CN119176566A - RHO type structure molecular sieve containing metal cations and synthesis method and application thereof - Google Patents
RHO type structure molecular sieve containing metal cations and synthesis method and application thereof Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 98
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 150000001768 cations Chemical class 0.000 title claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 19
- 239000002184 metal Substances 0.000 title claims abstract description 19
- 238000001308 synthesis method Methods 0.000 title claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 238000002425 crystallisation Methods 0.000 claims abstract description 25
- 230000008025 crystallization Effects 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000005342 ion exchange Methods 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 239000011734 sodium Substances 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 230000002194 synthesizing effect Effects 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 10
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052792 caesium Inorganic materials 0.000 claims description 10
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 10
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 10
- 239000001569 carbon dioxide Substances 0.000 claims description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 9
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical group NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 8
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 3
- 229910001593 boehmite Inorganic materials 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- KOPBYBDAPCDYFK-UHFFFAOYSA-N Cs2O Inorganic materials [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- AKUNKIJLSDQFLS-UHFFFAOYSA-M dicesium;hydroxide Chemical compound [OH-].[Cs+].[Cs+] AKUNKIJLSDQFLS-UHFFFAOYSA-M 0.000 claims description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims 4
- 229910052681 coesite Inorganic materials 0.000 claims 2
- 229910052906 cristobalite Inorganic materials 0.000 claims 2
- 239000000377 silicon dioxide Substances 0.000 claims 2
- 235000012239 silicon dioxide Nutrition 0.000 claims 2
- 229910052682 stishovite Inorganic materials 0.000 claims 2
- 229910052905 tridymite Inorganic materials 0.000 claims 2
- 230000002431 foraging effect Effects 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 21
- 238000000926 separation method Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 239000008367 deionised water Substances 0.000 description 22
- 229910021641 deionized water Inorganic materials 0.000 description 22
- 238000001914 filtration Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 239000003463 adsorbent Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 7
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 7
- 235000011130 ammonium sulphate Nutrition 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 235000013339 cereals Nutrition 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001612 separation test Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Geology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
本发明涉及分子筛技术领域，尤其涉及一种含金属阳离子的RHO型结构分子筛及其合成方法和应用，该合成方法包括以下步骤：1）导向剂的制备；2）合成溶胶的制备；3）合成溶胶经晶化、烘干、焙烧后，即得Na+,Cs‑RHO分子筛原粉；4）将所得Na+,Cs‑RHO分子筛原粉经第一离子交换为NH4 +,Csx‑RHO分子筛后，将NH4 +,Csx‑RHO分子筛经第二离子交换，得M,Csx‑RHO分子筛。本发明具有的优点是合成条件温和、晶化时间短、分子筛具有较高的比表面积和孔体积，特别在气体吸附分离过程中，具有良好的吸附活性和选择性吸附CO2性能，为CO2捕集提供有力的技术保障。
The present invention relates to the technical field of molecular sieves, and in particular to a RHO-type molecular sieve containing metal cations and a synthesis method and application thereof, wherein the synthesis method comprises the following steps: 1) preparation of a directing agent; 2) preparation of a synthetic sol; 3) crystallization, drying and roasting of the synthetic sol to obtain Na + , Cs-RHO molecular sieve raw powder; 4) exchanging the obtained Na + , Cs-RHO molecular sieve raw powder into NH4 + , Csx - RHO molecular sieve through a first ion exchange, and then exchanging the NH4 + , Csx- RHO molecular sieve through a second ion exchange to obtain M, Csx - RHO molecular sieve. The present invention has the advantages of mild synthesis conditions, short crystallization time, and a molecular sieve having a high specific surface area and pore volume, especially in a gas adsorption separation process, having good adsorption activity and selective CO2 adsorption performance, and providing a strong technical guarantee for CO2 capture.
Description
Technical Field
The invention relates to the technical field of molecular sieves, in particular to an RHO type structure molecular sieve containing metal cations, and a synthesis method and application thereof.
Background
In recent years, the severe global warming situation caused by excessive emissions of carbon dioxide (CO 2) has become increasingly prominent, which constitutes an unprecedented challenge for the ecological balance of the earth and the environment in which humans survive. Among the numerous strategies to deal with, CO 2 capture and separation technologies have been attracting attention as an effective means of reducing emissions. This technical system encompasses various methods such as solvent absorption, solid adsorption, membrane separation, and cryogenic fractionation.
The solid adsorption method has the unique advantages of the solid adsorption method, and the solid adsorbent has the efficient and reversible adsorption capacity of CO 2 in the mixed gas, so that the CO 2 is effectively separated and collected. The method has the remarkable characteristics of low energy consumption, simple and convenient operation, large adsorption capacity, excellent cycle performance, non-corrosiveness and the like, and provides powerful technical support for coping with climate change and promoting sustainable development. The molecular sieve has excellent performance in the fields of mixed gas adsorption separation, nitrogen oxide removal and the like by virtue of the unique pore channel structure, the adjustable active site and the excellent hydrothermal stability.
The RHO molecular sieve is a small pore molecular sieve with a three-dimensional 8-membered ring channel structure of 3.6A multiplied by 3.6A, and has good performance in a plurality of catalytic reactions and adsorption separation processes. CHATELAIN et al (MicroporousMaterials, 1995,4,231.) report the synthesis of RHO molecular sieves by introducing organic 18-crown-6 as a templating agent. Patent CN106799202a reports a synthetic method of RHO molecular sieve with high silicon-aluminum ratio and adsorption property, which has obvious advantages in gas adsorption selectivity and adsorption interval. However, the synthesis method is not only limited by the high price of 18-crown ether-6, but also obviously increases the production complexity and energy consumption due to the removal of the organic template agent by subsequent high-temperature roasting, and increases the production cost of the molecular sieve. Mintova et al (ChemistryofMaterials, 2020,32 (14): 5985-5993.) the synthesis of Na +, cs-RHO molecular sieves with molecular sieve crystallites of less than 100nm using a method without an organic template. The extremely small grain size brings great difficulty to the solid-liquid separation process after crystallization is completed, and higher requirements are put on the subsequent process optimization. Therefore, there is a need for a synthetic method of RHO type molecular sieve adsorbents that does not require a template agent and has more suitable grain size.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide the RHO type structure molecular sieve containing metal cations, and the synthesis method and application thereof, wherein the synthesis method has the advantages of high synthesis speed, proper grain size, low-cost and environment-friendly raw materials; the RHO type structure molecular sieve can preferentially adsorb a large amount of carbon dioxide when applied to carbon dioxide, nitrogen and/or methane mixed gas.
The invention is realized by the following technical scheme that on one hand, the invention provides a synthetic method of RHO type structure molecular sieve containing metal cations, which comprises the following steps:
1) Preparing a guiding agent;
fully mixing a material containing a silicon source, an aluminum source, a sodium source and a cesium source with water, stirring and ageing to obtain a directing agent sol, and transferring the directing agent sol into a reaction kettle for primary crystallization to obtain a directing agent;
2) Preparing synthetic sol;
Fully mixing materials containing a silicon source, an aluminum source, a sodium source and a cesium source with water according to a certain proportion, uniformly stirring, adding the guiding agent according to a certain proportion, and aging to obtain synthetic sol;
3) Crystallizing, drying and roasting the synthesized sol to obtain Na + and Cs-RHO molecular sieve raw powder;
4) And (3) exchanging the obtained Na + and Cs-RHO molecular sieve raw powder with a NH 4,Csx -RHO molecular sieve through a first ion, and exchanging the NH 4 +,Csx -RHO molecular sieve with a second ion to obtain an M, cs x -RHO molecular sieve, wherein x is (the mass fraction of the molecular sieve Cs + after exchanging the NH 4)2SO4 solution, and M is one or more of Na +、K+、Mg2+、Cu2+、Zn2+ and Fe 3+ in metal cations).
Further, in step 1), the silicon source, aluminum source, sodium source, cesium source and water are added in the following molar ratios:
the molar ratio of SiO 2/Al2O3 is 5-15:1;
the molar ratio of Na 2O/Al2O3 is 4-12:1;
The molar ratio of Cs 2O/Al2O3 is 0.1-1:1;
the molar ratio of H 2O/Al2O3 is 20-100:1.
Further, in step 1), the crystallization temperature of the first crystallization is 90 ℃ to 120 ℃ and the crystallization time is 2h to 12h.
Further, in the step 2), the molar ratio of the silicon source, the aluminum source, the sodium source, the cesium source and the water is as follows, and the molar ratio of SiO 2：Al2O3：Na2O：Cs2O：H2 O is 9-20:0.8-1.2:1-12:0.5-1.5:200-450.
Further, in the step 2), the addition amount of the guiding agent is 2.4wt% to 10wt% of the total weight of SiO 2 in the silicon source.
Further, in the step 2), the stirring temperature is 20-60 ℃, and the aging time is 4-12 hours.
Further, in the step 3), the crystallization temperature is 90 ℃ to 120 ℃, and the crystallization time is 2h to 12h.
Further, in the step 3), the drying temperature is 120 ℃, the drying time is 5-10 h, and the roasting temperature is 200-350 ℃.
Further, in the step 4), the temperature of the first ion exchange is 40-100 ℃, the exchange time is 2-24 hours, or the temperature of the second ion exchange is 60-100 ℃, and the exchange time is 3-10 hours.
Further, the method comprises the steps of, the silicon source is any one of white carbon black, silica sol and water glass, and a mixture of two or more of the white carbon black, the silica sol and the water glass synthesized according to any proportion;
or the aluminum source is any one of pseudo-boehmite, aluminum sol, aluminum sulfate, sodium aluminate and boehmite, or a mixture of two or more of the pseudo-boehmite, the aluminum sol, the aluminum sulfate, the sodium aluminate and the boehmite synthesized according to any proportion;
or the sodium source is sodium hydroxide;
Or the cesium source is cesium hydroxide.
Also provides the M, cs x -RHO molecular sieve prepared by the synthetic method of the RHO type structure molecular sieve containing metal cations.
Finally, the application of the molecular sieve in the selective adsorption separation of carbon dioxide in the mixed gas is provided.
Preferably, the mixed gas comprises nitrogen and/or methane.
Advantageous effects
1) The molecular sieve synthesis method provided by the invention has the advantages that the adopted raw materials are cheap and environment-friendly.
2) According to the invention, the guiding agent is used for inducing and synthesizing the Na +, the Cs-RHO type molecular sieve and the Na + for the first time, so that the crystallization time of the Cs-RHO type molecular sieve is short, the crystallization reaction can be completed within 12 hours, the industrial production efficiency is improved, and the energy consumption is reduced.
3) According to the invention, the guiding agent is used for inducing and synthesizing the Na + and Cs-RHO type molecular sieve for the first time, so that the synthesized Na + and Cs-RHO type molecular sieve can be ensured to have uniform and moderate grain size (500-700 nm), the high efficiency of production and filtration is ensured, and the small grain size is beneficial to rapid adsorption and desorption of small molecular gas.
4) The cation modified RHO molecular sieve adsorbent provided by the invention can preferentially adsorb a large amount of carbon dioxide in the mixed gas of carbon dioxide, methane and nitrogen.
Drawings
FIG. 1 is an SEM image of a Na +, cs-RHO molecular sieve described in example 1;
FIG. 2 is an XRD pattern of the Na +, cs-RHO and modified RHO molecular sieves described in examples 1-9;
FIG. 3 is a graph of adsorption isotherms of the Na 7.5 +,Cs5.0 -RHO molecular sieve mixture described in example 4;
Detailed Description
The present invention will be described in further detail with reference to specific embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The experimental procedures, which do not address the specific conditions in the examples below, are generally carried out under conventional conditions or under conditions recommended by the manufacturer. All percentages, ratios, proportions or parts are by weight unless otherwise indicated.
The reagents, materials and laboratory equipment used in the examples and comparative examples of the present invention were all commercially available conventional materials and equipment unless otherwise specified.
Example 1
10.8G of deionized water, 7.4g of sodium hydroxide and 2.2g of cesium hydroxide are weighed and sequentially added, and are uniformly stirred at room temperature for 30min to obtain a transparent solution, 1.9g of sodium aluminate is added, and is stirred for 30min to obtain a transparent solution, 18.8g of silica sol (the mass fraction of SiO 2 is 40%) is added, and after being uniformly stirred, the mixture is aged for 12h at room temperature, and then crystallized for 8h at 90 ℃ to obtain the final directing agent sol. In addition, 100.1g of deionized water, 8.5g of sodium hydroxide and 4.4g of cesium hydroxide are weighed and added in sequence, and are stirred uniformly at 40 ℃ for 30min to obtain a transparent solution, 3.82g of sodium aluminate is added, and is stirred for 30min to obtain a transparent solution, 57.8g of sodium silicate (the mass fraction of SiO 2 is 30.5%, the mass fraction of Na 2 O is 8.2%) and 0.43g of a directing agent are added, and after being stirred uniformly, the final sol is obtained after ageing for 12h at room temperature. Wherein, the mass of SiO 2 in the embodiment is 17.6g, and the proportion of the guiding agent is 2.4%.
Transferring the sol into a reaction kettle, and heating the reaction kettle to 100 ℃ for staying for 12 hours to enable the mixed sol to finish hydrothermal synthesis crystallization reaction. After the reaction is completed, the reaction kettle is rapidly cooled, and the formed crystals are filtered and washed until the pH value of the washing liquid is 7-9, the obtained solid product is dried at 120 ℃ for 7 hours and then baked at 300 ℃ to obtain Na +, cs-RHO molecular sieve raw powder, SEM results are shown in figure 1, and XRD results are RHO type structures shown in figure 2 a.
Example 2
10.8G of deionized water, 7.4g of sodium hydroxide and 2.2g of cesium hydroxide are weighed and sequentially added, and are uniformly stirred at room temperature for 30min to obtain a transparent solution, 1.9g of sodium aluminate is added, and is stirred for 30min to obtain a transparent solution, 18.8g of silica sol (the mass fraction of SiO 2 is 40%) is added, and after being uniformly stirred, the mixture is aged for 12h at room temperature, and then crystallized for 8h at 90 ℃ to obtain the final directing agent sol. In addition, 100.1g of deionized water, 8.5g of sodium hydroxide and 4.4g of cesium hydroxide are weighed and added in sequence, and are stirred uniformly at 40 ℃ for 30min to obtain a transparent solution, 3.82g of sodium aluminate is added, and is stirred for 30min to obtain a transparent solution, 57.8g of sodium silicate (the mass fraction of SiO 2 is 30.5%, the mass fraction of Na 2 O is 8.2%) and 1.23g of a guiding agent are added, and after being stirred uniformly, the final sol is obtained after ageing for 12h at room temperature. Wherein, the mass of SiO 2 in the embodiment is 17.6g, and the proportion of the guiding agent is 7.0%.
Transferring the sol into a reaction kettle, and heating the reaction kettle to 100 ℃ for staying for 12 hours to enable the mixed sol to finish hydrothermal synthesis crystallization reaction. After the reaction is finished, the reaction kettle is cooled down rapidly, the formed crystal is filtered and washed until the pH value of the washing liquid is 7-9, the obtained solid product is dried at 120 ℃ for 7h and then baked at 300 ℃ to obtain Na +, cs-RHO molecular sieve raw powder, and the XRD result is RHO type structure as shown in figure 2b.
Example 3
10.8G of deionized water, 7.4g of sodium hydroxide and 2.2g of cesium hydroxide are weighed and sequentially added, and are uniformly stirred at room temperature for 30min to obtain a transparent solution, 1.9g of sodium aluminate is added, and is stirred for 30min to obtain a transparent solution, 18.8g of silica sol (the mass fraction of SiO 2 is 40%) is added, and after being uniformly stirred, the mixture is aged for 12h at room temperature, and then crystallized for 8h at 90 ℃ to obtain the final directing agent sol. In addition, 100.1g of deionized water, 8.5g of sodium hydroxide and 4.4g of cesium hydroxide are weighed and added in sequence, and are stirred uniformly at 40 ℃ for 30 minutes to obtain a transparent solution, 3.82g of sodium aluminate is added and stirred for 30 minutes to obtain a transparent solution, 57.8g of sodium silicate (the mass fraction of SiO 2 is 30.5 percent, the mass fraction of Na 2 O is 8.2 percent) and 1.76g of a guiding agent are added and are stirred uniformly, and then the final sol is obtained after ageing for 12 hours at room temperature. Wherein, the mass of SiO 2 in the embodiment is 17.6g, and the proportion of the guiding agent is 10.0%.
Transferring the sol into a reaction kettle, and heating the reaction kettle to 100 ℃ for staying for 12 hours to enable the mixed sol to finish hydrothermal synthesis crystallization reaction. After the reaction is finished, the reaction kettle is cooled down rapidly, the formed crystal is filtered and washed until the pH value of the washing liquid is 7-9, the obtained solid product is dried at 120 ℃ for 7h and then baked at 300 ℃ to obtain Na +, cs-RHO molecular sieve raw powder, and the XRD result is RHO type structure, as shown in figure 2C.
Example 4
The ratio of mass of Cs-RHO molecular sieve sample to volume of ammonium sulfate solution (3 mol/L) S/l=1g:30 ml was stirred and mixed at 80 ℃ for 6 hours for filtration according to the Na + described in example 1, the process was repeated 3 times, the obtained sample was washed with deionized water, and dried at 100 ℃ for 12 hours to obtain NH 4 +,Cs5.0 -RHO molecular sieve;
The NH 4 +,Cs5.0 -RHO molecular sieve sample is stirred and mixed with 0.5mol/L sodium chloride solution for 6 hours at 80 ℃ according to the solid-liquid S/L=1g:30mL ratio, then the mixture is filtered, the obtained sample is washed by deionized water, dried for 12 hours at 100 ℃, then placed in a muffle furnace and roasted for 4 hours at 550 ℃, so as to obtain the Na 7.5 +,Cs5.0 -RHO molecular sieve, the mixed gas adsorption isothermal diagram of the Na 7.5 +,Cs5.0 -RHO molecular sieve is shown in figure 3, and the XRD result of the Na 7.5 +,Cs5.0 -RHO molecular sieve is of RHO type structure, as shown in figure 2 d.
Example 5
The ratio of mass of Cs-RHO molecular sieve sample to volume of ammonium sulfate solution (3 mol/L) S/l=1g:30 ml was stirred and mixed at 80 ℃ for 6 hours for filtration according to the Na + described in example 1, the process was repeated 3 times, the obtained sample was washed with deionized water, and dried at 100 ℃ for 12 hours to obtain NH 4 +,Cs5.0 -RHO molecular sieve;
NH 4 +,Cs5.0 -RHO molecular sieve sample and 0.5mol/L potassium chloride solution are stirred and mixed for 6 hours at 80 ℃ according to the solid-liquid S/L=1 g:30mL ratio, then the mixture is filtered, the obtained sample is washed by deionized water and dried for 12 hours at 100 ℃, then the dried sample is placed in a muffle furnace and baked for 4 hours at 550 ℃ to obtain K 8.9 +,Cs5.0 -RHO molecular sieve, and XRD result is RHO type structure, as shown in figure 2 e.
Example 6
The ratio of mass of Cs-RHO molecular sieve sample to volume of ammonium sulfate solution (3 mol/L) S/l=1g:30 ml was stirred and mixed at 80 ℃ for 6 hours for filtration according to the Na + described in example 1, the process was repeated 3 times, the obtained sample was washed with deionized water, and dried at 100 ℃ for 12 hours to obtain NH 4 +,Cs5.0 -RHO molecular sieve;
NH 4 +,Cs5.0 -RHO molecular sieve sample and 0.5mol/L magnesium chloride solution are stirred and mixed for 6 hours at 80 ℃ according to the solid-liquid S/L=1g:30mL ratio, then the mixture is filtered, the obtained sample is washed by deionized water and dried for 12 hours at 100 ℃, then the dried sample is placed in a muffle furnace and baked for 4 hours at 550 ℃, and Mg 5.9 2+,Cs5.0 -RHO molecular sieve is obtained, and XRD result is RHO type structure, as shown in figure 2 f.
Example 7
The ratio of mass of Cs-RHO molecular sieve sample to volume of ammonium sulfate solution (3 mol/L) S/l=1g:30 ml was stirred and mixed at 80 ℃ for 6 hours for filtration according to the Na + described in example 1, the process was repeated 3 times, the obtained sample was washed with deionized water, and dried at 100 ℃ for 12 hours to obtain NH 4 +,Cs5.0 -RHO molecular sieve;
NH 4 +,Cs5.0 -RHO molecular sieve sample and 0.5mol/L copper chloride solution are stirred and mixed for 6 hours at 80 ℃ according to the solid-liquid S/L=1g:30mL ratio, then the mixture is filtered, the obtained sample is washed by deionized water, dried for 12 hours at 100 ℃, then placed in a muffle furnace and roasted for 4 hours at 550 ℃, and the Cu 6.6 2+,Cs5.0 -RHO molecular sieve is obtained, wherein the XRD result is of RHO type structure, and is shown in figure 2 g.
Example 8
The ratio of mass of Cs-RHO molecular sieve sample to volume of ammonium sulfate solution (3 mol/L) S/l=1g:30 ml was stirred and mixed at 80 ℃ for 6 hours for filtration according to the Na + described in example 1, the process was repeated 3 times, the obtained sample was washed with deionized water, and dried at 100 ℃ for 12 hours to obtain NH 4 +,Cs5.0 -RHO molecular sieve;
NH 4 +,Cs5.0 -RHO molecular sieve sample and 0.5mol/L zinc chloride solution are stirred and mixed for 6 hours at 80 ℃ according to the solid-liquid S/L=1g:30mL ratio, then the mixture is filtered, the obtained sample is washed by deionized water, dried for 12 hours at 100 ℃, then placed in a muffle furnace and roasted for 4 hours at 550 ℃, and a Zn 6.5 2+,Cs5.0 -RHO molecular sieve is obtained, and the XRD result is of RHO type structure, as shown in figure 2 h.
Example 9
The ratio of the mass of the Na, cs-RHO molecular sieve sample to the volume of the ammonium sulfate solution (3 mol/L) S/L=1g:30 mL is stirred and mixed for 6 hours at 80 ℃ for filtration, the process is repeated for 3 times, the obtained sample is washed by deionized water and dried for 12 hours at 100 ℃ to obtain the NH 4 +,Cs5.0 -RHO molecular sieve;
NH 4 +,Cs5.0 -RHO molecular sieve sample and 0.5mol/L ferric chloride solution are stirred and mixed for 6 hours at 80 ℃ according to the solid-liquid S/L=1 g:30mL ratio, then the mixture is filtered, the obtained sample is washed by deionized water and dried for 12 hours at 100 ℃, then the dried sample is placed in a muffle furnace and baked for 4 hours at 550 ℃, and Fe 5.8 3+,Cs5.0 -RHO molecular sieve is obtained, and XRD result is RHO type structure, as shown in figure 2 i.
Comparative example 1
The ratio of mass of Cs-RHO molecular sieve sample to volume of ammonium sulfate solution (0.3 mol/L) S/l=1g:30 ml was stirred and mixed at 80 ℃ for 6 hours for filtration according to the Na + described in example 1, the procedure was repeated 1 time, the obtained sample was washed with deionized water, dried at 100 ℃ for 12 hours, and then placed in a muffle furnace for calcination at 550 ℃ for 4 hours to obtain Na 6.0 +,Cs22.0 -RHO molecular sieve.
Comparative example 2
95.3G of deionized water and 6.88g of sodium hydroxide are weighed, stirred for 20min to be fully dissolved, and the solution is equally divided into two beakers marked as A solution and B solution. 13.2g of sodium aluminate was added to the solution A and stirred for 20min until the solution was clear. 23.3g of water glass was added to the B solution and stirred for 20min until the solution was clear. Slowly pouring the solution B into the solution A, stirring for 10min to form sol, sealing a beaker, placing the beaker in a 100 ℃ oven, filtering and washing the formed crystals after the crystallization for 4h reaction is finished until the pH value of the washing solution is 7-9, drying the obtained solid product at 120 ℃ for 7h, and roasting at 300 ℃ to obtain NaA molecular sieve raw powder. The obtained sample was washed with deionized water, dried at 100 ℃ for 12 hours, and then placed in a muffle furnace for roasting at 550 ℃ for 4 hours, to obtain Na 4.8 a molecular sieve.
Comparative example 3
The preparation method comprises the steps of synthesizing according to a method described in CN111039303A, wherein the silicon content is Si/(Si+Al+P) molar ratio=0.145, the crystallization temperature is 200 ℃, the crystallization time is 72 hours, after the reaction is completed, rapidly cooling the reaction kettle, filtering and washing until the pH value of a washing solution is 7-9, mixing the obtained crystal with 0.5mol/L lithium chloride solution according to the solid-liquid S/L=1 g:30mL ratio at 80 ℃ for 6 hours, filtering, washing the obtained sample with deionized water, drying at 100 ℃ for 12 hours, and then roasting in a muffle furnace at 550 ℃ for 4 hours to obtain the Li 5.8 -SAPO-RHO molecular sieve.
Comparative example 4
According to the method of literature (JColloidInterfaceSci, 2021, 582:90-101), activated carbon is prepared from rice hulls by carbonization and KOH activation. The prepared activated carbon and chitosan are fully ground and mixed according to a ratio of 1:1, and then the mixture is placed in a muffle furnace to be roasted for 4 hours at 550 ℃ to obtain the N-AC adsorbent.
Effect example 1
The RHO molecular sieve adsorbents prepared in examples 1-9 and the sample adsorbents prepared in comparative examples 1-4 were subjected to mixed gas selective adsorption separation test, all molecular sieve samples were subjected to activation treatment at 350 ℃ under vacuum for 6 hours before the test, the single component gas isothermal adsorption and desorption test was performed after the samples were cooled to room temperature at 25 ℃ under a test pressure of 0-1.0 bar, and the samples in examples 1-9 and comparative examples 1-4 were subjected to test for CO 2、CH4 and N 2 at 25 ℃ and 1.0 bar.
TABLE 1
The analysis of the data shows that the Na + and Cs-RHO molecular sieve adopted by the application has mild synthesis conditions, short crystallization time and no need of an organic template agent. After modification by different metal cations, the prepared modified M, cs-RHO (m=na +、K+、Mg2+、Cu2+、Zn2+ and Fe 3+) molecular sieve adsorbent, in particular, a Na + modified RHO framework molecular sieve adsorbent, shows excellent carbon dioxide selective adsorption capacity and adsorption separation capacity of carbon dioxide, methane and nitrogen.
It should be noted that the foregoing description is only a preferred embodiment of the present invention, and although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood that modifications, equivalents, improvements and modifications to the technical solution described in the foregoing embodiments may occur to those skilled in the art, and all modifications, equivalents, and improvements are intended to be included within the spirit and principle of the present invention.
Claims (10)
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