CN115286007A - SSZ-13 molecular sieve with high specific surface area, preparation method and application thereof - Google Patents
SSZ-13 molecular sieve with high specific surface area, preparation method and application thereof Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 105
- 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 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000013078 crystal Substances 0.000 claims abstract description 48
- 238000000498 ball milling Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 20
- 239000010703 silicon Substances 0.000 claims abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005530 etching Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 150000001339 alkali metal compounds Chemical class 0.000 claims abstract description 10
- -1 hydroxide ions Chemical class 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000000908 ammonium hydroxide Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003929 acidic solution Substances 0.000 claims description 5
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000019743 Choline chloride Nutrition 0.000 claims description 4
- 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 4
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 4
- 229960003178 choline chloride Drugs 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 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
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical compound C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 16
- 238000003756 stirring Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000005303 weighing Methods 0.000 description 6
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 4
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/723—CHA-type, e.g. Chabazite, LZ-218
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- B01J35/61—
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
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- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- 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
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Abstract
The invention relates to an SSZ-13 molecular sieve with high specific surface area, a preparation method and application thereof, comprising the following steps: processing an SSZ-13 molecular sieve precursor by adopting an acid etching auxiliary ball milling mode to prepare SSZ-13 seed crystals; and carrying out hydrothermal reaction on a mixed reaction system containing a silicon source, an aluminum source, hydroxide ions, an alkali metal compound, a template and SSZ-13 seed crystals to prepare the SSZ-13 molecular sieve with high specific surface area. The invention has the beneficial effects that: the method provided by the invention adopts the SSZ-13 molecular sieve which is subjected to acid etching assisted ball milling as the seed crystal, and the SSZ-13 molecular sieve prepared by adopting untreated SSZ-13 as the seed crystal has better crystallinity and specific surface area; meanwhile, the dosage of the SSZ-13 crystal seeds subjected to acid etching assisted ball milling in the method can be obviously lower than that of the untreated SSZ-13 crystal seeds.
Description
Technical Field
The invention relates to the technical field of molecular sieves, in particular to an SSZ-13 molecular sieve with high specific surface area, a preparation method and application thereof.
Background
The SSZ-13 molecular sieve is an ellipsoidal Cage (CHA) with an eight-membered ring structure orderly arranged by connecting AlO4 and SiO4 tetrahedrons end to end through oxygen atoms, and a window of the cage is formed by connecting a D6R unit with a four-membered ring to form a specific three-dimensional crossed pore channel structure. The SSZ-13 has a developed pore structure and good thermal stability due to the special ordered framework composition, and is an excellent adsorbent or catalyst carrier. In addition, al- (OH) -Si bridge hydroxyl is formed at the oxygen atom connected with silicon and aluminum in the framework of the SSZ-13 molecular sieve, so that the SSZ-13 molecular sieve has certain acidity and cation exchange performance, and the SSZ-13 molecular sieve has good acidity catalysis, shape-selective catalysis and the like.
SSZ-13 molecular sieves were first reported in a patent form in 1985 by Zones, inc. of Chevron (Chevron), USA (US 4544538). Due to the need to use expensive N, N, N-trimethyl-1-amantadine cation as organic template agent, the synthesis cost of SSZ-13 is too high, which limits its large scale application. To address this problem, zones reduced the amount of N, N, N-trimethyl-1-adamantanamine cation used as an organic templating agent by adding benzyltrimethylammonium cation in 2006 (US 60/826882). Miller in the US 7597874 patent teaches that the synthesis of SSZ-13 molecular sieve can be promoted by seeding with SSZ-13 molecular sieve, and that only benzyltrimethylammonium cation can be used as a template. Patent CN201310645906.4 discloses a preparation method of SSZ-13 by Chen Daihua et al of Beijing university of chemical industry, which takes choline chloride as a template agent and SSZ-13 as a seed crystal. The preparation of SSZ-13 molecular sieve by the seed crystal method (SSZ-13 seed crystal) reported in patent CN201511018804.5 can reduce the use amount of cationic template. However, in order to obtain a high quality SSZ-13 molecular sieve, the amount of seed crystals added needs to be 5% or more of the amount of SiO2 charged.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides an SSZ-13 molecular sieve with high specific surface area, a preparation method and application thereof.
In a first aspect, there is provided a process for the preparation of an SSZ-13 molecular sieve having a high specific surface area, comprising:
s1, processing an SSZ-13 molecular sieve precursor by adopting an acid etching auxiliary ball milling mode to prepare SSZ-13 seed crystals;
s2, carrying out hydrothermal reaction on a mixed reaction system containing a silicon source, an aluminum source, hydroxide ions, an alkali metal compound, a template agent and the SSZ-13 seed crystal to prepare the SSZ-13 molecular sieve with high specific surface area.
Preferably, in S1, an SSZ-13 molecular sieve precursor and an acidic solution are mixed and placed in a ball milling device for acid etching auxiliary ball milling treatment, and then washing, centrifuging and drying treatment are carried out to prepare the SSZ-13 seed crystal; wherein the pH value of the acidic solution is 1-4.
Preferably, in S2, the silicon source includes a tetravalent silicon source, and the tetravalent silicon source includes SiO 2 One or a combination of two or more of tetraethoxysilane and silica sol;
the aluminum source comprises a trivalent aluminum source; the trivalent aluminum source comprises any one or the combination of two or more of sodium metaaluminate, aluminum hydroxide and aluminum sulfate;
the alkali metal compound comprises sodium hydroxide and/or potassium hydroxide;
the template agent comprises any one or the combination of two or more of N, N, N-trimethyl-1-adamantane ammonium hydroxide, choline chloride, benzyl trimethyl ammonium cation, N, N, N-trimethyl-1, 3,5, 7-tetraazatricyclo [3.3.1.1] -decane-2-ammonium hydroxide.
Preferably, in S2, a silicon source, an aluminum source, hydroxide ions, an alkali metal compound, a template agent, and the SSZ-13 seed crystal are mixed to form the mixed reaction system, and then a hydrothermal reaction is performed at 130 to 170 ℃ to prepare the SSZ-13 molecular sieve.
Preferably, in S1, the SSZ-13 molecular sieve precursor comprises H-SSZ-13 molecular sieve, na-SSZ-13 molecular sieve and NH 4 -any one or a combination of two or more of SSZ-13 molecular sieves; the ball milling device comprises a planetary ball mill; the acid solution comprises any one or the combination of two or more of hydrochloric acid, acetic acid and sulfuric acid.
Preferably, in S2, the mass ratio of the silicon source to the SSZ-13 seed crystal is: 1:0.005 to 1:0.1.
preferably, in S2, the specific surface area of the SSZ-13 molecular sieve is more than 550m 2 g -1 。
In a second aspect, a method for preparing a Cu-SSZ-13 molecular sieve is provided, wherein the SSZ-13 molecular sieve is obtained by Cu ion exchange of the SSZ-13 molecular sieve in the first aspect.
In a third aspect, there is provided the use of the SSZ-13 molecular sieve of the first aspect or the Cu-SSZ-13 molecular sieve of the second aspect for the purification of diesel exhaust or power plant exhaust, wherein the SSZ-13 molecular sieve or the Cu-SSZ-13 molecular sieve selectively catalyzes the reduction of nitrogen oxides over a wide temperature range.
The beneficial effects of the invention are:
1. the method provided by the invention adopts the SSZ-13 molecular sieve subjected to acid etching assisted ball milling as the seed crystal, and the SSZ-13 molecular sieve prepared by adopting untreated SSZ-13 as the seed crystal has better crystallinity and specific surface area.
2. The dosage of the SSZ-13 crystal seeds subjected to acid etching assisted ball milling in the method provided by the invention can be obviously lower than that of the untreated SSZ-13 crystal seeds.
3. Compared with the SSZ-13 molecular sieve prepared by the traditional crystal seed method, the SSZ-13 molecular sieve prepared by the invention is subjected to Cu 2+ The exchanged product has more excellent denitration performance.
Drawings
FIG. 1 is a schematic view of the H-SSZ-13 before ball-milling in example 1 of the present invention;
FIG. 2 is a schematic representation of the SSZ-13 seed crystal in example 1 of the present invention;
FIG. 3 is a micro-topography of the SSZ-13 molecular sieve in example 1 of the invention;
FIG. 4 is a micro-topography of the SSZ-13 molecular sieve in example 2 of the invention;
FIG. 5 is a microscopic morphology of the SSZ-13 molecular sieve of comparative example 1 of the present invention;
FIG. 6 is a microscopic morphology of SSZ-13 seed crystal in comparative example 2 of the present invention;
FIG. 7 is a microscopic morphology of SSZ-13 seed crystal in comparative example 2 of the present invention;
FIG. 8 is an XRD pattern of SSZ-13 molecular sieves prepared in example 1, example 2, comparative example 1 and comparative example 2 of the present invention;
FIG. 9 is a graph of the SCR performance of Cu-SSZ-13 in inventive example 4 and comparative example 3.
Detailed Description
The present invention will be further described with reference to the following examples. The following examples are set forth merely to aid in the understanding of the invention. It should be noted that modifications can be made to the invention by a person skilled in the art without departing from the principle of the invention, and these modifications and modifications also fall within the scope of the claims of the invention.
SSZ-13 molecular sieve precursor which is subjected to acid etching auxiliary ball milling is used as seed crystal to prepare the SSZ-13 molecular sieve, and SSZ-13 molecular sieve seed crystal particles which are subjected to acid etching auxiliary ball milling are cracked and are rich in defects, so that more sites can be provided for the growth of SSZ-13 in the synthesis process, the crystal quality of the SSZ-13 molecular sieve can be improved, and the using amount of the SSZ-13 molecular sieve seed crystal can be effectively reduced.
Specifically, as one aspect of the technical scheme of the invention, the preparation method of the SSZ-13 molecular sieve comprises the following steps:
s1, processing an SSZ-13 molecular sieve precursor by adopting an acid etching auxiliary ball milling mode to prepare SSZ-13 seed crystals.
Specifically, an SSZ-13 molecular sieve precursor and an acidic solution are mixed and placed in a ball milling device for acid etching auxiliary ball milling treatment, and then washing, centrifuging and drying treatment are carried out to prepare SSZ-13 seed crystals; wherein the pH value of the acid solution is 1-4. The ball milling process is to crush and mix materials by using an impact action of falling milling bodies (steel balls or ceramic balls) and a milling action of the milling bodies and inner walls of the ball mill, and the ball mill is preferably a planetary ball mill, but not limited thereto.
In S1, the precursors of the SSZ-13 molecular sieve comprise H-SSZ-13 molecular sieve, na-SSZ-13 molecular sieve and NH 4 -any one or a combination of two or more of the SSZ-13 molecular sieves, without being limited thereto; the acidic solution includes any one or a combination of two or more of hydrochloric acid, acetic acid, and sulfuric acid, and is not limited thereto.
S2, carrying out hydrothermal reaction on a mixed reaction system containing a silicon source, an aluminum source, hydroxide ions, an alkali metal compound, a template and SSZ-13 seed crystals to prepare the SSZ-13 molecular sieve with high specific surface area.
Specifically, a silicon source, an aluminum source, hydroxide ions, an alkali metal compound, a template agent and SSZ-13 seed crystals are mixed to form a mixed reaction system, and then hydrothermal reaction is carried out at 130-170 ℃ to prepare the SSZ-13 molecular sieve.
Wherein the silicon source includes a tetravalent silicon source, without being limited thereto. The tetravalent silicon source comprises SiO 2 Any one or a combination of two or more of tetraethoxysilane and silica sol, without being limited thereto;
the aluminum source includes a trivalent aluminum source, and is not limited thereto; the trivalent aluminum source comprises any one or a combination of two or more of sodium metaaluminate, aluminum hydroxide and aluminum sulfate, and is not limited to the above;
the alkali metal compound includes sodium hydroxide and/or potassium hydroxide, and is not limited thereto;
the template includes any one or a combination of two or more of N, N, N-trimethyl-1-adamantane ammonium hydroxide, choline chloride, benzyltrimethyl ammonium cation, N, N, N-trimethyl-1, 3,5, 7-tetraazatricyclo [3.3.1.1] -decane-2-ammonium hydroxide, and is not limited thereto.
In S2, the mass ratio of the silicon source to the SSZ-13 seed crystal is as follows: 1:0.005 to 1:0.1.
in S2, the specific surface area of the SSZ-13 molecular sieve is more than 550m 2 g -1 。
In another aspect of the technical scheme of the invention, the Cu-SSZ-13 molecular sieve is also provided, and the Cu-SSZ-13 molecular sieve is obtained by performing Cu ion exchange on the SSZ-13 molecular sieve.
In another aspect of the technical scheme of the invention, the application of the SSZ-13 molecular sieve or the Cu-SSZ-13 molecular sieve in the purification of diesel vehicle tail gas or power plant tail gas is also provided, and specifically, the SSZ-13 molecular sieve or the Cu-SSZ-13 molecular sieve is used for selectively catalyzing and reducing nitrogen oxides in a wide temperature range.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples below were obtained from conventional biochemicals unless otherwise specified.
Example 1:
(1) Adding 5 microliters of concentrated hydrochloric acid with the mass fraction of 36.5% into 5mL of deionized water to enable the pH value to be 2, then weighing 1g of H-SSZ-13 molecular sieve, adding the molecular sieve into the acidic deionized water, uniformly mixing, transferring the mixture into a ball milling tank, and carrying out ball milling at the rotation speed of 350 revolutions per minute for 3 hours. After the ball milling is finished, washing, centrifuging and drying to obtain SSZ-13 seed crystals. The morphology of H-SSZ-13 before ball milling is shown in FIG. 1, and the morphology of H-SSZ-13 after acid etching assisted ball milling is shown in FIG. 2. It is clear that the H-SSZ-13 particles after acid etch assisted ball milling are broken up to form a large number of small particles and the surface roughness, i.e. defects, are increased.
(2) Firstly, 1.658g of sodium metaaluminate (aluminum source) and 10.14g of pure water are mixed, after complete dissolution, 1.100g of sodium hydroxide is added, after stirring for 15 minutes, 33.76g of 25wt% aqueous solution of N, N-trimethyl-1-adamantane ammonium hydroxide is added, and the mixture is stirred vigorously to be completely mixed;
(3) 0.6g of (SiO) SSZ-13 seed crystal of step (1) was added under vigorous stirring 2 5 percent of the feeding amount) and stirring for 15 minutes;
(4) 12g of SiO are added with vigorous stirring 2 After stirring for 2h, the mixture is transferred into a reaction kettle and reacted at 160 ℃ for 3 days to obtain the SSZ-13 molecular sieve, wherein the micro-morphology of the SSZ-13 molecular sieve prepared in this example is shown in FIG. 3, and the XRD thereof is shown in FIG. 8.
Example 2:
the SSZ-13 seed charge in step (3) of example 1 was changed to 0.108g (SiO) 2 0.9% of the charge), the other steps are the same as in example 1. The microscopic morphology of the product is shown in FIG. 4, and the XRD thereof is shown in FIG. 8.
Example 3:
the amount of hydrochloric acid added in step (1) in example 1 was changed to 3. Mu.l, and the other steps were the same as in example 1.
Example 4:
the preparation method for preparing the Cu-SSZ-13 molecular sieve comprises the following steps:
(1) 10g of the SSZ-13 molecular sieve of example 1 was weighed into 1M NH 4 NO 3 Stirring the solution at the temperature of 80 ℃ for reaction for 6h, washing, centrifuging and drying to obtain NH 4 -SSZ-13；
(2) Weighing 1.0g of blue vitriol and dissolving in 20mL of water to prepare a blue vitriol solution;
(3) Weighing 1g of NH in the step (1) 4 Adding SSZ-13 molecular sieve into the copper sulfate solution in the step (2) and stirring for reaction at the temperature of 80 ℃ for 3 hours;
(4) Washing the product in the step (3) by deionized water, centrifuging and drying at 80 ℃;
(5) And (4) placing the molecular sieve powder in the step (4) into a muffle furnace, calcining at 560 ℃ for 4h, and naturally cooling to obtain the Cu-SSZ-13 molecular sieve.
Comparative example 1:
the traditional crystal seed method for preparing the SSZ-13 molecular sieve specifically comprises the following steps: the SSZ-13 molecular sieve which is not subjected to acid etching assisted ball milling is used as a seed crystal, other steps are the same as those of the example 1, and the microstructure of the product is shown in figure 5, and the XRD thereof is shown in figure 8.
Comparative example 2:
SSZ-13 molecular sieve is prepared by SSZ-13 seed crystal prepared by a general ball milling method, which comprises the following steps:
the preparation process of the SSZ-13 seed crystal in the step (1) of example 1 is changed to the preparation process of the SSZ-13 seed crystal by ball milling without adding hydrochloric acid, the microstructure of the SSZ-13 seed crystal is shown in fig. 6, and the preparation process specifically comprises the following steps:
weighing 1g of H-SSZ-13 molecular sieve, adding the H-SSZ-13 molecular sieve into 5mL of ionized water, uniformly mixing, transferring the mixture into a ball milling tank, and carrying out ball milling for 3 hours at the rotating speed of 350 r/min. After the ball milling is finished, washing, centrifuging and drying are carried out, so that the SSZ-13 seed crystal is obtained, the microstructure of the SSZ-13 seed crystal is shown in figure 7, and the XRD of the SSZ-13 seed crystal is shown in figure 8.
The other steps were the same as in example 1.
Comparative example 3:
preparation of Cu-SSZ-13 based on comparative example 1:
(1) 10g of the SSZ-13 molecular sieve prepared in comparative example 1 was weighed out and added to 1M NH 4 NO 3 Stirring the solution at the temperature of 80 ℃ for reaction for 6h, washing, centrifuging and drying to obtain NH 4 -SSZ-13；
(2) Weighing 1.0g of blue vitriol and dissolving in 20mL of water to prepare a blue vitriol solution;
(3) Weighing 1g of NH in the step (1) 4 Adding SSZ-13 molecular sieve into the copper sulfate solution in the step (2) and stirring for reaction at the temperature of 80 ℃ for 3 hours;
(4) Washing the product in the step (3) by deionized water, centrifuging and drying at 80 ℃;
(5) And (5) placing the molecular sieve powder in the step (4) into a muffle furnace, calcining for 4h at 560 ℃, and naturally cooling to obtain the Cu-SSZ-13 molecular sieve.
The BET results for the SSZ-13 molecular sieves prepared in example 1, comparative example 1 and comparative example 2 are shown in Table 1.
TABLE 1BET results
| Name (R) | BET specific surface area | Pore volume |
| SSZ-13 (example 1) | 635.7m 2 g -1 | 0.326cm 3 g -1 |
| SSZ-13 (comparative example 1) | 549.1m 2 g -1 | 0.301cm 3 g -1 |
| SSZ-13 (comparative example 2) | 602.4m 2 g -1 | 0.317cm 3 g -1 |
The SCR performance of Cu-SSZ-13 in example 4 and comparative example 3 is shown in FIG. 9.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
Claims (9)
1. A method for preparing an SSZ-13 molecular sieve with high specific surface area, which is characterized by comprising the following steps:
s1, processing an SSZ-13 molecular sieve precursor by adopting an acid etching auxiliary ball milling mode to prepare SSZ-13 seed crystals;
s2, carrying out hydrothermal reaction on a mixed reaction system containing a silicon source, an aluminum source, hydroxide ions, an alkali metal compound, a template and the SSZ-13 seed crystal to prepare the SSZ-13 molecular sieve with high specific surface area.
2. The method for preparing the SSZ-13 molecular sieve with high specific surface area according to claim 1, wherein in S1, an SSZ-13 molecular sieve precursor is mixed with an acidic solution, and the mixture is placed in a ball milling device for acid etching assisted ball milling treatment, and then the SSZ-13 seed crystal is prepared through washing, centrifugation and drying treatment; wherein the pH value of the acid solution is 1-4.
3. The method of claim 1, wherein in S2, the silicon source comprises a tetravalent silicon source, and the tetravalent silicon source comprises SiO 2 One or a combination of two or more of tetraethoxysilane and silica sol;
the aluminum source comprises a trivalent aluminum source; the trivalent aluminum source comprises any one or the combination of two or more of sodium metaaluminate, aluminum hydroxide and aluminum sulfate;
the alkali metal compound comprises sodium hydroxide and/or potassium hydroxide;
the template agent comprises any one or the combination of two or more of N, N, N-trimethyl-1-adamantane ammonium hydroxide, choline chloride, benzyl trimethyl ammonium cation and N, N, N-trimethyl-1, 3,5, 7-tetraazatricyclo [3.3.1.1] -decane-2-ammonium hydroxide.
4. The method of claim 1, wherein in S2, a silicon source, an aluminum source, hydroxide ions, an alkali metal compound, and a template are mixed with the SSZ-13 seed crystal to form the mixed reaction system, and then the mixed reaction system is hydrothermally reacted at 130 to 170 ℃ to obtain the SSZ-13 molecular sieve.
5. The method of claim 2, wherein in S1, the SSZ-13 molecular sieve precursor comprises H-SSZ-13 molecular sieve, na-SSZ-13 molecular sieve, NH 4 -any one or a combination of two or more of the SSZ-13 molecular sieves; the ball milling device comprises a planetary ball mill; the acid solution comprises any one or the combination of two or more of hydrochloric acid, acetic acid and sulfuric acid.
6. The method for preparing SSZ-13 molecular sieve with high specific surface area according to claim 1, wherein in S2, the mass ratio of the silicon source to the SSZ-13 seed crystal is: 1:0.005 to 1:0.1.
7. the process for the preparation of the SSZ-13 molecular sieve having a high specific surface area according to any one of claims 1 to 6, characterized in that, in S2, the specific surface area of the SSZ-13 molecular sieve is more than 550m 2 g -1 。
8. A method for preparing a Cu-SSZ-13 molecular sieve, wherein the molecular sieve of claim 1 is subjected to Cu ion exchange to obtain the SSZ-13 molecular sieve.
9. Use of the SSZ-13 molecular sieve of claim 1 or the Cu-SSZ-13 molecular sieve of claim 8 for the purification of diesel exhaust or power plant exhaust, wherein the SSZ-13 molecular sieve or Cu-SSZ-13 molecular sieve selectively catalyzes the reduction of nitrogen oxides over a wide temperature range.
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