CN115893445A - SSZ-39 molecular sieve and method for preparing SSZ-39 molecular sieve by using cheap template agent - Google Patents
SSZ-39 molecular sieve and method for preparing SSZ-39 molecular sieve by using cheap template agent Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 129
- 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 129
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- 238000002425 crystallisation Methods 0.000 claims abstract description 24
- 230000008025 crystallization Effects 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 230000032683 aging Effects 0.000 claims abstract description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000007790 solid phase Substances 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 150000002500 ions Chemical class 0.000 claims description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 16
- -1 orthosilicate ester Chemical class 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 6
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 6
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 6
- 235000019353 potassium silicate Nutrition 0.000 claims description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-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
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 3
- 229910001593 boehmite Inorganic materials 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000011863 silicon-based powder Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 20
- 238000001878 scanning electron micrograph Methods 0.000 description 16
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 150000003053 piperidines Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 description 3
- NEUNMNDZSAVWGE-UHFFFAOYSA-N tetraethyl(hydroxy)-lambda5-phosphane Chemical compound CCP(O)(CC)(CC)CC NEUNMNDZSAVWGE-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- 230000004075 alteration Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000011426 transformation method Methods 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses an SSZ-39 molecular sieve and a method for preparing the SSZ-39 molecular sieve by using a cheap template agent, wherein the method comprises the following steps: s1, mixing and stirring a silicon source, an aluminum source, an alkali source, an organic template agent A and water uniformly, and then aging to obtain a prepared gel; s2, firstly, placing the prepared gel in a reaction container, adding an organic template agent B, and then aging; then controlling the reaction container to stir at room temperature; finally, crystallization treatment is carried out under the condition of keeping the stirring of the reaction vessel; s3, taking out products in the reaction container after the crystallization treatment is finished, and sequentially carrying out: filtering, washing and drying the filtered solid-phase component; and then roasting the dried product to obtain the SSZ-39 molecular sieve after roasting is finished. The invention obviously reduces the preparation cost of the SSZ-39 molecular sieve, and compared with the existing high-cost SSZ-39 molecular sieve, the prepared SSZ-39 molecular sieve has similar purity, specific surface area and reaction activity.
Description
Technical Field
The invention relates to the technical field related to molecular sieve preparation, in particular to an SSZ-39 molecular sieve and a method for preparing the SSZ-39 molecular sieve by using a cheap template agent.
Background
The SSZ-39 molecular sieve is a molecular sieve with AEI topological structure, and is formed by connecting AlO4 tetrahedron and SiO4 tetrahedron end to end through oxygen atoms to form a secondary structural unit (SBU) of double six-membered ring, the two adjacent layers of double six-membered ring are stirred for 180 degrees around a z axis and are distributed and arranged in a crossing way, the double six-membered ring is connected and arranged through four-membered ring to form AEI cage (asymmetric pear-shaped cage) with eight-membered ring structure and three-dimensional pore structure, and the pore size is
Due to the characteristics of ordered pore channel structure, high specific surface area, good hydrothermal stability, more surface proton acid centers, excellent cation exchangeability and the like, the SSZ-39 molecular sieve shows excellent performance in industrial catalytic processes of NH 3-selective catalytic reduction (NH 3-SCR), methanol-to-olefin catalytic reaction (MTO) and the like in recent years.
The prior art methods for preparing SSZ-39 molecular sieves, which are generally hydrothermal, suffer from the following problems in the existing synthesis processes: 1. the piperidine derivatives such as N, N,3, 5-tetramethylpiperidine hydroxide and N, N,2, 6-tetramethylpiperidine hydroxide are used as template agents, the cost of the piperidine derivatives in industrial production is always high due to the narrow application range of the piperidine derivatives, and the cost is further promoted to be high in the process of converting the piperidine derivatives into quaternary ammonium base by adopting an electrolysis or ion exchange method to ensure the purity and the conversion rate of the quaternary ammonium base. 2. The use of expensive organic templating agents such as: tetraethyl phosphorus hydroxide and N, N-dimethyl-N, N-bicyclononane directly cause the preparation cost of the SSZ-39 molecular sieve to be high.
Disclosure of Invention
The invention aims to provide a method for preparing an SSZ-39 molecular sieve by using a cheap template agent, so as to solve the problem of high cost of the industrial preparation of the existing SSZ-39 molecular sieve.
In order to achieve the purpose, the invention provides the following technical scheme: a method for preparing an SSZ-39 molecular sieve using an inexpensive templating agent comprising:
s1, preparing gel:
mixing and stirring a silicon source, an aluminum source, an alkali source, an organic template agent A and water uniformly, and aging at the temperature of 0-100 ℃ for 0.1-100h to obtain a prepared gel; the organic template A comprises: an organic ionic salt and/or an organic ionic base;
s2, crystallization treatment:
firstly, placing prepared gel in a reaction container, adding an organic template agent B, and aging for 0.1-5h; then controlling the reaction container to stir for 0-3h at room temperature; finally, the temperature in the reaction container is raised to 120-210 ℃ under the condition of keeping the stirring of the reaction container, and crystallization treatment is carried out for 30-120h; the organic template B comprises C4-C16 fatty amine;
s3, preparing an SSZ-39 molecular sieve:
after the crystallization treatment is finished, when the temperature in the reaction container is reduced to be below 40 ℃, taking out products in the reaction container to carry out the following steps in sequence: filtering, washing the filtered solid phase component, and drying; and then roasting the dried product to obtain the SSZ-39 molecular sieve after roasting is finished.
Further, the silicon source in step S1 includes: at least one of silicon dioxide, silica sol, silicate, orthosilicate ester, solid water glass, liquid water glass and silicon powder.
Further, step S1 said aluminum source comprises: at least one of USY molecular sieve, ZSM-5 molecular sieve, beta molecular sieve, sodium metaaluminate, aluminum hydroxide, pseudoboehmite, aluminum isopropoxide, aluminum sol and boehmite.
Further, the alkali source in step S1 includes: one or a mixture of two of sodium hydroxide and potassium hydroxide.
Further, in the organic template a in step S1, the organic ions include: n, N-diethyl-2, 6-dimethylpiperidinium ion, 3, 5-dimethyl-N, N-dimethylpiperidinium ion, N-diethyl-2-ethylpiperidinium ion, N-ethyl-N-propyl-2, 6-dimethylpiperidinium ion, N-methyl-N-ethyl-2-ethylpiperidinium ion, 2, 5-dimethyl-N, at least one of N-diethylpyrrole ion, 2, 6-dimethyl-N, N-dimethylpiperidine ion, 2-ethyl-N, N-dimethylpiperidine ion, 2, 6-tetramethyl-N-methyl-N-ethylpiperidine ion, and 2, 6-tetramethyl-N, N-dimethylpiperidine ion.
Further, the organic ions are: 3, 5-dimethyl-N, N-dimethylhydroxypiperidine.
Further, the molar ratio of the silicon source, the aluminum source, the alkali source, the organic template agent A, the organic template agent B and the water satisfies the following conditions: si: al =2.5-90: si =0-1, H 2 O: si =3-80: si =0-0.1: 1. rb: si =0-0.5: 1. ra: rb =0-1, where Ra is the number of moles of organic templating agent a and Rb is the number of moles of organic templating agent B.
Further, the organic template B in step S2 includes: at least one of n-butylamine, diisopropylethylamine, tri-n-propylamine, di-n-butylamine, triethylamine, diethylamine, dodecylamine, octadecylamine, cyclohexylamine and hexylamine.
Further, in the step S2, the time for controlling the stirring of the reaction vessel at room temperature is: 0.5-1h; the crystallization treatment time is as follows: 50-100h.
The second purpose of the invention is to provide an SSZ-39 molecular sieve, wherein the SSZ-39 molecular sieve is prepared by the method for preparing the SSZ-39 molecular sieve by using the cheap template agent; the particle size of the SSZ-39 molecular sieve is as follows: 0.1-10 μm.
The invention has at least one of the following advantages:
1. the invention adopts the mixed solution of amines with low cost and the conventional template to replace the prior high-cost template, thereby obviously reducing the preparation cost of the SSZ-39 molecular sieve.
2. Compared with the SSZ-39 molecular sieve prepared by adopting a high-cost template agent in the prior art, the SSZ-39 molecular sieve prepared by the invention has similar purity, specific surface area and reaction activity.
Drawings
FIG. 1 is a surface SEM image of an SSZ-39 molecular sieve obtained in example 1 of the present invention.
FIG. 2 is a surface SEM image of the SSZ-39 molecular sieve obtained in example 2 of the present invention.
FIG. 3 is a surface SEM picture of the SSZ-39 molecular sieve obtained in example 3 of the invention.
FIG. 4 is a surface SEM image of the SSZ-39 molecular sieve obtained in example 4 of the invention.
FIG. 5 is a surface SEM image of the SSZ-39 molecular sieve obtained in example 5 of the invention.
FIG. 6 is a surface SEM image of SSZ-39 molecular sieve obtained in example 6 of the invention.
FIG. 7 is a surface SEM image of SSZ-39 molecular sieve obtained in example 7 of the present invention.
FIG. 8 is a surface SEM image of the SSZ-39 molecular sieve obtained in comparative example 1 of the present invention.
FIG. 9 is a surface SEM image of the SSZ-39 molecular sieve obtained in comparative example 2 of the invention.
FIG. 10 is a surface SEM image of the SSZ-39 molecular sieve obtained in comparative example 4 of the present invention.
FIG. 11 is an XRD pattern of the SSZ-39 molecular sieve obtained in examples 1-7 of the invention.
FIG. 12 is an XRD pattern of the SSZ-39 molecular sieve obtained in comparative examples 1-2 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and technical effects to be solved by the present invention more clear and clear, the technical solutions of the present invention are described in detail below in combination with the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
In order to solve the problem of overhigh preparation cost of the SSZ-39 molecular sieve in the prior art, the invention exemplarily provides a method for preparing the SSZ-39 molecular sieve by using an inexpensive template, which comprises the following steps:
s1, preparing gel:
mixing and stirring a silicon source, an aluminum source, an alkali source, an organic template agent A and water uniformly, and aging at the temperature of 0-100 ℃ for 0.1-100h to obtain a prepared gel;
s2, crystallization treatment:
firstly, placing prepared gel in a reaction container, adding an organic template agent B, and aging for 0.1-5h; then controlling the reaction container to stir for 0-3h at room temperature; finally, the temperature in the reaction container is raised to 120-210 ℃ under the condition of keeping the stirring of the reaction container, and crystallization treatment is carried out for 30-120h;
s3, preparing an SSZ-39 molecular sieve:
after the crystallization treatment is finished, when the temperature in the reaction container is reduced to be below 40 ℃, taking out products in the reaction container to carry out the following steps in sequence: filtering, washing the filtered solid phase component, and drying; and then roasting the dried product to obtain the SSZ-39 molecular sieve after roasting is finished.
Wherein: the organic template A comprises: an organic ionic salt and/or an organic ionic base.
The present invention illustratively provides an organic ion salt and/or an organic ion base, wherein the organic ion comprises: n, N-diethyl-2, 6-dimethylpiperidinium ion, 3, 5-dimethyl-N, N-dimethylpiperidinium ion, N-diethyl-2-ethylpiperidinium ion, N-ethyl-N-propyl-2, 6-dimethylpiperidinium ion, N-methyl-N-ethyl-2-ethylpiperidinium ion, 2, 5-dimethyl-N, at least one of N-diethylpyrrole ion, 2, 6-dimethyl-N, N-dimethylpiperidine ion, 2-ethyl-N, N-dimethylpiperidine ion, 2, 6-tetramethyl-N-methyl-N-ethylpiperidine ion and 2, 6-tetramethyl-N, N-dimethylpiperidine ion.
The organic template B comprises: at least one of n-butylamine, diisopropylethylamine, tri-n-propylamine, di-n-butylamine, triethylamine, diethylamine, dodecylamine, octadecylamine, cyclohexylamine and hexylamine.
Compared with the piperidine template adopted in the prior art, the direct preparation cost of each kilogram of SSZ-39 molecular sieve can be reduced by about dozens to hundred yuan according to the market price, and generally can be relatively reduced by 20-30 percent. For example, in consideration of the cost increase caused by the fact that the industrial production has to be matched with corresponding processing and storage equipment due to the narrow application range of the piperidine template in the industrial process and the preparation cost increase caused by adopting an electrolysis or ion exchange method to convert the piperidine derivative into the quaternary ammonium base so as to ensure the purity and the conversion rate of the piperidine template, the total preparation cost of each kilogram of the SSZ-39 molecular sieve can be reduced by about one hundred yuan according to the market price, and generally can be relatively reduced by 30-40%. Compared with the high-cost nitrogen-containing organic derivative template and phosphine derivative template adopted in the prior art, the total preparation cost of each kilogram of SSZ-39 molecular sieve can be reduced by about dozens of yuan to hundred yuan according to the market price, and generally can be relatively reduced by about 25 percent. Therefore, the preparation method can obviously reduce the preparation cost of the SSZ-39 molecular sieve.
The invention provides a silicon source, which comprises: at least one of silicon dioxide, silica sol, silicate, orthosilicate ester, solid water glass, liquid water glass and silicon powder.
The present invention illustratively provides an aluminum source comprising: at least one of USY molecular sieve, ZSM-5 molecular sieve, beta molecular sieve, sodium metaaluminate, aluminum hydroxide, pseudoboehmite, aluminum isopropoxide, aluminum sol and boehmite.
The invention exemplarily provides an aluminum source, which is as follows: USY molecular sieve.
The present invention illustratively provides an alkali source comprising: one or a mixture of two of sodium hydroxide and potassium hydroxide.
The present invention illustratively provides an organic ion that is: 3, 5-dimethyl-N, N-dimethylhydroxypiperidine.
The invention provides a silicon source, an aluminum source, an alkali source, an organic template agent A, an organic template agent B and water in a molar ratio exemplarily, which comprises the following steps: the molar ratio of the silicon source, the aluminum source, the alkali source, the organic template agent A, the organic template agent B and the water meets the following requirements: si: al =2.5-90: si =0-1 2 O: si =3-80: si =0-0.1: 1. rb: si =0-0.5: 1. ra: rb =0-1, where Ra is the number of moles of organic templating agent a and Rb is the number of moles of organic templating agent B.
Only by adding the reactants at the molar ratio defined by the invention can the SSZ-39 molecular sieve with good performance be prepared by using the cheap template agent provided by the invention.
The invention exemplarily provides a method for controlling the stirring time of a reaction vessel at room temperature, which comprises the following steps: 0.5-1h.
The invention provides a crystallization processing time which is as follows: 50-100h.
In addition, the invention also exemplarily provides an SSZ-39 molecular sieve, and the SSZ-39 molecular sieve is prepared by the method for preparing the SSZ-39 molecular sieve by using the cheap template agent. The SSZ-39 molecular sieve has the particle size as follows: 0.1 μm to 10 μm, preferably 2 to 5 μm. The crystallinity is more than 90 percent through SCR diffraction spectrum measurement and calculation.
To explain the technical solution of the present application in more detail, the following describes the present application in more detail with reference to specific examples and comparative examples.
Example 1
An SSZ-39 molecular sieve is prepared by the following steps:
s1, fully mixing sodium hydroxide, pure water, silica sol with the concentration of 40wt%, 3, 5-dimethyl-N, N-dimethyl piperidine hydroxide (serving as an organic template A) with the concentration of 25wt% and a USY molecular sieve to obtain a raw material composition with the following mole ratio: siO 2 2 /Al 2 O 3 =50, organic template A (SDA for short)/SiO 2 ＝0.03、OH-/SiO 2 ＝0.65、H 2 O/SiO 2 And (5) =20, and aging is performed at room temperature for 3 hours to obtain a synthetic gel.
S2, adding the synthesized gel into an autoclave, adding a diisopropylethylamine solution (an organic template agent B), and controlling the addition amount of the organic template agent B to be a molar ratio: organic template agent B/SiO 2 Aging for 3h and then controlling the reaction vessel to stir at room temperature for 2h; and finally, raising the temperature in the reaction vessel to 170 ℃ under the condition of keeping the stirring of the reaction vessel for crystallization treatment for 40 hours.
S3, after the crystallization treatment is finished, taking out products in the reaction container to sequentially carry out when the temperature in the reaction container is reduced to be below 40 ℃: filtering, washing and drying the filtered solid-phase component; and then roasting the dried product at 550 ℃ for 4 hours to obtain the SSZ-39 molecular sieve after roasting is completed.
FIG. 1 is an SEM image of an SSZ-39 molecular sieve sample of this example, which was measured to have a length of about 1 μm to about 2 μm, a thickness of about 0.5 μm to about 1.0 μm, and a crystallinity of about 93% formed from N 2 The specific surface area of the adsorption and desorption is 745 +/-10 m 2 ·g -1 。
Example 2
An SSZ-39 molecular sieve is prepared by the following method:
s1, fully mixing sodium hydroxide, pure water, tetraethoxysilane, 3, 5-dimethyl-N, N-dimethyl piperidine hydroxide (serving as an organic template A) aqueous solution with the concentration of 25wt% and a USY molecular sieve to obtain a raw material composition with the following mole ratio: siO 2 2 /Al 2 O 3 =100, organic template A (SDA)/SiO 2 ＝0.03、OH-/SiO 2 ＝0.30、H 2 O/SiO 2 =25, aging at room temperature for 0.5h to give a synthetic gel.
S2, adding the synthesized gel into an autoclave, and adding a mixed solution (organic template agent B) of diisopropylethylamine and isobutylamine, wherein the molar ratio of diisopropylethylamine to isobutylamine is as follows: diisopropylethylamine/isobutylamine =7/10. Controlling the addition amount of the organic template agent B as a molar ratio: organic template agent B/SiO 2 Aging for 1h, and then controlling the reaction vessel to stir for 0.5h at room temperature; and finally, raising the temperature in the reaction container to 140 ℃ under the condition of keeping the stirring of the reaction container, and carrying out crystallization treatment for 100 hours.
S3, after the crystallization treatment is finished, taking out products in the reaction container to sequentially carry out when the temperature in the reaction container is reduced to be below 40 ℃: filtering, washing the filtered solid phase component, and drying; and then roasting the dried product at 550 ℃ for 4h to obtain the SSZ-39 molecular sieve after roasting is finished.
FIG. 2 is an SEM image of an SSZ-39 molecular sieve sample of this example having particles 2.2-3.0 μm in length and 1.0-2.0 μm in thickness and an SCR spectrum calculated to have a crystallinity of about 96% from N 2 Specific surface area of adsorption and desorptionProduct of 730 + -10 m 2 ·g -1 。
Example 3
An SSZ-39 molecular sieve is prepared by the following steps:
s1, fully mixing sodium hydroxide, pure water, silica sol with the concentration of 40wt%, 3, 5-dimethyl-N, N-dimethyl piperidine hydroxide (as an organic template A) aqueous solution with the concentration of 25wt% and a USY molecular sieve to obtain a raw material composition with the following mole ratio: siO 2 2 /Al 2 O 3 =60 organic template agent A (SDA for short)/SiO 2 ＝0.02、OH-/SiO 2 ＝0.5、H 2 O/SiO 2 And (5) =20, and aging is performed at room temperature for 0.5h to obtain a synthetic gel.
S2, adding the synthesized gel into an autoclave, adding a diisopropylethylamine solution (an organic template agent B), and controlling the addition amount of the organic template agent B to be a molar ratio: organic template agent B/SiO 2 =0.18 and aged for 2h, then the reaction vessel was controlled to stir at room temperature for 0.5h; and finally, raising the temperature in the reaction vessel to 170 ℃ under the condition of keeping the reaction vessel rotating, and performing crystallization treatment for 40 hours.
S3, after the crystallization treatment is finished, taking out products in the reaction container to sequentially carry out when the temperature in the reaction container is reduced to be below 40 ℃: filtering, washing and drying the filtered solid-phase component; and then roasting the dried product at 550 ℃ for 4h to obtain the SSZ-39 molecular sieve after roasting is finished.
FIG. 3 is a SEM picture of a sample of the SSZ-39 molecular sieve of this example, the particles of which have a length of 2.5-3.5 μm, a thickness of 1.2-2.0. Mu.m, a crystallinity of about 91%, and a specific surface area of 740. + -.10 m 2 ·g -1 。
Example 4
An SSZ-39 molecular sieve is prepared by the following method:
s1, fully mixing sodium hydroxide, pure water, sodium silicate, 25wt% of N, N-diethyl-2, 6-dimethyl hydrogen piperidine (serving as an organic template A) aqueous solution and a USY molecular sieve to obtain a raw material composition with the following mole ratio: siO 2 2 /Al 2 O 3 =40, organic template A: (SDA for short)
/SiO 2 ＝0.04、OH-/SiO 2 ＝0.6、H 2 O/SiO 2 And (5) =20, and aging is performed at room temperature for 1h to obtain a synthetic gel.
S2, adding the synthesized gel into an autoclave, and adding a mixed solution (organic template agent B) of n-butylamine, triethylamine and di-n-propylamine, wherein the molar ratio of the n-butylamine, the triethylamine and the di-n-propylamine meets the following requirements: n-butylamine: triethylamine: di-n-propyl = 6. Controlling the addition amount of the organic template agent B as a molar ratio: organic template agent B/SiO 2 =0.16 and aged for 2h, then the reaction vessel was controlled to rotate at room temperature for 0.5h; and finally, raising the temperature in the reaction container to 180 ℃ under the condition of keeping the reaction container rotating, and carrying out crystallization treatment for 30 hours.
S3, after the crystallization treatment is finished, taking out products in the reaction container to sequentially carry out when the temperature in the reaction container is reduced to be below 40 ℃: filtering, washing the filtered solid phase component, and drying; and then roasting the dried product at 550 ℃ for 4h to obtain the SSZ-39 molecular sieve after roasting is finished.
FIG. 4 is an SEM photograph of a sample of the SSZ-39 molecular sieve of this example, the particles of which have a length of 2.5-3.8 μm, a thickness of 1.0-1.5. Mu.m, a crystallinity of about 95% and a specific surface area of 730. + -.10 m 2 ·g -1 。
Example 5
This example is identical to example 1 with respect to the other steps, except that: the organic template agent A is N, N-diethyl-2-ethyl hydroxyl piperidine. FIG. 5 is an SEM image of an SSZ-39 molecular sieve sample of this example, with the results: the sample particles had a length of 2.5 to 3.2 μm, a thickness of 1.3 to 2.0. Mu.m, a crystallinity of about 95%, and a specific surface area of 730. + -.10 m 2 ·g -1 。
Example 6
This example is identical to example 1 with respect to the other steps, except that: the organic template agent A is 2, 5-dimethyl-N, N-diethyl hydroxyl pyrrole. FIG. 6 is an SEM image of a sample of the SSZ-39 molecular sieve of this example, with the results: the sample particles had a length of 2.5 to 3.6 μm, a thickness of 1.2 to 2.1. Mu.m, a crystallinity of about 95%, and a specific surface area of 730. + -.10 m 2 ·g -1 。
Example 7
This example is identical to example 1 with respect to the other steps, except that: the organic template agent A is 2-ethyl-N, N-dimethyl hydroxyl piperidine and 3, 5-dimethyl-N, N-dimethyl hydroxyl piperidine according to a molar ratio of 1:1, a mixed template agent. FIG. 7 is an SEM image of a sample of the SSZ-39 molecular sieve of this example, with the results: the sample particles had a length of 2.0 to 3.0 μm, a thickness of 1.0 to 1.8 μm, a crystallinity of about 95%, and a specific surface area of 730. + -.10 m 2 ·g -1 。
Comparative example 1
The SSZ-39 molecular sieve is synthesized by adopting N, N,2, 6-tetramethyl piperidine hydroxide and the existing matched hydrothermal method. Such as: an SSZ-39 molecular sieve with the silicon-aluminum ratio of 15 is synthesized by taking an FAU molecular sieve and sodium silicate as raw materials and N, N,2, 6-tetramethyl piperidine hydroxide as a template agent under the condition that the feeding silicon-aluminum ratio is 30. FIG. 8 is an SEM picture of an SSZ-39 molecular sieve sample of this comparative example, which has a length of about 2.0 μm to 3.5 μm, a thickness of about 1.5 μm to 2 μm, a crystallinity of about 93%, and a specific surface area of 725. + -.10 m 2 ·g -1 。
Comparative example 2
The SSZ-39 molecular sieve is synthesized by adopting tetraethyl phosphorus hydroxide and the existing matched hydrothermal method. Such as: tetraethyl phosphorus hydroxide is used as a template agent, a high-silicon FAU molecular sieve treated by water vapor and acid is used as a silicon source and an aluminum source, and the SSZ-39 molecular sieve with the silicon-aluminum ratio of 17 is synthesized by conversion through a crystal transformation method. FIG. 9 is an SEM image of an SSZ-39 molecular sieve sample of this comparative example measured to be about 1.5 μm to 2.5 μm in length and about 1.0 μm to 1.6 μm in thickness, having a crystallinity of about 93% and a specific surface area of 655 + -10 m 2 ·g -1 。
Comparative example 3
An SSZ-39 molecular sieve is prepared by the following steps:
s1, fully mixing sodium hydroxide, pure water, silica sol with the concentration of 40wt%, 3, 5-dimethyl-N, N-dimethyl piperidine hydroxide (as an organic template A) aqueous solution with the concentration of 25wt% and a USY molecular sieve to obtain a raw material composition with the following mole ratio: siO 2 2 /Al 2 O 3 =50, organic template A (SDA for short)/SiO 2 ＝0.03、OH-/SiO 2 ＝0.65、H 2 O/SiO 2 =20, aging at room temperature for 3h to give a synthetic gel.
S2, adding the synthesized gel into an autoclave, and controlling a reaction container to stir for 2 hours at room temperature; and finally, raising the temperature in the reaction container to 170 ℃ under the condition of keeping the stirring of the reaction container, and carrying out crystallization treatment for 40 hours.
S3, after the crystallization treatment is finished, taking out products in the reaction container to sequentially carry out when the temperature in the reaction container is reduced to be below 40 ℃: filtering, washing and drying the filtered solid-phase component; and roasting the dried product at 550 ℃ for 4h to obtain a solid after roasting, wherein the solid is detected to be not SSZ-39 zeolite. It can be seen that in the present invention, the SSZ-39 molecular sieve cannot be prepared by using only the organic template A without using the organic template B.
Comparative example 4
The remaining steps are the same as in example 1, except that: organic template agent A (SDA for short)
/SiO 2 =0.06, organic template B/SiO 2 =0.66 preparation of solid. FIG. 10 is an SEM image of an SSZ-39 molecular sieve sample of a comparative example.
The existence of the mixed crystal can be seen from the SEM picture. It is understood that although the organic template A and the organic template B are required to be used in combination in the present invention, the addition amount of the two is strictly limited. The increase of the amount of the template agent does not lead to the increase of the whole reaction rate, but leads to the existence of impurities in the product, and the pure-phase SSZ-39 molecular sieve cannot be prepared.
To characterize the properties of the SSZ-39 molecular sieve prepared in accordance with the present invention, NH was used 3 -SCR reaction performance is a performance test of SSZ-39 molecular sieve, using the following test method:
1) Ammonium exchange of molecular sieve: the SSZ-39 molecular sieves prepared in examples 1-6, the SSZ-39 molecular sieve prepared in comparative example 1, were mixed according to ammonium nitrate: molecular sieve: water (mass ratio) =1:1:10, adjusting pH to 8-8.5 with ammonia water, and stirring at 9Exchanging at 0 ℃ for 1h, filtering, washing, drying and roasting at 550 ℃ for 4h. Repeating the above process for 3 times until Na in the molecular sieve 2 The content of O is less than 0.1 percent.
2) Loading molecular sieve copper: dissolving copper acetate with 5 percent of CuO load equivalent to the molecular sieve in 50 times of water, adding the molecular sieve after ammonium exchange under stirring, adjusting the pH value to 8-8.5 by ammonia water, filtering, washing, drying, and roasting at 550 ℃ for 4 hours.
3) The Cu-SSZ-39 composite molecular sieves prepared in examples 1-6 and comparative example 1, which were subjected to ammonium exchange and Cu loading, were subjected to tablet forming, pulverization, sieving, and sieving at 10% H 2 After hydrothermal aging for 100h at 650 ℃ in an O +90% nitrogen atmosphere, 0.5g of a 40-60 mesh sample is taken and used for NH 3 -SCR reaction, wherein the composition of the reaction mixture is: 1000ppmNO, 1100ppmNH 3 、10Vol％O 2 、10Vol％H 2 O，N 2 As balance gas, the volume space velocity is 120000h -1 And the reaction temperature is 200-600 ℃, and an MKS infrared gas analyzer is used for detecting the concentration of NOx in the tail gas on line. The test results are shown in table 1.
4)NO x The conversion is defined as:
TABLE 1 conversion of nitrogen oxides in reaction mixture at different temperatures (150-350 ℃ C.)
From the data in table 1, it can be seen that:
1. the Cu-SSZ-39 molecular sieve prepared by the invention has DeNOx activity and N in the temperature range of 150-550 DEG C 2 The selectivity is higher than that of the high-cost SSZ-39 molecular sieve prepared by adopting the high-cost template agent at different temperaturesEqual and superior to the molecular sieve prepared in comparative example 1. As is clear from comparison between FIGS. 11 and 12, the products produced in examples 1 to 7 according to the present invention have substantially the same characteristic peaks in XRD, and it can be considered that the products produced in examples 1 to 7 are the same products. The characteristic peaks of XRD of the products prepared in examples 1-7 are similar to those of comparative examples 1-2, which shows that the products prepared in examples 1-7 are the same as those of comparative examples 1-2, while comparative examples 1-2 adopt the existing preparation method for preparing SSZ-39 molecular sieve, and the products are SSZ-39 molecular sieve, so that the following can be obtained: the invention can prepare the pure-phase SSZ-39 molecular sieve with a structure similar to that of the existing high-cost preparation method by using the cheap amine template and the conventional mixed template. The DeNOx activity of the catalyst prepared at the same time is basically similar to that of the existing high-cost SSZ-39 molecular sieve, which indicates that the preparation method can be adopted to reduce the industrial production cost of the SSZ-39 molecular sieve by reducing the cost of the template agent.
2. As can be seen from comparison between comparative example 3 and example 1, the absence of template B can seriously affect the properties of the SSZ-39 molecular sieve prepared by the invention, specifically: SSZ-39 zeolite could not be prepared.
3. As can be seen from comparison of comparative example 4 and example 1, when the organic template A and the organic template B are added in amounts not in accordance with the invention, and especially when the organic template B is too high, the SSZ-39 molecular sieve is generated and even not obtained.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A method for preparing SSZ-39 molecular sieve by using cheap template agent is characterized by comprising the following steps:
s1, preparation of gel:
mixing and stirring a silicon source, an aluminum source, an alkali source, an organic template agent A and water uniformly, and then aging at the temperature of 0-100 ℃ for 0.1-100 hours to obtain a prepared gel; the organic template A comprises: an organic ionic salt and/or an organic ionic base;
s2, crystallization treatment:
firstly, placing prepared gel in a reaction container, adding an organic template agent B, and then aging for 0.1-5h; then controlling the reaction container to stir for 0-3h at room temperature; finally, the temperature in the reaction container is raised to 120-210 ℃ under the condition of keeping the stirring of the reaction container for crystallization treatment for 30-120h, wherein the organic template agent B comprises C 4 -C 16 The fatty amine of (a);
s3, preparing an SSZ-39 molecular sieve:
after the crystallization treatment is finished, when the temperature in the reaction container is reduced to be below 40 ℃, taking out products in the reaction container to carry out the following steps in sequence: filtering, washing the filtered solid phase component, and drying; and then roasting the dried product to obtain the SSZ-39 molecular sieve after roasting is finished.
2. The method for preparing SSZ-39 molecular sieve using cheap template agent according to claim 1, wherein the silicon source in step S1 comprises: at least one of silicon dioxide, silica sol, silicate, orthosilicate ester, solid water glass, liquid water glass and silicon powder.
3. The method for preparing SSZ-39 molecular sieve using cheap templating agent according to claim 1, wherein the aluminum source of step S1 comprises: at least one of USY molecular sieve, ZSM-5 molecular sieve, beta molecular sieve, sodium metaaluminate, aluminum hydroxide, pseudoboehmite, aluminum isopropoxide, aluminum sol and boehmite.
4. The method of claim 1, wherein the alkali source of step S1 comprises: one or a mixture of two of sodium hydroxide and potassium hydroxide.
5. The method for preparing SSZ-39 molecular sieve by using cheap template agent according to claim 1, wherein in the organic template agent A in step S1, the organic ions comprise: n, N-diethyl-2, 6-dimethylpiperidinium ion, 3, 5-dimethyl-N, N-dimethylpiperidinium ion, N-diethyl-2-ethylpiperidinium ion, N-ethyl-N-propyl-2, 6-dimethylpiperidinium ion, N-methyl-N-ethyl-2-ethylpiperidinium ion, 2, 5-dimethyl-N, at least one of N-diethylpyrrole ion, 2, 6-dimethyl-N, N-dimethylpiperidine ion, 2-ethyl-N, N-dimethylpiperidine ion, 2, 6-tetramethyl-N-methyl-N-ethylpiperidine ion, and 2, 6-tetramethyl-N, N-dimethylpiperidine ion.
6. The method of claim 5, wherein the organic ion is selected from the group consisting of: 3, 5-dimethyl-N, N-dimethylhydroxypiperidine.
7. The method of claim 1, wherein the molar ratio of the silicon source, the aluminum source, the alkali source, the organic template A, the organic template B and the water satisfies the following condition: si: al =2.5-90: si =0-1 2 O: si =3-80: si =0-0.1: 1. rb: si =0-0.5: 1. ra: rb =0-1, wherein Ra is the number of moles of organic templating agent a and Rb is the number of moles of organic templating agent B.
8. The method for preparing SSZ-39 molecular sieve using cheap template agent according to claim 1, wherein the organic template agent B in step S2 comprises: at least one of n-butylamine, diisopropylethylamine, tri-n-propylamine, di-n-butylamine, triethylamine, diethylamine, dodecylamine, octadecylamine, cyclohexylamine and hexylamine.
9. The method for preparing SSZ-39 molecular sieve using cheap template agent according to claim 1, characterized in that the stirring time of the reaction vessel at room temperature in step S2 is controlled as follows: 0.5-1h; the crystallization treatment time is as follows: 50-100h.
10. An SSZ-39 molecular sieve, which is prepared by the method for preparing the SSZ-39 molecular sieve by using the cheap template agent according to any one of claims 1 to 9; the particle size of the SSZ-39 molecular sieve is as follows: 0.1-10 μm, and crystallinity higher than 90%.
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