for 12h, taking out, and adding N 2 Purging for 6h, and vacuum treating for 6h to remove surface free water. It was then subjected to CO using the conditions in the gas adsorption assay described above 2 And (5) performing adsorption test.
[ examples ] A method for producing a compound
< example 1>
To 6.8877g of TPAOH aqueous solution (TPAOH mass = 40%) was added 0.1016g of water followed by the sequential addition of 6.12g of TEOS (mass about 98%), 0.52g of anhydrous copper acetate (mass about 98%), followed by aging at room temperature for 12h to give the initial solution. Adding the initial solution into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, sealing, and dynamically crystallizing for 2 hours at the reaction temperature of 200 ℃ and the autogenous pressure. And after the hydrothermal reaction is finished, cooling, filtering and washing the reaction liquid to obtain a crystallized product. The crystals obtained were dried at 100 ℃ for 12h and then calcined in air: heating to 580 ℃ at the speed of 5 ℃/min, maintaining for 6H at 580 ℃, and then cooling to 100 ℃ to obtain H-MFI-Cu/10 (the naming rule of all self-made molecular sieves H-MFI-Cu/10 is H-MFI-Cu/10, wherein H is a balanced cation type, MFI is a molecular sieve configuration, cu is a framework heteroatom type, and 10 is a silicon-to-heteroatom atomic ratio, the same applies below). The dried sample is taken out and placed in a drying dish for storage, the phase analysis of the obtained product is carried out by XRD, the interplanar spacing of the characteristic peak in H-MFI-Cu/10 is shown in Table 1, the schematic diagram of the XRD test result is shown in figure 1, and the synthesized molecular sieve has the MFI molecular sieve configuration identified by IZA.
The above H-MFI-Cu/10 was used for CO 2 And (4) adsorbing. The adsorption isotherm of the sample was measured on an adsorption apparatus Autosorb-iQ2 from Quantachrome. The adsorbed gas is CO 2 (99.99%). In order to study the water vapor to molecular sieve CO 2 And (2) testing the molecular sieve into two groups of drying and moisture pretreatment, wherein the first group is drying treatment, in order to avoid the influence of water physically adsorbed in the molecular sieve on an adsorption result, a sample is dehydrated in Autosorb-iQ2, and is heated to 100 ℃ at the speed of 3 ℃/min under the extremely low vacuum degree (below 0.005 mmHg), maintained at 100 ℃ for 30min, then continuously heated to 350 ℃ at the speed of 3 ℃/min, and maintained at 350 ℃ for 6h. The second group is moisture treatment, the molecular sieve is firstly treated in a saturated steam atmosphere at 40 ℃ for 12h, and then taken out and treated with N 2 Purging for 6h, and vacuum treating for 6h to remove water in a surface free state. The temperature of gas adsorption is controlled by constant temperature water bath (precision 0.01 ℃), and the adsorption temperature is 288-308K. Under the normal pressure of 298K, two groups of H-MFI-Cu/10 are opposite to CO 2 The adsorption amounts are shown in Table 11.
TABLE 1 characteristic interplanar spacings of H-MFI-Cu/10
| Interplanar spacing (d) | |
| 1 | 11.141 |
| 2 | 9.992 |
| 3 | 6.710 |
| 4 | 4.365 |
| 5 | 4.003 |
| 6 | 3.846 |
| 7 | 3.756 |
Table 1 shows the interplanar spacings of H-MFI-Cu/10 at which 7 characteristic peaks are located, said 7 characteristic peaks corresponding to the characteristic peaks indicated by the 7 arrows in FIG. 1, the same applies hereinafter.
< example 2>
To 6.8877g of TPAOH aqueous solution (TPAOH mass = 40%) was added 0.1016g of water followed by the sequential addition of 6.12g of TEOS (mass about 98%), 0.26g of anhydrous copper acetate (mass about 98%), followed by aging at room temperature for 12h to give the initial solution. Adding the initial solution into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, sealing, and dynamically crystallizing for 2 hours at the reaction temperature of 200 ℃ and the autogenous pressure. And after the hydrothermal reaction is finished, cooling, filtering and washing the reaction liquid to obtain a crystallized product. The crystals obtained were dried at 100 ℃ for 12h and then calcined in air: heating to 580 deg.C at a rate of 5 deg.C/min, maintaining at 580 deg.C for 6H, and cooling to 100 deg.C to obtain H-MFI-Cu/20. The dried sample is taken out and placed in a drying dish for storage, the phase analysis of the obtained product is carried out by XRD, the interplanar spacing of the characteristic peak in H-MFI-Cu/20 is shown in Table 2, the schematic diagram of the XRD test result is shown in figure 2, and the synthesized molecular sieve has the MFI molecular sieve configuration identified by IZA.
The above-mentioned H-MFI-Cu/20 was used for CO 2 And (4) adsorbing. The adsorption isotherm of the sample was measured on an Autosorb-iQ2 from Quantachrome. The adsorbed gas is CO 2 (99.99%). In order to study the water vapor to molecular sieve CO 2 And (2) testing the molecular sieve into two groups of drying and moisture pretreatment, wherein the first group is drying treatment, in order to avoid the influence of water physically adsorbed in the molecular sieve on an adsorption result, a sample is dehydrated in Autosorb-iQ2, and is heated to 100 ℃ at the speed of 3 ℃/min under the extremely low vacuum degree (below 0.005 mmHg), maintained at 100 ℃ for 30min, then continuously heated to 350 ℃ at the speed of 3 ℃/min, and maintained at 350 ℃ for 6h. The second group is moisture treatment, the molecular sieve is firstly treated in a saturated steam atmosphere at 40 ℃ for 12h, and then taken out and treated with N 2 Purging for 6h, and vacuum treating for 6h to remove water in a surface free state. The temperature of gas adsorption is controlled by constant temperature water bath (precision 0.01 ℃), and the adsorption temperature is 288-308K. Under the normal pressure of 298K, two groups of H-MFI-Cu/10 are opposite to CO 2 The adsorption amount of (D) is shown in Table 11.
TABLE 2 characteristic interplanar spacings of H-MFI-Cu/20
| Interplanar spacing (d) | |
| 1 | 11.112 |
| 2 | 9.993 |
| 3 | 6.683 |
| 4 | 4.353 |
| 5 | 4.076 |
| 6 | 3.845 |
| 7 | 3.744 |
< example 3>
To 6.8877g of TPAOH aqueous solution (TPAOH mass = 40%) was added 0.1016g of water followed by the sequential addition of 6.12g of TEOS (mass about 98%), 0.17g of anhydrous copper acetate (mass about 98%), followed by aging at room temperature for 12h to give the initial solution. Adding the initial solution into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, sealing, and dynamically crystallizing for 2 hours at the reaction temperature of 200 ℃ and the autogenous pressure. And after the hydrothermal reaction is finished, cooling, filtering and washing the reaction liquid to obtain a crystallized product. The crystals obtained were dried at 100 ℃ for 12h and then calcined in air: heating to 580 ℃ at the rate of 5 ℃/min, maintaining for 6H at 580 ℃, and then cooling to 100 ℃ to obtain H-MFI-Cu/30. The dried sample is taken out and placed in a drying dish for storage, the phase analysis of the obtained product is carried out by XRD, the interplanar spacing of the characteristic peak in H-MFI-Cu/30 is shown in Table 3, the schematic diagram of the XRD test result is shown in figure 3, and the synthesized molecular sieve has the MFI molecular sieve configuration identified by IZA.
The above-mentioned H-MFI-Cu/30 was used for CO 2 And (4) adsorbing. The adsorption isotherm of the sample was measured on an Autosorb-iQ2 of Quantachrome. The adsorbed gas is CO 2 (99.99%). In order to study the water vapor on the molecular sieve CO 2 Influence of adsorption, willThe molecular sieve is divided into two groups for drying and moisture pretreatment, wherein the first group is drying treatment, in order to avoid the influence of water physically adsorbed in the molecular sieve on the adsorption result, a sample is dehydrated in Autosorb-iQ2, and is heated to 100 ℃ at the speed of 3 ℃/min under the extremely low vacuum degree (below 0.005 mmHg), the temperature is maintained at 100 ℃ for 30min, then the molecular sieve is continuously heated to 350 ℃ at the speed of 3 ℃/min, and the temperature is maintained at 350 ℃ for 6h. The second group is moisture treatment, the molecular sieve is firstly treated in a saturated steam atmosphere at 40 ℃ for 12h, and then taken out and treated with N 2 Purging for 6h, and vacuum treating for 6h to remove surface free water. The temperature of gas adsorption is controlled by constant temperature water bath (precision 0.01 ℃), and the adsorption temperature is 288-308K. Under the normal pressure of 298K, two groups of H-MFI-Cu/30 pairs of CO 2 The adsorption amount of (D) is shown in Table 11.
TABLE 3 characteristic interplanar spacings of N H-MFI-Cu/30
< example 4>
To 6.8877g of TPAOH aqueous solution (TPAOH mass = 40%) was added 0.1016g of water followed by the sequential addition of 6.12g of TEOS (mass about 98%), 0.13g of anhydrous copper acetate (mass about 98%), followed by aging at room temperature for 12h to give the initial solution. Adding the initial solution into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, sealing, and dynamically crystallizing for 2 hours at the reaction temperature of 200 ℃ and the autogenous pressure. And after the hydrothermal reaction is finished, cooling, filtering and washing the reaction liquid to obtain a crystallized product. The crystals obtained were dried at 100 ℃ for 12h and then calcined in air: heating to 580 deg.C at a rate of 5 deg.C/min, maintaining at 580 deg.C for 6H, and cooling to 100 deg.C to obtain H-MFI-Cu/40. The dried sample is taken out and placed in a drying dish for storage, the phase analysis of the obtained product is carried out by XRD, the interplanar spacing of the characteristic peak in H-MFI-Cu/40 is shown in Table 4, the schematic diagram of the XRD test result is shown in figure 4, and the synthesized molecular sieve has the MFI molecular sieve configuration identified by IZA.
The above-mentioned H-MFI-Cu/40 was used for CO 2 And (4) adsorbing. The adsorption isotherm of the sample was measured on an Autosorb-iQ2 from Quantachrome. The adsorbed gas is CO 2 (99.99%). In order to study the water vapor on the molecular sieve CO 2 And (2) testing the molecular sieve into two groups of drying and moisture pretreatment, wherein the first group is drying treatment, in order to avoid the influence of water physically adsorbed in the molecular sieve on an adsorption result, a sample is dehydrated in Autosorb-iQ2, and is heated to 100 ℃ at the speed of 3 ℃/min under the extremely low vacuum degree (below 0.005 mmHg), maintained at 100 ℃ for 30min, then continuously heated to 350 ℃ at the speed of 3 ℃/min, and maintained at 350 ℃ for 6h. The second group is moisture treatment, the molecular sieve is firstly treated in a saturated steam atmosphere at 40 ℃ for 12h, and then taken out and treated with N 2 Purging for 6h, and vacuum treating for 6h to remove water in a surface free state. The temperature of gas adsorption is controlled by constant temperature water bath (precision 0.01 ℃), and the adsorption temperature is 288-308K. At 298K under normal pressure, two groups of H-MFI-Cu/40 pairs of CO 2 The adsorption amounts are shown in Table 11.
TABLE 4 characteristic interplanar spacings of H-MFI-Cu/40
| Interplanar spacing (d) | |
| 1 | 11.076 |
| 2 | 9.951 |
| 3 | 5.962 |
| 4 | 4.355 |
| 5 | 3.993 |
| 6 | 3.837 |
| 7 | 3.301 |
< example 5>
To 6.8877g of TPAOH aqueous solution (TPAOH mass = 40%) was added 0.1016g of water followed by the sequential addition of 6.12g of TEOS (mass about 98%), 0.10g of anhydrous copper acetate (mass about 98%), followed by aging at room temperature for 12h to give the initial solution. Adding the initial solution into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, sealing, and dynamically crystallizing for 2 hours at the reaction temperature of 200 ℃ and the autogenous pressure. And after the hydrothermal reaction is finished, cooling, filtering and washing the reaction liquid to obtain a crystallized product. The crystals obtained were dried at 100 ℃ for 12h and then calcined in air: heating to 580 deg.C at a rate of 5 deg.C/min, maintaining at 580 deg.C for 6H, and cooling to 100 deg.C to obtain H-MFI-Cu/50. The dried sample is taken out and placed in a drying dish for storage, the phase analysis of the obtained product is carried out by XRD, the interplanar spacing of the characteristic peak in H-MFI-Cu/50 is shown in Table 5, the schematic diagram of the XRD test result is shown in figure 5, and the synthesized molecular sieve has the MFI molecular sieve configuration identified by IZA.
The above H-MFI-Cu/50 was used for CO 2 And (4) adsorbing. The adsorption isotherm of the sample was measured on an Autosorb-iQ2 from Quantachrome. The adsorbed gas is CO 2 (99.99%). In order to study the water vapor on the molecular sieve CO 2 The influence of adsorption is tested by dividing the molecular sieve into two groups of drying and moisture pretreatment, wherein one group is drying treatment to avoid water physically adsorbed in the molecular sieve from adsorbing the adsorption junctionEffect of the fruit, the sample was dehydrated in Autosorb-iQ2, heated to 100 ℃ at a rate of 3 ℃/min under a very low vacuum (below 0.005 mmHg), maintained at 100 ℃ for 30min, then further heated to 350 ℃ at a rate of 3 ℃/min, maintained at 350 ℃ for 6h. The second group is moisture treatment, the molecular sieve is firstly treated in a saturated steam atmosphere at 40 ℃ for 12h, and then taken out and treated with N 2 Purging for 6h, and vacuum treating for 6h to remove water in a surface free state. The temperature of gas adsorption is controlled by constant temperature water bath (precision 0.01 ℃), and the adsorption temperature is 288-308K. Under the normal pressure of 298K, two groups of H-MFI-Cu/50 are used for CO 2 The adsorption amounts are shown in Table 11.
TABLE 5 characteristic interplanar spacings of H-MFI-Cu/50
| Interplanar spacing (d) | |
| 1 | 11.071 |
| 2 | 9.978 |
| 3 | 6.679 |
| 4 | 4.348 |
| 5 | 3.997 |
| 6 | 3.843 |
| 7 | 3.744 |
Example 6
0.1016g of water was added to 6.8877g of TPAOH aqueous solution (TPAOH mass = 40%), followed by 6.12g of TEOS (about 98 mass%), 0.6988g of manganese acetate tetrahydrate (about 98 mass%), followed by aging at room temperature for 12h to obtain an initial solution. Adding manganese acetate tetrahydrate into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, sealing, and dynamically crystallizing for 2 hours at the reaction temperature of 200 ℃ and the autogenous pressure. And after the hydrothermal reaction is finished, cooling, filtering and washing the reaction liquid to obtain a crystallized product. The crystals obtained were dried at 100 ℃ for 12h and then calcined in air: heating to 580 deg.C at a rate of 5 deg.C/min, maintaining at 580 deg.C for 6H, and cooling to 100 deg.C to obtain H-MFI-Mn/10. The dried sample is taken out and placed in a drying dish for storage, the obtained product is subjected to phase analysis by XRD, the interplanar spacing of the characteristic peak in H-MFI-Mn/10 is shown in Table 6, and the schematic diagram of the XRD test result is shown in figure 6, which shows that the synthesized molecular sieve has the MFI molecular sieve configuration identified by IZA.
The above H-MFI-Mn/10 is used for CO 2 And (4) adsorbing. The adsorption isotherm of the sample was measured on an Autosorb-iQ2 of Quantachrome. The adsorbed gas being CO 2 (99.99%). In order to study the water vapor on the molecular sieve CO 2 And (2) testing the molecular sieve into two groups of drying and moisture pretreatment, wherein the first group is drying treatment, in order to avoid the influence of water physically adsorbed in the molecular sieve on an adsorption result, a sample is dehydrated in Autosorb-iQ2, and is heated to 100 ℃ at the speed of 3 ℃/min under the extremely low vacuum degree (below 0.005 mmHg), maintained at 100 ℃ for 30min, then continuously heated to 350 ℃ at the speed of 3 ℃/min, and maintained at 350 ℃ for 6h. The second group is moisture treatment, firstly the molecular sieve is put in the saturated steam atmosphere at 40 ℃ for 12h, and then taken out and treated with N 2 Purging for 6h, and vacuum treating for 6h to remove surface free water. Controlling the temperature of gas adsorption by constant temperature water bath (precision 0.01 ℃), and controlling the adsorption temperature288-308K. Under the normal pressure of 298K, two groups of H-MFI-Mn/10 are opposite to CO 2 The adsorption amount of (D) is shown in Table 11.
TABLE 6 characteristic interplanar spacings of H-MFI-Mn/10
| Interplanar spacing (d) | |
| 1 | 11.110 |
| 2 | 9.973 |
| 3 | 6.353 |
| 4 | 4.360 |
| 5 | 4.000 |
| 6 | 3.842 |
| 7 | 3.753 |
< example 7>
To 6.8877g of TPAOH aqueous solution (TPAOH mass = 40%) was added 0.1016g of water, followed by the sequential addition of 6.12g of TEOS (mass about 98%), 0.3494g of manganese acetate tetrahydrate (mass about 98%), followed by aging at room temperature for 12h to obtain the initial solution. Adding the initial solution into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, sealing, and dynamically crystallizing for 2 hours at the reaction temperature of 200 ℃ and the autogenous pressure. And after the hydrothermal reaction is finished, cooling, filtering and washing the reaction liquid to obtain a crystallized product. The crystals obtained were dried at 100 ℃ for 12h and then calcined in air: heating to 580 deg.C at a rate of 5 deg.C/min, maintaining at 580 deg.C for 6H, and cooling to 100 deg.C to obtain H-MFI-Mn/20. The dried sample is taken out and placed in a drying dish for storage, the obtained product is subjected to phase analysis by XRD, the interplanar spacing of the characteristic peak in H-MFI-Mn/20 is shown in Table 7, and the schematic diagram of the XRD test result is shown in FIG. 7, which shows that the synthesized molecular sieve has the MFI molecular sieve configuration identified by IZA.
The above H-MFI-Mn/20 was used for CO 2 And (4) adsorbing. The adsorption isotherm of the sample was measured on an Autosorb-iQ2 of Quantachrome. The adsorbed gas is CO 2 (99.99%). In order to study the water vapor on the molecular sieve CO 2 And (2) testing the molecular sieve into two groups of drying and moisture pretreatment, wherein the first group is drying treatment, in order to avoid the influence of water physically adsorbed in the molecular sieve on an adsorption result, a sample is dehydrated in Autosorb-iQ2, and is heated to 100 ℃ at the speed of 3 ℃/min under the extremely low vacuum degree (below 0.005 mmHg), maintained at 100 ℃ for 30min, then continuously heated to 350 ℃ at the speed of 3 ℃/min, and maintained at 350 ℃ for 6h. The second group is moisture treatment, the molecular sieve is firstly treated in a saturated steam atmosphere at 40 ℃ for 12h, and then taken out and treated with N 2 Purging for 6h, and vacuum treating for 6h to remove surface free water. The temperature of gas adsorption is controlled by constant temperature water bath (precision 0.01 ℃), and the adsorption temperature is 288-308K. Under the normal pressure of 298K, two groups of H-MFI-Mn/20 pairs of CO 2 The adsorption amounts are shown in Table 11.
TABLE 7 characteristic interplanar spacings of H-MFI-Mn/20
< example 8>
0.1016g of water was added to 6.8877g of TPAOH aqueous solution (TPAOH mass = 40%), followed by the sequential addition of 6.12g of TEOS (mass about 98%), 0.2306g of manganese acetate tetrahydrate (mass about 98%), followed by 12h aging at room temperature to obtain the initial solution. Adding the initial solution into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, sealing, and dynamically crystallizing for 2 hours at the reaction temperature of 200 ℃ and the autogenous pressure. And after the hydrothermal reaction is finished, cooling, filtering and washing the reaction liquid to obtain a crystallized product. The crystals obtained were dried at 100 ℃ for 12h and then calcined in air: heating to 580 deg.C at a rate of 5 deg.C/min, maintaining at 580 deg.C for 6H, and cooling to 100 deg.C to obtain H-MFI-Mn/30. The dried sample is taken out and placed in a drying dish for storage, the obtained product is subjected to phase analysis by XRD, the interplanar spacing of the characteristic peak in H-MFI-Mn/30 is shown in Table 8, and the schematic diagram of the XRD test result is shown in FIG. 8, which indicates that the synthesized molecular sieve has the MFI molecular sieve configuration identified by IZA.
The above H-MFI-Mn/30 is used for CO 2 And (4) adsorbing. The adsorption isotherm of the sample was measured on an Autosorb-iQ2 of Quantachrome. The adsorbed gas is CO 2 (99.99%). In order to study the water vapor to molecular sieve CO 2 And (2) testing the molecular sieve into two groups of drying and moisture pretreatment, wherein the first group is drying treatment, in order to avoid the influence of water physically adsorbed in the molecular sieve on an adsorption result, a sample is dehydrated in Autosorb-iQ2, and is heated to 100 ℃ at the rate of 3 ℃/min under the extremely low vacuum degree (below 0.005 mmHg) and maintained at 100 ℃ for 30min, and then is continuously heated to 350 ℃ at the rate of 3 ℃/min and maintained at 350 ℃ for 6h. The second group is moisture treatment, the molecular sieve is firstly treated in a saturated steam atmosphere at 40 ℃ for 12h, and then taken out and treated with N 2 Purging for 6h, and vacuum treating for 6h to remove water in a surface free state. The temperature of gas adsorption is controlled by constant temperature water bath (precision 0.01 ℃), and the adsorption temperature is 288-308K. Under the normal pressure of 298K, two groups of H-MFI-Mn/30 pairs of CO 2 The adsorption amount of (D) is shown in Table 11.
TABLE 8 characteristic interplanar spacings of H-MFI-Mn/30
| Interplanar spacing (d) | |
| 1 | 11.065 |
| 2 | 9.940 |
| 3 | 6.679 |
| 4 | 4.353 |
| 5 | 3.994 |
| 6 | 3.835 |
| 7 | 3.748 |
< example 9>
0.1016g of water was added to 6.8877g of TPAOH aqueous solution (TPAOH mass = 40%), followed by 6.12g of TEOS (about 98 mass%), 0.1747g of manganese acetate tetrahydrate (about 98 mass%), followed by aging at room temperature for 12h to obtain an initial solution. Adding the initial solution into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, sealing, and dynamically crystallizing for 2 hours at the reaction temperature of 200 ℃ and the autogenous pressure. And after the hydrothermal reaction is finished, cooling, filtering and washing the reaction liquid to obtain a crystallized product. The crystals obtained were dried at 100 ℃ for 12h and then calcined in air: heating to 580 deg.C at a rate of 5 deg.C/min, maintaining at 580 deg.C for 6H, and cooling to 100 deg.C to obtain H-MFI-Mn/40. The dried sample is taken out and placed in a drying dish for storage, the obtained product is subjected to phase analysis by XRD, the interplanar spacing of the characteristic peak in H-MFI-Mn/40 is shown in Table 9, and the schematic diagram of the XRD test result is shown in FIG. 9, which shows that the synthesized molecular sieve has the MFI molecular sieve configuration identified by IZA.
The above H-MFI-Mn/40 was used for CO 2 And (4) adsorbing. The adsorption isotherm of the sample was measured on an Autosorb-iQ2 of Quantachrome. The adsorbed gas being CO 2 (99.99%). In order to study the water vapor to molecular sieve CO 2 And (2) testing the molecular sieve into two groups of drying and moisture pretreatment, wherein the first group is drying treatment, in order to avoid the influence of water physically adsorbed in the molecular sieve on an adsorption result, a sample is dehydrated in Autosorb-iQ2, and is heated to 100 ℃ at the speed of 3 ℃/min under the extremely low vacuum degree (below 0.005 mmHg), maintained at 100 ℃ for 30min, then continuously heated to 350 ℃ at the speed of 3 ℃/min, and maintained at 350 ℃ for 6h. The second group is moisture treatment, the molecular sieve is firstly treated in a saturated steam atmosphere at 40 ℃ for 12h, and then taken out and treated with N 2 Purging for 6h, and vacuum treating for 6h to remove water in a surface free state. The temperature of gas adsorption is controlled by constant temperature water bath (precision 0.01 ℃), and the adsorption temperature is 288-308K. Under the normal pressure of 298K, two groups of H-MFI-Mn/40 are used for CO 2 The adsorption amounts are shown in Table 11.
TABLE 9 characteristic interplanar spacings of H-MFI-Mn/40
| Interplanar spacing (d) | |
| 1 | 11.168 |
| 2 | 10.025 |
| 3 | 6.729 |
| 4 | 4.369 |
| 5 | 4.007 |
| 6 | 3.847 |
| 7 | 3.759 |
< example 10>
To 6.8877g of TPAOH aqueous solution (TPAOH mass = 40%) was added 0.1016g of water, followed by sequentially adding 6.12g of TEOS (mass about 98%), 0.1397g of manganese acetate tetrahydrate (mass about 98%), followed by aging at room temperature for 12 hours to obtain an initial solution. Adding the initial solution into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, sealing, and dynamically crystallizing for 2 hours at the reaction temperature of 200 ℃ and the autogenous pressure. And after the hydrothermal reaction is finished, cooling, filtering and washing the reaction liquid to obtain a crystallized product. The crystals obtained were dried at 100 ℃ for 12h and then calcined in air: heating to 580 ℃ at the rate of 5 ℃/min, maintaining for 6H at 580 ℃, and then cooling to 100 ℃ to obtain H-MFI-Mn/50. The dried sample is taken out and placed in a drying dish for storage, the obtained product is subjected to phase analysis by XRD, the interplanar spacing of the characteristic peak in H-MFI-Mn/50 is shown in Table 10, and the schematic diagram of the XRD test result is shown in FIG. 10, which shows that the synthesized molecular sieve has the MFI molecular sieve configuration identified by IZA.
The above H-MFI-Mn/50 was used for CO 2 And (4) adsorbing. The adsorption isotherm of the sample was measured on an Autosorb-iQ2 of Quantachrome. The adsorbed gas being CO 2 (99.99%). In order to study the water vapor on the molecular sieve CO 2 And (2) testing the molecular sieve into two groups of drying and moisture pretreatment, wherein the first group is drying treatment, in order to avoid the influence of water physically adsorbed in the molecular sieve on an adsorption result, a sample is dehydrated in Autosorb-iQ2, and is heated to 100 ℃ at the speed of 3 ℃/min under the extremely low vacuum degree (below 0.005 mmHg), maintained at 100 ℃ for 30min, then continuously heated to 350 ℃ at the speed of 3 ℃/min, and maintained at 350 ℃ for 6h. The second group is moisture treatment, the molecular sieve is firstly treated in a saturated steam atmosphere at 40 ℃ for 12h, and then taken out and treated with N 2 Purging for 6h, and vacuum treating for 6h to remove water in a surface free state. The temperature of gas adsorption is controlled by constant temperature water bath (precision 0.01 ℃), and the adsorption temperature is 288-308K. At 298K and normal pressure, two groups of H-MFI-Mn/50 pairs of CO 2 The adsorption amounts are shown in Table 11.
TABLE 10 characteristic interplanar spacings of H-MFI-Mn/50
< example 11>
Examples were compared between the decrease in the amount of adsorption under dry conditions and the decrease in the amount of adsorption under wet conditions<4>Preparing H-MFI-Cu/40 for CO 2 /N 2 The adsorption separation is carried out, ICP element analysis is carried out on the adsorption separation, and the analysis result shows that the chemical element composition of H-MFI-Cu/40 is H ≤2.61 Si 94.69 Cu 2.61 O 192 The zeolite molecular sieve Si/Cu =36.25, cu wt% is 2.5%. The TEM scanning is performed at the same time, and the scanning result and Mapping are shown in FIG. 11.The adsorption isotherm of the sample was measured on an Autosorb-iQ2 of Quantachrome. The adsorbed gas being CO 2 (99.99％)、N 2 (99.99%). In order to avoid the influence of physically adsorbed water in the molecular sieve on the adsorption result, the sample is dehydrated in the Autosorb-iQ2, heated to 100 ℃ at the rate of 3 ℃/min under the extremely low vacuum degree (below 0.005 mmHg), maintained at 100 ℃ for 30min, then continuously heated to 350 ℃ at the rate of 3 ℃/min, and maintained at 350 ℃ for 6h. The temperature of gas adsorption is controlled by constant temperature water bath (precision 0.01 ℃), and the adsorption temperature is 288-308K. Under the normal pressure of 298K, H-MFI-Cu/40 is to CO 2 、N 2 The adsorption amount, heat of adsorption and adsorption selectivity (selectivity calculated from IAST theory, the same applies hereinafter) are shown in Table 13.
< example 12>
Examples were compared between the decrease in the amount of adsorption under dry conditions and the decrease in the amount of adsorption under wet conditions<8>Preparing H-MFI-Mn/30 for CO 2 /N 2 The adsorption separation is carried out, ICP element analysis is carried out on the mixture, and the analysis result shows that the chemical element composition of H-MFI-Mn/30 is H ≤3.2 Si 94.4 Mn 3.2 O 192 The zeolite molecular sieve Si/Mn =29.53, mn wt% 2.7%, while TEM scanning was performed, the scanning results and Mapping are shown in fig. 12. The adsorption isotherm of the sample was measured on an Autosorb-iQ2 from Quantachrome. The adsorbed gas is CO 2 (99.99％)、N 2 (99.99%). In order to avoid the influence of physically adsorbed water in the molecular sieve on the adsorption result, the sample is dehydrated in the Autosorb-iQ2, heated to 100 ℃ at the rate of 3 ℃/min under the extremely low vacuum degree (below 0.005 mmHg), maintained at 100 ℃ for 30min, then continuously heated to 350 ℃ at the rate of 3 ℃/min, and maintained at 350 ℃ for 6h. The temperature of gas adsorption is controlled by constant temperature water bath (precision 0.01 ℃), and the adsorption temperature is 288-308K. At 298K and normal pressure, H-MFI-Mn/30 is to CO 2 、N 2 The adsorption amount, heat of adsorption and selectivity of adsorption of (A) are shown in Table 13.
< comparative example 1>
Taking a certain amount of commercial H-type molecular sieves with different configurations (the naming rule of the commercial molecular sieves is A-B/D, wherein A is a balanced cation type, B is a molecular sieve commodity/configuration name, D is a silica-alumina ratio, and the commercial molecular sieves are all silica-alumina molecular sieves), calcining the commercial H-type molecular sieves in air to ensure that impurities are removed: heating to 580 deg.C at a rate of 5 deg.C/min, maintaining at 580 deg.C for 6h, and cooling to 100 deg.C. The dried sample was taken out and stored in a drying dish.
Use of the above commercial molecular sieves for CO 2 And (4) adsorbing. The adsorption isotherm of the sample was measured on an Autosorb-iQ2 of Quantachrome. The adsorbed gas being CO 2 (99.99%). In order to study the water vapor on the molecular sieve CO 2 And (2) testing the molecular sieve into two groups of drying and moisture pretreatment, wherein the first group is drying treatment, in order to avoid the influence of water physically adsorbed in the molecular sieve on an adsorption result, a sample is dehydrated in Autosorb-iQ2, and is heated to 100 ℃ at the speed of 3 ℃/min under the extremely low vacuum degree (below 0.005 mmHg), maintained at 100 ℃ for 30min, then continuously heated to 350 ℃ at the speed of 3 ℃/min, and maintained at 350 ℃ for 6h. The second group is moisture treatment, the molecular sieve is firstly treated in a saturated steam atmosphere at 40 ℃ for 12h, and then taken out and treated with N 2 Purging for 6h, and vacuum treating for 6h to remove surface free water. Controlling the adsorption temperature of the gas by using a constant-temperature water bath (the precision is 0.01 ℃), wherein the adsorption temperature is 298K, and CO is adsorbed by different commercial molecular sieves under normal pressure 2 The adsorption amounts are shown in Table 12.
< comparative example 2>
Two commercial H-type ZSM-5 molecular sieves (SAR =30, 50, mizusawa Industrial Chemicals) were taken for comparison of adsorption performance. It was calcined in air to ensure removal of impurities: heating to 580 deg.C at a rate of 5 deg.C/min, maintaining at 580 deg.C for 6h, and cooling to 100 deg.C. The dried sample was taken out and stored in a drying dish.
The samples were also used for CO 2 /N 2 And (5) adsorbing and separating. The adsorption isotherm of the sample was measured on an Autosorb-iQ2 of Quantachrome. The adsorbed gas is CO 2 (99.99％)、N 2 (99.99%). In order to avoid the influence of physically adsorbed water in the molecular sieve on the adsorption result, the sample is dehydrated in the Autosorb-iQ2, under the extremely low vacuum degree (below 0.005 mmHg),heating to 100 deg.C at 3 deg.C/min, maintaining at 100 deg.C for 30min, heating to 350 deg.C at 3 deg.C/min, and maintaining at 350 deg.C for 6h. Controlling the adsorption temperature of the gas by a constant temperature water bath (precision 0.01 ℃), wherein the adsorption temperature is 288-308K, and the molecular sieve is used for CO at normal pressure of 298K 2 、N 2 The adsorption amount, adsorption selectivity and adsorption heat of (A) are shown in Table 13.
Table 11298K for different H-MFI-Cu and H-MFI-Mn molecular sieves on CO under dry and wet conditions 2 Amount of adsorption
TABLE 8978 Zxft 8978K different commercial molecular sieves on CO under dry and wet conditions 2 Amount of adsorption
TABLE 13298K H-MFI-Cu/40, H-MFI-Mn/30, H-ZSM-5/30 and H-ZSM-5/50 on CO 2 、N 2 Amount of adsorption, heat of adsorption and selectivity of adsorption
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (9)
1. A transition metal doped molecular sieve is characterized in that the molecular sieve has a chemical composition molar ratio of aYO 2 ：bZO：cM 2 O, wherein a is more than or equal to 10 and less than or equal to 50,0.1 and less than or equal to b is more than or equal to 1,0 and more than c and less than or equal to 2.5, Y is a tetravalent element, Z is a divalent transition metal element, M is an H element,and the molecular sieve has a characteristic peak at least in the following 4 interplanar spacings (d), the first interplanar spacing d =11.0 + -0.3, the second interplanar spacing d =9.9 + -0.2, the third interplanar spacing d =4.3 + -0.2, and the fourth interplanar spacing d =3.8 + -0.2, as measured by X-ray diffraction.
2. A transition metal doped molecular sieve according to claim 1, wherein the molecular sieve has an MFI molecular sieve configuration as defined by the international molecular sieve association (IZA); the element composition contains more tetravalent elements Y and less divalent elements Z, and a is more than or equal to 10 and less than or equal to 20,0.05 and less than or equal to b is more than or equal to 0.4,0 and more than c is less than or equal to 2.5 measured by nuclear magnetic resonance spectroscopy and inductively coupled plasma spectroscopy.
3. The transition metal-doped molecular sieve of claim 1, wherein Y in the chemical composition is a tetravalent element comprising one or more of Si, ge, sn, preferably Si;
z in the chemical composition is a divalent transition metal element, and comprises one or more of Mg, mn, zn, fe and Cu, preferably Cu or Mn, and more preferably Cu.
4. A method of making a transition metal doped molecular sieve as claimed in any of claims 1~3 comprising the steps of: carrying out hydrothermal synthesis reaction on a mixed aqueous solution at least containing tetrapropylammonium hydroxide, nitrate, acetate or oxalate of divalent transition metal Z and a compound raw material containing a tetravalent element Y to obtain a precursor of the molecular sieve; and then filtering, washing and drying the precursor of the molecular sieve, and then placing the precursor in an air atmosphere for high-temperature calcination to obtain the molecular sieve.
5. The method of claim 4, further comprising the steps of:
(a) Sequentially adding tetrapropylammonium hydroxide and deionized water into a reaction kettle, heating and stirring to fully dissolve and uniformly mix, and then adding the mixture according to (10-50) YO 2 : adding the oxide mol ratio of ZO into nitrate, acetate or oxalate of divalent transition metal Z and compound raw materials containing tetravalent element Y in the molecular sieve composition, stirring and aging to obtain initial gel solution, transferring the initial gel solution into a closed reaction kettle, and performing hydrothermal synthesis reaction to obtain a precursor of the molecular sieve;
(b) Filtering, washing and drying the molecular sieve precursor after the reaction in the step (a), and then putting the molecular sieve precursor in an air atmosphere for calcination and activation to remove organic matters in the molecular sieve precursor, thereby preparing the molecular sieve.
6. The method for preparing the transition metal-doped molecular sieve of claim 5, wherein in the step (a), the mass ratio of deionized water to tetrapropylammonium hydroxide is 1 to 12, preferably 3 to 10; the mass of the tetrapropylammonium hydroxide is 5 to 20% of the mass of the compound raw material containing the tetravalent element Y.
7. The process for preparing a transition metal doped molecular sieve according to claim 5, wherein in step (a), the aging time is selected from 12 to 80 hours, preferably from 24 to 60 hours; the aging temperature is selected from 0-100 deg.C, preferably 10-60 deg.C; the reaction temperature of the hydrothermal synthesis is 90 to 300 ℃, preferably 120 to 250 ℃, and more preferably 140 to 220 ℃; the reaction time is 1 to 4 hours; preferably 2 to 3h.
8. The method of claim 5, wherein in the step (b), the drying temperature is selected from 60 to 200 ℃, preferably from 80 to 100 ℃, the drying time is selected from 12 to 36 hours, preferably from 12 to 24 hours, the dried molecular sieve precursor is heated and calcined to remove the internal template agent for having the adsorption and catalytic properties, the calcining temperature is selected from 400 to 800 ℃, preferably from 500 to 600 ℃, and the constant-temperature calcining time is selected from 0.5 to 24 hours, preferably from 1 to 24 hours, more preferably from 3 to 10 hours.
9. Use of a transition metal doped molecular sieve according to claim 1 for the absorption separation of carbon dioxide in an atmosphere of a carbon dioxide-nitrogen system.
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| CN116237011A (en) * | 2023-04-07 | 2023-06-09 | 天津理工大学 | Hydrophobically modified zeolite molecular sieve and preparation method and application thereof |
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