CN116850954A - Heteroatom MOR type zeolite, preparation method thereof and application thereof in selective adsorption of nitrogen oxides - Google Patents
Heteroatom MOR type zeolite, preparation method thereof and application thereof in selective adsorption of nitrogen oxides Download PDFInfo
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- CN116850954A CN116850954A CN202310632339.2A CN202310632339A CN116850954A CN 116850954 A CN116850954 A CN 116850954A CN 202310632339 A CN202310632339 A CN 202310632339A CN 116850954 A CN116850954 A CN 116850954A
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 181
- 239000010457 zeolite Substances 0.000 title claims abstract description 177
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 176
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 172
- 125000005842 heteroatom Chemical group 0.000 title claims abstract description 66
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000002184 metal Substances 0.000 claims abstract description 45
- 238000005342 ion exchange Methods 0.000 claims abstract description 24
- 150000003839 salts Chemical class 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 12
- 239000010413 mother solution Substances 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 21
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 229910021645 metal ion Inorganic materials 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 11
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 150000008044 alkali metal hydroxides Chemical group 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000003841 chloride salts Chemical class 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 1
- -1 NO x Chemical compound 0.000 abstract description 14
- 239000011148 porous material Substances 0.000 abstract description 11
- 239000003546 flue gas Substances 0.000 abstract description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- ODUCDPQEXGNKDN-UHFFFAOYSA-N Nitrogen oxide(NO) Natural products O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 71
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 51
- 238000012360 testing method Methods 0.000 description 47
- 238000001035 drying Methods 0.000 description 34
- 238000003756 stirring Methods 0.000 description 27
- 239000007788 liquid Substances 0.000 description 22
- 239000006185 dispersion Substances 0.000 description 20
- 238000002425 crystallisation Methods 0.000 description 17
- 230000008025 crystallization Effects 0.000 description 17
- 238000001914 filtration Methods 0.000 description 17
- 238000005406 washing Methods 0.000 description 17
- 230000035515 penetration Effects 0.000 description 12
- 238000004364 calculation method Methods 0.000 description 11
- 238000001816 cooling Methods 0.000 description 11
- 239000012452 mother liquor Substances 0.000 description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000006229 carbon black Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- 230000001105 regulatory effect Effects 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910020514 Co—Y Inorganic materials 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910001631 strontium chloride Inorganic materials 0.000 description 2
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical group [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229910001427 strontium ion Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
-
- 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
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/402—Dinitrogen oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention provides a heteroatom MOR zeolite, a preparation method thereof and application thereof in selective adsorption of nitrogen oxides, and relates to the technical fields of nitrogen oxide treatment and zeolite synthesis. Mixing MOR zeolite, water and soluble metal salt for ion exchange to obtain the heteroatom MOR zeolite; the metal element in the soluble metal salt comprises one or more of a group IIA metal element and a transition metal element. The invention carries out ion exchange on MOR zeolite through specific metal salt, carries out heteroatom metal doping on MOR zeolite, improves the pore channel characteristics of MOR zeolite, and the prepared heteroatom MOR zeolite has excellent selective adsorption of Nitrogen Oxide (NO) x ) Can be derived from flue gas (including NO x 、CO 2 And O 2 ) Medium and high efficiency selective adsorption of NO x 。
Description
Technical Field
The invention relates to the technical field of nitrogen oxide treatment and zeolite synthesis, in particular to a heteroatom MOR zeolite, a preparation method thereof and application thereof in selectively adsorbing nitrogen oxides.
Background
Nitrogen Oxides (NO) x ) Is an important source of atmospheric pollution, and causes a plurality of environmental problems, including photochemical smog, acid rain, ozone layer damage and the like, which are harmful to health. In recent years, NO is x Emission restrictions are becoming more stringent, and effective removal of NO from flue gases is sought x Has become a subject of extensive attention. In which Selective Catalytic Reduction (SCR) technology is widely used but is not suitable for low concentration NO x The ammonia leakage, easy poisoning and deactivation of the catalyst and the like; the adsorption method has simple process and high removal efficiency, and is very suitable for low-concentration NO x Has good application prospect.
The adsorption separation based on the solid inorganic porous material adsorbent is a novel gas adsorption separation technology, and has the following advantages: the purity of the product is high; the method can generally work at room temperature and low pressure, the bed layer is not heated during regeneration, and the product purity is high; the equipment is simple, and the operation and maintenance are simple and convenient; continuous cyclic operation can fully achieve automation. Therefore, when this new technology comes out, it is attracting attention from various industries. The core of this technology is the development of solid porous adsorbents.
Zeolite is an inorganic porous aluminosilicate and is widely used in petrochemical industry, ion exchange, adsorption and separation fields. The framework of zeolite is composed of TO 4 (t=si or Al) tetrahedral co-angular architecture, forming periodic and highly stable 1D to 3D channels with unique porous structure, pore size typically<2nm, covering most of the industrially important small molecular sizes. Nowadays, the framework element type of T is further extended to P, fe, B, ga, ti, ge et al, 255 zeolite structures being accepted by the international zeolite association-structure committee.
MOR zeolites are also known asMordenite has excellent heat-resistant, acid-resistant and water vapor-resistant properties, and is widely used industrially as an adsorbent for separation of gas or liquid mixtures and a catalyst for reactions such as hydrocarbon cracking, hydrocracking, dimethylamine synthesis, isomerization of alkanes, alkylation of polycyclic aromatic compounds, and the like, and is also useful as a desiccant, adsorbent, and the like. Although adsorption of gas molecules to zeolites has been reported, NO separation of NO has been achieved using MOR zeolite x Is a case of (2).
Disclosure of Invention
In view of the above, the present invention aims to provide a heteroatom MOR type zeolite, a process for its preparation and its use in the selective adsorption of nitrogen oxides. The heteroatom MOR zeolite prepared by the invention can efficiently and selectively adsorb Nitrogen Oxides (NO) x )。
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of heteroatom MOR zeolite, which comprises the following steps:
mixing MOR zeolite, water and soluble metal salt for ion exchange to obtain the heteroatom MOR zeolite; the metal element in the soluble metal salt comprises one or more of a group IIA metal element and a transition metal element.
Preferably, the group IIA metal element comprises magnesium and/or strontium; the transition metal element includes one or more of zinc, nickel, manganese, iron, cobalt, and copper.
Preferably, the soluble metal salt includes one or more of chloride, nitrate and sulfate.
Preferably, the mass ratio of the MOR zeolite to the water is 1:10-1:1000, and the concentration of metal ions of the soluble metal salt in the mixed solution obtained by mixing is 0.1-2 mol/L.
Preferably, the temperature of the ion exchange is 80-100 ℃ and the time is 0.5-3 h.
Preferably, the process for preparing the MOR zeolite comprises the steps of:
mixing an alkali source, an aluminum source, a silicon source and water to obtainTo mother liquor; the alkali source is alkali metal hydroxide and/or alkali metal oxide, and the alkali source, the aluminum source, the silicon source and the alkali metal oxide and the Al are respectively used 2 O 3 、SiO 2 And H 2 O is calculated, alkali metal oxide and Al are contained in the mother solution 2 O 3 、SiO 2 And H 2 The mol ratio of O is (3-10) 1 (15-60) 350-1000;
carrying out hydrothermal crystallization on the mother solution to obtain MOR zeolite; the temperature of the hydrothermal crystallization is 150-200 ℃ and the time is 24-72 h.
The invention provides the heteroatom MOR zeolite prepared by the preparation method in the technical scheme, wherein the heteroatom in the heteroatom MOR zeolite comprises one or more of group IIA metal elements and transition metal elements.
Preferably, the doping amount of the hetero atom in the hetero atom MOR type zeolite is 0.1-2 wt%.
The invention provides application of the heteroatom MOR zeolite in selective adsorption of nitrogen oxides.
Preferably, the nitrogen oxides are derived from a group comprising CO 2 And O 2 Is a mixed gas of (a) and (b).
The invention provides a preparation method of heteroatom MOR zeolite, which comprises the following steps: mixing MOR zeolite, water and soluble metal salt for ion exchange to obtain the heteroatom MOR zeolite; the metal element in the soluble metal salt comprises one or more of a group IIA metal element and a transition metal element. The invention carries out ion exchange on MOR type zeolite through specific metal salt, carries out heteroatom metal doping on MOR type zeolite, improves the pore path characteristics of MOR type zeolite on one hand, is shown by changing the size of the pore path of the zeolite, and partial ions enter a MOR type zeolite framework or a side pocket to change the zeolite structure, so that Nitrogen Oxides (NO) are more easily captured x ) The method comprises the steps of carrying out a first treatment on the surface of the On the other hand, changing the balance cation in MOR zeolite makes it more affinity to NO x . The heteroatom MOR zeolite prepared by the invention has excellent selective adsorption of Nitrogen Oxides (NO) x ) Can be derived from flue gas (including NO x 、CO 2 And O 2 ) Medium and high efficiency selective adsorption of NO x 。
Drawings
FIG. 1 shows XRD patterns of the hetero atom MOR-type zeolites prepared in examples 1 to 8, and curves a to h in FIG. 1 correspond to examples 1 to 8 in order;
FIG. 2 is a graph of the heteroatom MOR zeolite vs. NO prepared in example 1 x A dynamic penetration graph;
FIG. 3 is a graph of the heteroatom MOR zeolite vs. NO prepared in example 2 x A dynamic penetration graph;
FIG. 4 is a graph of the heteroatom MOR zeolite vs. NO prepared in example 3 x A dynamic penetration graph;
FIG. 5 is a graph of the heteroatom MOR zeolite vs. NO prepared in example 4 x A dynamic penetration graph;
FIG. 6 is a graph of the heteroatom MOR zeolite vs. NO prepared in example 5 x A dynamic penetration graph;
FIG. 7 is a graph of the heteroatom MOR zeolite vs. NO prepared in example 6 x A dynamic penetration graph;
FIG. 8 is a graph of the heteroatom MOR zeolite vs. NO prepared in example 7 x A dynamic penetration graph;
FIG. 9 is a graph of the heteroatom MOR zeolite vs. NO prepared in example 8 x A dynamic penetration graph;
FIG. 10 is a graph of MOR zeolite vs. NO prepared in comparative example 1 x A dynamic penetration graph;
FIG. 11 is a graph of ion-exchanged commercial Y-type zeolite vs. NO for comparative example 2 x A dynamic penetration graph;
FIG. 12 is a commercial ZSM-5 type zeolite vs. NO in comparative example 3 x Dynamic penetration graph.
Detailed Description
The invention provides a preparation method of heteroatom MOR zeolite, which comprises the following steps:
mixing MOR zeolite, water and soluble metal salt for ion exchange to obtain the heteroatom MOR zeolite; the metal element in the soluble metal salt comprises one or more of a group IIA metal element and a transition metal element.
MOR type molecular sieves were first synthesized by Barre et al in 1952. The idealized MOR framework (space group: cmcm) is constructed from MOR (t-tes) as the secondary building block (CBU). Each mor (t-tes) connects 4-membered rings in space, yielding a two-dimensional (2D) channel system with 12-ring openings and 8-ring openings. In addition, the MOR molecular sieve is provided with parallel 12-Membered Ring (MR) one-dimensional pore canal along the c-axis direction, and the pore size is thatTo->The MOR molecular sieve has important application in the field of catalysis, such as Methanol To Olefin (MTO), dimethyl ether carbonylation, adsorption and other fields. Although adsorption of gas molecules to zeolites has been reported, NO separation using MOR has been achieved x Mainly because the pore structure and charge properties of the zeolite are known to be not fully satisfactory for NO x Conditions for depth separation. The invention carries out heteroatom metal doping on MOR zeolite by ion exchange, improves the pore canal characteristics of MOR zeolite and is suitable for NO x Is separated by selective adsorption. The following is a detailed description:
in the present invention, the process for preparing the MOR zeolite preferably comprises the steps of:
mixing an alkali source, an aluminum source, a silicon source and water to obtain a mother solution; the alkali source is alkali metal hydroxide and/or alkali metal oxide, and the alkali source, the aluminum source, the silicon source and the alkali metal oxide and the Al are respectively used 2 O 3 、SiO 2 And H 2 O is calculated, alkali metal oxide and Al are contained in the mother solution 2 O 3 、SiO 2 And H 2 The mol ratio of O is (3-10) 1 (15-60) 350-1000;
and carrying out hydrothermal crystallization on the mother solution to obtain MOR zeolite.
In the present invention, the alkali metal hydroxide preferably includes sodium hydroxide and/or potassium hydroxide, and the alkali metal oxide preferably is sodium oxide; the aluminum isThe source preferably comprises one or more of sodium aluminate, aluminium hydroxide and pseudo-boehmite; the silicon source preferably comprises one or more of white carbon black, silica sol and ethyl orthosilicate. In the present invention, the method for mixing the alkali source, the aluminum source, the silicon source and the water is preferably as follows: adding the alkali source into water for first mixing to obtain a first solution; adding an aluminum source into the first solution for second mixing to obtain a second solution; adding the residual water into the second solution for third mixing to obtain a third solution; and cooling the third solution to room temperature, and adding a silicon source into the third solution to carry out fourth mixing to obtain mother solution. In the invention, the first mixing, the second mixing, the third mixing and the fourth mixing are all preferably performed under the condition of stirring, and the speed and the time of stirring are not particularly required, so that the components are uniformly mixed. In the invention, alkali metal oxide and Al are contained in the mother liquor 2 O 3 、SiO 2 And H 2 The molar ratio of O is (3-10) 1 (15-60) 350-1000, preferably (6-10) 1 (15-30) 780-1000.
In the present invention, the temperature of the hydrothermal crystallization is preferably 150 to 200 ℃, more preferably 150 to 180 ℃, and the time is preferably 24 to 72 hours, more preferably 24 to 36 hours. The mother liquor is preferably transferred into a stainless steel reaction kettle with a polytetrafluoroethylene lining for carrying out the hydrothermal crystallization. After the hydrothermal crystallization is finished, the obtained crystallization product is preferably filtered, washed and dried in sequence to obtain MOR zeolite; the pH value of the washed product is preferably 7-10, the drying temperature is preferably 80 ℃, and the time is preferably 24 hours. In the present invention, the yield of MOR zeolite is as defined for Al 2 O 3 And higher than 95%.
In the present invention, the metal element in the soluble metal salt includes one or more of a group IIA metal element and a transition metal element; the group IIA metal element preferably comprises magnesium and/or strontium; the transition metal element preferably includes one or more of zinc, nickel, manganese, iron, cobalt and copper; the soluble metal salt preferably comprises one or more of chloride, nitrate and sulfate. In the embodiment of the invention, the soluble metal salt is specifically one or more of nickel nitrate, strontium chloride, magnesium nitrate, manganese nitrate, ferric sulfate, cobalt nitrate, copper nitrate and zinc nitrate.
In the present invention, the method of mixing MOR zeolite, water and soluble metal salt is preferably: dispersing the MOR zeolite in water to obtain zeolite dispersion liquid; the soluble metal salt is dissolved in a zeolite dispersion. In the present invention, the mass ratio of MOR zeolite to water is preferably 1:10 to 1:1000, more preferably 1:100, the water is preferably deionized water; the concentration of the metal ion of the soluble metal salt in the mixed solution obtained by the mixing is preferably 0.1 to 2mol/L, more preferably 1mol/L. In the present invention, the temperature of the ion exchange is preferably 80 to 100 ℃, more preferably 80 to 90 ℃, and the time is preferably 0.5 to 3 hours, more preferably 1 to 2 hours; the metal ions in the soluble metal salt as heteroatoms are ion exchanged into the MOR zeolite. After the ion exchange is completed, the obtained reaction liquid is preferably cooled to room temperature, and then is filtered, washed and dried in sequence, so that the heteroatom MOR zeolite is obtained.
The invention provides the heteroatom MOR zeolite prepared by the preparation method in the technical scheme, wherein the heteroatom in the heteroatom MOR zeolite comprises one or more of group IIA metal elements and transition metal elements, and the doping amount of the heteroatom in the heteroatom MOR zeolite is preferably 0.1-2 wt%. The invention carries out heteroatom metal doping on MOR type zeolite, on one hand, improves the pore canal characteristics of MOR type zeolite, which is characterized in that the size of the pore canal of zeolite is changed, and partial ions enter the MOR type zeolite framework or side bags to change the zeolite structure, so that NO is more easily captured x The method comprises the steps of carrying out a first treatment on the surface of the On the other hand, changing the balance cation in MOR zeolite makes it more affinity to NO x . In an embodiment of the present invention, the heteroatom MOR type zeolite is denoted as X-MOR type zeolite, wherein X represents a heteroatom, i.e., ion-exchanging the corresponding metal element.
The invention provides application of the heteroatom MOR zeolite in selective adsorption of nitrogen oxides. The invention relates to the Nitrogen Oxide (NO) x ) Nitrogen oxides well known to those skilled in the art are available without particular requirements, and in the present invention, the nitrogen oxides preferably come from the group consisting of CO 2 And O 2 Is a mixed gas of (a) and (b). The heteroatom MOR zeolite prepared by the invention has excellent selective adsorption of Nitrogen Oxides (NO) x ) Can be derived from flue gas (including NO x 、CO 2 And O 2 ) Medium and high efficiency selective adsorption of NO x 。
The heteroatom MOR type zeolite, its preparation and its use in the selective adsorption of nitrogen oxides provided by the present invention are described in detail below with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The preparation of the heteroatom MOR zeolite comprises the following steps:
adding 19g of sodium hydroxide into 40g of water, and stirring until the sodium hydroxide is uniformly dissolved to form a solution 1; adding 14.3g of aluminum hydroxide into the solution 1, and uniformly stirring to form a solution 2; adding 645g of water into the solution 2 to form a solution 3, adding 98.2g of white carbon black into the solution 3 after the solution is cooled to room temperature, and stirring uniformly to form a mother solution, wherein the ratio (molar ratio) of the mother solution is 6Na 2 O:Al 2 O 3 :30SiO 2 :780H 2 O；
Transferring the mother liquor into a stainless steel reaction kettle with a polytetrafluoroethylene lining for hydrothermal crystallization, wherein the crystallization temperature is 150 ℃, and the crystallization time is 24 hours; and collecting crystallized products by filtering, washing and drying, wherein the pH value of the washed products is less than 10, the drying temperature is 80 ℃ and the drying time is 24 hours, so as to obtain the primary product, namely MOR zeolite.
The MOR zeolite is prepared by the following steps of (1) solid-liquid mass ratio: 100 in deionized water to obtain zeolite dispersion; dissolving strontium chloride in zeolite dispersion liquid, and regulating the concentration of strontium ions to be 1mol/L; heating the obtained mixed solution to 80 ℃, and preserving heat for 2 hours to perform ion exchange; and cooling, filtering, washing and drying to obtain the Sr-MOR zeolite doped with strontium.
XRD testing was performed on the obtained strontium-doped Sr-MOR zeolite product, the test results are shown as a curve in figure 1, and the product is consistent with the MOR zeolite standard spectrum.
Test of strontium doped Sr-MOR zeolite in NOx, CO 2 And O 2 The ability to dynamically capture NOx in the mixed gas was tested as follows:
the gas concentration (volume percent) is: 200ppm NO x 、14％O 2 、4.5％CO 2 The balance gas was nitrogen, the mass of the Sr-MOR zeolite doped with strontium was 2.25g, the gas flow rate was 250mL/min, and the test temperature was room temperature (298K). The test results are shown in FIG. 2 (dynamic penetration graph), and the adsorption amounts obtained by integral calculation are shown in Table 1.
Example 2
The preparation of the heteroatom MOR zeolite comprises the following steps:
31g of sodium hydroxide is added into 40g of water, and stirred until the sodium hydroxide is uniformly dissolved to form solution 1; adding 14.3g of aluminum hydroxide into the solution 1, and uniformly stirring to form a solution 2; adding 838g of water into the solution 2 to form a solution 3, cooling the solution to room temperature, adding 49.1g of white carbon black into the solution 3, and uniformly stirring to form a mother solution, wherein the ratio (molar ratio) of the mother solution is 10Na 2 O:Al 2 O 3 :15SiO 2 :1000H 2 O；
Transferring the mother liquor into a stainless steel reaction kettle with a polytetrafluoroethylene lining for hydrothermal crystallization, wherein the crystallization temperature is 200 ℃, and the crystallization time is 72 hours; the crystallized product is collected by filtering, washing and drying, wherein the pH value of the washed product is less than 10, the drying temperature is 80 ℃ and the drying time is 24 hours, so as to obtain the primary product, namely MOR zeolite.
The MOR zeolite is prepared by the following steps of (1) solid-liquid mass ratio: 100 in deionized water to obtain zeolite dispersion; dissolving nickel nitrate in zeolite dispersion liquid, and regulating the concentration of metal ions to be 1mol/L; heating the obtained mixed solution to 80 ℃, and preserving heat for 2 hours to perform ion exchange; after cooling, filtering, washing and drying are carried out to obtain the Ni-MOR zeolite doped with nickel.
XRD testing was performed on the nickel-doped Ni-MOR zeolite product, the test results are shown in the graph b in FIG. 1, and the product is consistent with the MOR zeolite standard spectrum.
TestingNickel doped Ni-MOR zeolite in NO x 、CO 2 And O 2 Dynamic NO capture in mixed gas x The test conditions were the same as in example 1, the test results are shown in FIG. 3, and the adsorption amounts obtained by the integral calculation are shown in Table 1.
Example 3
The preparation of the heteroatom MOR zeolite comprises the following steps:
13.2g of potassium hydroxide is added into 40g of water and stirred until the potassium hydroxide is uniformly dissolved to form solution 1; adding 19.85g of pseudo-boehmite into the solution 1, and uniformly stirring to form a solution 2; adding 267g of water into the solution 2 to form a solution 3, adding 49.1g of white carbon black into the solution 3 after the solution is cooled to room temperature, and stirring uniformly to form a mother solution, wherein the ratio (molar ratio) of the mother solution is 3K 2 O:Al 2 O 3 :15SiO 2 :350H 2 O；
Transferring the mother liquor into a stainless steel reaction kettle with a polytetrafluoroethylene lining for hydrothermal crystallization, wherein the crystallization temperature is 180 ℃, and the crystallization time is 72 hours; and collecting crystallized products by filtering, washing and drying, wherein the pH value of the washed products is less than 10, the drying temperature is 80 ℃ and the drying time is 24 hours, so as to obtain the primary product, namely MOR zeolite.
The MOR zeolite is prepared by the following steps of (1) solid-liquid mass ratio: 100 in deionized water to obtain zeolite dispersion; dissolving manganese nitrate in zeolite dispersion liquid, regulating the concentration of metal ions to be 1mol/L, heating the obtained mixed liquid to 80 ℃, and preserving heat for 2 hours for ion exchange; and cooling, filtering, washing and drying to obtain Mn-MOR zeolite doped with manganese.
XRD testing was performed on the Mn-MOR type zeolite product doped with Mn, and the test result is shown in the curve c in FIG. 1, and the product is consistent with the MOR type zeolite standard pattern.
Testing Mn-MOR zeolite doped with manganese in NO x 、CO 2 And O 2 Dynamic NO capture in mixed gas x The test conditions were the same as in example 1, the test results are shown in FIG. 4, and the adsorption amounts obtained by the integral calculation are shown in Table 1.
Example 4
The preparation of the heteroatom MOR zeolite comprises the following steps:
adding 44g of sodium hydroxide into 40g of water, and stirring until the sodium hydroxide is uniformly dissolved to form a solution 1; adding 19.85g of pseudo-boehmite into the solution 1, and uniformly stirring to form a solution 2; adding 267g of water into the solution 2 to form a solution 3, adding 49.1g of white carbon black into the solution 3 after the solution is cooled to room temperature, and uniformly stirring to form a mother solution, wherein the ratio (molar ratio) of the mother solution is 10Na 2 O:Al 2 O 3 :15SiO 2 :350H 2 O；
Transferring the mother liquor into a stainless steel reaction kettle with a polytetrafluoroethylene lining for hydrothermal crystallization, wherein the crystallization temperature is 180 ℃, and the crystallization time is 72 hours; and collecting crystallized products by filtering, washing and drying, wherein the pH value of the washed products is less than 10, the drying temperature is 80 ℃ and the drying time is 24 hours, so as to obtain the primary product, namely MOR zeolite.
The MOR zeolite is prepared by the following steps of (1) solid-liquid mass ratio: 100 in deionized water to obtain zeolite dispersion; dissolving ferric sulfate in zeolite dispersion liquid, regulating the concentration of metal ions to be 1mol/L, heating the obtained mixed liquid to 80 ℃, and preserving heat for 2 hours for ion exchange; after cooling, filtering, washing and drying to obtain Fe-MOR zeolite doped with iron.
XRD testing was performed on the obtained Fe-MOR zeolite product doped with iron, and the test result is shown as a d curve in FIG. 1, and the product is consistent with the MOR zeolite standard pattern.
Testing Fe-MOR zeolite doped with iron in NO x 、CO 2 And O 2 Dynamic NO capture in mixed gas x The test conditions were the same as in example 1, the test results are shown in FIG. 5, and the adsorption amounts obtained by the integral calculation are shown in Table 1.
Example 5
The preparation of the heteroatom MOR zeolite comprises the following steps:
adding 19g of sodium hydroxide into 40g of water, and stirring until the sodium hydroxide is uniformly dissolved to form a solution 1; adding 14.3g of aluminum hydroxide into the solution 1, and uniformly stirring to form a solution 2; adding 645g of water into the solution 2 to form a solution 3, adding 98.2g of white carbon black into the solution 3 after the solution is cooled to room temperature, and stirring uniformly to form a mother solution, wherein the mother solution is prepared(molar ratio) of 6Na 2 O:Al 2 O 3 :30SiO 2 :780H 2 O；
Transferring the mother liquor into a stainless steel reaction kettle with a polytetrafluoroethylene lining for hydrothermal crystallization, wherein the crystallization temperature is 150 ℃, and the crystallization time is 24 hours; and collecting crystallized products by filtering, washing and drying, wherein the pH value of the washed products is less than 10, the drying temperature is 80 ℃ and the drying time is 24 hours, so as to obtain the primary product, namely MOR zeolite.
The MOR zeolite is prepared by the following steps of (1) solid-liquid mass ratio: 100 in deionized water to obtain zeolite dispersion; dissolving magnesium nitrate in zeolite dispersion liquid, and regulating the concentration of metal ions to be 1mol/L; heating the obtained mixed solution to 80 ℃, and preserving heat for 2 hours to perform ion exchange; after cooling, filtering, washing and drying to obtain Mg-MOR zeolite doped with magnesium.
XRD testing was performed on the obtained Mg-MOR zeolite product doped with magnesium, and the test result is shown as a curve e in FIG. 1, and the product is consistent with the MOR zeolite standard pattern.
Testing magnesium doped Mg-MOR zeolite in NO x 、CO 2 And O 2 The ability to dynamically capture NOx in the mixed gas was the same as in example 1, the test results are shown in fig. 6, and the adsorption amounts obtained by the integral calculation are shown in table 1.
Example 6
The preparation of the heteroatom MOR zeolite comprises the following steps:
adding 19g of sodium hydroxide into 40g of water, and stirring until the sodium hydroxide is uniformly dissolved to form a solution 1; adding 14.3g of aluminum hydroxide into the solution 1, and uniformly stirring to form a solution 2; adding 645g of water into the solution 2 to form a solution 3, adding 98.2g of white carbon black into the solution 3 after the solution is cooled to room temperature, and stirring uniformly to form a mother solution, wherein the ratio (molar ratio) of the mother solution is 6Na 2 O:Al 2 O 3 :30SiO 2 :780H 2 O；
Transferring the mother liquor into a stainless steel reaction kettle with a polytetrafluoroethylene lining for hydrothermal crystallization, wherein the crystallization temperature is 150 ℃, and the crystallization time is 24 hours; and collecting crystallized products by filtering, washing and drying, wherein the pH value of the washed products is less than 10, the drying temperature is 80 ℃ and the drying time is 24 hours, so as to obtain the primary product, namely MOR zeolite.
The MOR zeolite is prepared by the following steps of (1) solid-liquid mass ratio: 100 in deionized water to obtain zeolite dispersion; dissolving cobalt nitrate in zeolite dispersion liquid, and regulating the concentration of metal ions to be 1mol/L; heating the obtained mixed solution to 80 ℃, and preserving heat for 2 hours to perform ion exchange; and cooling, filtering, washing and drying to obtain Co-MOR zeolite doped with cobalt.
XRD testing was performed on the obtained Co-doped Co-MOR zeolite product, the test result is shown as curve f in FIG. 1, and the product is consistent with the MOR zeolite standard spectrum.
Testing Co-MOR zeolite doped with cobalt nitrate in NO x 、CO 2 And O 2 Dynamic NO capture in mixed gas x The test conditions were the same as in example 1, the test results are shown in FIG. 7, and the adsorption amounts obtained by the integral calculation are shown in Table 1.
Example 7
The preparation of the heteroatom MOR zeolite comprises the following steps:
adding 19g of sodium hydroxide into 40g of water, and stirring until the sodium hydroxide is uniformly dissolved to form a solution 1; adding 14.3g of aluminum hydroxide into the solution 1, and uniformly stirring to form a solution 2; adding 645g of water into the solution 2 to form a solution 3, adding 98.2g of white carbon black into the solution 3 after the solution is cooled to room temperature, and stirring uniformly to form a mother solution, wherein the ratio (molar ratio) of the mother solution is 6Na 2 O:Al 2 O 3 :30SiO 2 :780H 2 O；
Transferring the mother liquor into a stainless steel reaction kettle with a polytetrafluoroethylene lining for hydrothermal crystallization, wherein the crystallization temperature is 150 ℃, and the crystallization time is 24 hours; and collecting crystallized products by filtering, washing and drying, wherein the pH value of the washed products is less than 10, the drying temperature is 80 ℃ and the drying time is 24 hours, so as to obtain the primary product, namely MOR zeolite.
The MOR zeolite is prepared by the following steps of (1) solid-liquid mass ratio: 100 in deionized water to obtain zeolite dispersion; copper nitrate is dissolved in zeolite dispersion liquid, and the concentration of metal ions is regulated to be 1mol/L; heating the obtained mixed solution to 80 ℃, and preserving heat for 2 hours to perform ion exchange; after cooling, filtering, washing and drying are carried out to obtain the Cu-MOR zeolite doped with copper.
XRD testing was performed on the obtained Cu-MOR type zeolite product doped with copper, and the test result is shown as curve g in FIG. 1, and the product is consistent with the MOR type zeolite standard spectrum.
Testing copper nitrate doped Cu-MOR zeolite in NO x 、CO 2 And O 2 And dynamic NO capture in mixed gas x The test conditions were the same as in example 1, the test results are shown in FIG. 8, and the adsorption amounts obtained by the integral calculation are shown in Table 1.
Example 8
The preparation of the heteroatom MOR zeolite comprises the following steps:
adding 19g of sodium hydroxide into 40g of water, and stirring until the sodium hydroxide is uniformly dissolved to form a solution 1; adding 14.3g of aluminum hydroxide into the solution 1, and uniformly stirring to form a solution 2; adding 645g of water into the solution 2 to form a solution 3, adding 98.2g of white carbon black into the solution 3 after the solution is cooled to room temperature, and stirring uniformly to form a mother solution, wherein the ratio (molar ratio) of the mother solution is 6Na 2 O:Al 2 O 3 :30SiO 2 :780H 2 O；
Transferring the mother liquor into a stainless steel reaction kettle with a polytetrafluoroethylene lining for hydrothermal crystallization, wherein the crystallization temperature is 150 ℃, and the crystallization time is 24 hours; and collecting crystallized products by filtering, washing and drying, wherein the pH value of the washed products is less than 10, the drying temperature is 80 ℃ and the drying time is 24 hours, so as to obtain the primary product, namely MOR zeolite.
The MOR zeolite is prepared by the following steps of (1) solid-liquid mass ratio: 100 in deionized water to obtain zeolite dispersion; zinc nitrate is dissolved in zeolite dispersion liquid, and the concentration of metal ions is regulated to be 1mol/L; heating the obtained mixed solution to 80 ℃, and preserving heat for 2 hours to perform ion exchange; and cooling, filtering, washing and drying to obtain Zn-MOR zeolite doped with zinc.
XRD testing is carried out on the obtained Zn-MOR zeolite product doped with zinc, the test result is shown as curve h in figure 1, and the product is consistent with the MOR zeolite standard spectrum.
Testing of cobalt nitrate doped Zn-MORZeolite at NO x 、CO 2 And O 2 Dynamic NO capture in mixed gas x The test conditions were the same as in example 1, the test results are shown in FIG. 9, and the adsorption amounts obtained by the integral calculation are shown in Table 1.
Comparative example 1
The preparation of MOR type zeolite (non-heteroatom doped) is as follows:
adding 19g of sodium hydroxide into 40g of water, and stirring until the sodium hydroxide is uniformly dissolved to form a solution 1; adding 14.3g of aluminum hydroxide into the solution 1, and uniformly stirring to form a solution 2; adding 645g of water into the solution 2 to form a solution 3, adding 98.2g of white carbon black into the solution 3 after the solution is cooled to room temperature, and stirring uniformly to form a mother solution, wherein the ratio (molar ratio) of the mother solution is 6Na 2 O:Al 2 O 3 :30SiO 2 :780H 2 O；
Testing MOR zeolite in NO x 、CO 2 And O 2 Dynamic NO capture in mixed gas x The test conditions were the same as in example 1, the test results are shown in FIG. 10, and the adsorption amounts obtained by the integral calculation are shown in Table 1.
Comparative example 2
Commercial Y-type zeolite is prepared according to a solid-liquid mass ratio of 1:100 in deionized water to obtain zeolite dispersion; dissolving cobalt nitrate in zeolite dispersion liquid, and regulating the concentration of metal ions to be 1mol/L; heating the obtained mixed solution to 80 ℃, and preserving heat for 2 hours to perform ion exchange; and cooling, filtering, washing and drying to obtain the Co-Y zeolite doped with cobalt.
Testing Co-Y zeolite in NO x 、CO 2 And O 2 Dynamic NO capture in mixed gas x The test conditions were the same as in example 1, the test results are shown in FIG. 11, and the adsorption amounts obtained by the integral calculation are shown in Table 1.
Comparative example 3
Test of commercial ZSM-5 type zeolite in NO x 、CO 2 And O 2 Dynamic NO capture in mixed gas x The test conditions were the same as in example 1, the test results are shown in FIG. 12, and the adsorption amounts obtained by the integral calculation are shown in Table 1.
TABLE 1 dynamic NOx adsorption amounts of the zeolites obtained in examples 1 to 8 and comparative examples 1 to 3
As can be seen from the above examples, the present invention provides a hetero atom MOR zeolite having excellent selective adsorption of Nitrogen Oxides (NO) by hetero atom metal doping of MOR zeolite by ion exchange x ) Can be derived from flue gas (including NO x 、CO 2 And O 2 ) Medium and high efficiency selective adsorption of NO x 。
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A process for the preparation of a heteroatom MOR zeolite comprising the steps of:
mixing MOR zeolite, water and soluble metal salt for ion exchange to obtain the heteroatom MOR zeolite; the metal element in the soluble metal salt comprises one or more of a group IIA metal element and a transition metal element.
2. The method of preparation of claim 1, wherein the group IIA metal element comprises magnesium and/or strontium; the transition metal element includes one or more of zinc, nickel, manganese, iron, cobalt, and copper.
3. The method according to claim 1 or 2, wherein the soluble metal salt comprises one or more of chloride salt, nitrate salt and sulfate salt.
4. The preparation method according to claim 1, wherein the mass ratio of the MOR zeolite to water is 1:10-1:1000, and the concentration of metal ions of the soluble metal salt in the mixed solution obtained by mixing is 0.1-2 mol/L.
5. The method according to claim 1, wherein the ion exchange is carried out at a temperature of 80 to 100 ℃ for a time of 0.5 to 3 hours.
6. The process according to claim 1, wherein the process for preparing MOR zeolite comprises the steps of:
mixing an alkali source, an aluminum source, a silicon source and water to obtain a mother solution; the alkali source is alkali metal hydroxide and/or alkali metal oxide, and the alkali source, the aluminum source, the silicon source and the alkali metal oxide and the Al are respectively used 2 O 3 、SiO 2 And H 2 O is calculated, alkali metal oxide and Al are contained in the mother solution 2 O 3 、SiO 2 And H 2 The mol ratio of O is (3-10) 1 (15-60) 350-1000;
carrying out hydrothermal crystallization on the mother solution to obtain MOR zeolite; the temperature of the hydrothermal crystallization is 150-200 ℃ and the time is 24-72 h.
7. The heteroatom MOR zeolite prepared by the method of any one of claims 1-6, wherein the heteroatom in the heteroatom MOR zeolite comprises one or more of a group IIA metal element and a transition metal element.
8. The heteroatom MOR zeolite according to claim 7, wherein the doping amount of the heteroatom in the heteroatom MOR zeolite is 0.1 to 2wt%.
9. Use of a heteroatom MOR zeolite according to claim 7 or 8 for the selective adsorption of nitrogen oxides.
10. The use according to claim 9, wherein the nitrogen oxides are derived from a group comprising CO 2 And O 2 Is a mixed gas of (a) and (b).
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