CN112723369B - Preparation method of SUZ-4 molecular sieve - Google Patents
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 65
- 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 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 35
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound 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 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 60
- 238000002425 crystallisation Methods 0.000 claims description 24
- 230000008025 crystallization Effects 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 11
- 229910001868 water Inorganic materials 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 7
- 239000006229 carbon black Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 230000003068 static effect Effects 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 13
- 239000013078 crystal Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 239000012808 vapor phase Substances 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/005—Silicates, i.e. so-called metallosilicalites or metallozeosilites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a preparation method of an SUZ-4 type molecular sieve, which comprises the following steps: mixing an aluminum source, a silicon source, an alkali source, deionized water and the HZSM-5 type molecular sieve, and crystallizing, filtering and drying the mixture to obtain the SUZ-4 type molecular sieve. The method does not need to adopt a template agent, has low preparation cost and is suitable for industrial application.
Description
Technical Field
The invention belongs to the field of molecular sieve synthesis, and particularly relates to a preparation method of an SUZ-4 molecular sieve.
Background
The SUZ-4 molecular sieve has similar pore channel structure to ZSM-5 and FER molecular sieves, and the three-dimensional pore channel mainly consists of four, five, six, eight and ten membered rings, and comprises a pore channel which consists of eight membered rings and is parallel to the XY plane and a pore opening which consists of ten membered rings and is parallel to the XY planezTwo types of cross-shaped channels of the straight channels of the shaft. The SUZ-4 molecular sieve is applied to a plurality of catalytic fields of n-butene isomerization, selective catalytic reduction of nitrogen oxides and the like, and has potential industrial application prospects.
Currently, the reported conventional method for synthesizing SUZ-4 requires dynamic crystallization at a relatively high temperature (typically 150-180 ℃) in which a large amount of an expensive organic template is added for about 4-7 days. This makes the SUZ-4 molecular sieve impossible to be produced in large scale, and limits the application prospect of the molecular sieve. Meanwhile, the use of a large amount of organic template agent causes environmental pollution, and green and environment-friendly production cannot be achieved.
A method for preparing SUZ-molecular sieve without template is disclosed in the Journal of Chinese Journal of Chemical Engineering, 22 (1) 120-126 (2014) of Zhou Hualan et al, but the crystallization time is longer. The preparation process of a SUZ-4 molecular sieve membrane is published in Lei ya Meng et al, liaoning university of engineering technology, journal of science, vol.38, no. 2, and is successfully applied to the process of pervaporation ethyl acetate dehydration reaction, but the preparation process is complex and is not beneficial to large-scale production. Jianshan et al published a paper in university of maritime university, university of Dalian province 33, no. 4, to study the influence of the framework dealumination process of the SUZ-4 molecular sieve on the catalytic performance, and found that the acid center on the surface of the SUZ-4 molecular sieve is mainly the B acid center.
CN102241407 discloses a method for synthesizing the molecular sieve by SUZ-4 seed crystal glue, which greatly reduces the dosage of an organic template agent and shortens the synthesis time, but the molecular sieve needs to be synthesized under dynamic conditions. CN107285340 discloses a preparation method for obtaining SUZ-4 zeolite by using mother liquor. The method is characterized in that the mother liquor is evaporated to dryness to obtain dry glue, and the dry glue on the upper part of a reaction kettle is converted into the zeolite molecular sieve through mass transfer of a vapor phase, so that the preparation process of the method is complex. CN102249257 discloses a method for obtaining SUZ-4 molecular sieve by circulating and crystallizing mother liquor, and the crystallization time in the synthesis process is greatly shortened, and the SUZ-4 molecular sieve of template agent is reduced or not used.
At present, most of synthesis methods of the SUZ-4 molecular sieve are further synthesized by using an expensive and environmentally-friendly organic template and seed crystals or seed gels generated in the synthesis process of the SUZ-4 molecular sieve, and no relevant report about the synthesis of the SUZ-4 molecular sieve by using secondary structural units in heterogeneous seed crystals exists.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of SUZ-4. The method does not need to adopt a template agent, has low preparation cost and is suitable for industrial application.
The invention relates to a preparation method of an SUZ-4 type molecular sieve, which comprises the following steps: mixing an aluminum source, a silicon source, an alkali source, deionized water and the HZSM-5 type molecular sieve, and crystallizing, filtering and drying the mixture to obtain the SUZ-4 type molecular sieve.
In the method of the invention, the silicon source can be silica sol, water glass and white carbon black (SiO) 2 ) Silica, preferably silica sol, white carbon black; the aluminum source can be a mixture of one or more of aluminum metal sheets, aluminum oxide, aluminum hydroxide, pseudo-boehmite and aluminate, preferably aluminum metal sheets and aluminum oxide; the describedThe alkali source is at least potassium hydroxide, preferably KOH.
In the method, an aluminum source, a silicon source, an alkali source, deionized water and an HZSM-5 type molecular sieve are preferably mixed and stirred according to a certain proportion to be in a uniform state, the mixture is crystallized for 1 to 7 days at the temperature of between 100 and 200 ℃ under a sealed condition, the mixture obtained after crystallization is filtered, and the obtained white solid is washed and dried to obtain the SUZ-4 molecular sieve.
In the method, the feeding sequence in the synthesis process is as follows: weighing a proper amount of alkali source to dissolve in water, adding an aluminum source to dissolve, weighing a proper amount of HZSM-5 type molecular sieve to put into the mixed solution for stirring, adding a silicon source after uniformly stirring, stirring for 1-2 hours, and then crystallizing.
In the method, when the crystallization temperature is lower, the corresponding crystallization time is longer; on the contrary, when the crystallization temperature is higher, the crystallization time corresponding thereto is shorter. The optimal crystallization temperature and crystallization time are 140-180 ℃ and 2-4 days respectively.
In the method of the invention, the aluminum source is Al 2 O 3 The silicon source is SiO 2 Calculated as H, deionized water 2 Calculated by O, the alkali source is calculated by potassium hydroxide, and the molar ratio of the raw materials is SiO 2 ：Al 2 O 3 ：KOH：H 2 O =5 to 65, 2.4 to 5; the preferable molar ratio of the raw materials is as follows: siO 2 2 ：Al 2 O 3 ：KOH：H 2 O=15~30:0.8~1.8:4.0~14.0:400~900。
In the method, the crystallization process can be dynamic crystallization or static crystallization, the crystallization time of the static crystallization is longer, and the dynamic crystallization is preferably used as a crystallization mode.
In the method, the addition amount of the HZSM-5 type molecular sieve is 1-25% of the total mass of a mixed material system for synthesizing the SUZ-4 molecular sieve, and preferably 5-10%.
The method adopts the conventional ZSM-5 type molecular sieve as the seed crystal to prepare the SUZ-4 molecular sieve under the condition of not adding a template agent. The channel structure of the SUZ-4 molecular sieve is very similar to that of the ZSM-5 molecular sieve, the three-dimensional channel structure of the SUZ-4 is composed of four, five, six, eight and ten membered rings, and the ZSM-5 molecular sieve is a topological structure composed of the four, five, six and ten membered rings.The three-dimensional pore channel structure of the SUZ-4 molecular sieve comprises two mutually crossed pore channels, wherein one pore channel is a pore channel which is composed of eight-membered rings and is parallel to an XY plane; the other is a straight channel parallel to the z-axis, the orifice consisting of ten-membered rings. Unlike the structure of SUZ-4 molecular sieve, both openings of ZSM-5 molecular sieve are ten-membered rings, and the straight pore parallel to the z-axis is slightly larger than SUZ-4. The ZSM-5 molecular sieve is used as a seed crystal to be dissolved into a secondary structural unit with a metastable state consisting of four, five and six-membered rings in a synthesis system of the SUZ-4 molecular sieve, and the secondary structural unit is rearranged and combined according to the growth process of the SUZ-4 molecular sieve to prepare the SUZ-4 molecular sieve. The secondary structural unit in the metastable state plays a guiding role in the synthesis process of the SUZ-4 molecular sieve, and accelerates the synthesis process of the SUZ-4 molecular sieve. In the synthesis process of SUZ-4 molecular sieve, na + The presence of (a) may cause the formation of a competitive MOR phase in the system, and therefore the H-type ZSM-5 molecular sieve is used as seed in the preparation process. The SUZ-4 molecular sieve prepared by the method has short crystallization time, does not adopt a template agent, reduces the preparation cost and reduces the environmental pollution.
Compared with the prior art, the method provides a novel preparation method for the synthesis process of the SUZ-4 molecular sieve, and also provides a basis for the generation of secondary structure units of the heterogeneous seed crystals in the synthesis process of the zeolite and the guiding effect. The method does not use an organic template agent for preparing the SUZ-4 molecular sieve conventionally, and the used heterogeneous seed crystal HZSM-5 type molecular sieve has mature synthesis technology and lower purchase cost, thereby greatly reducing the preparation cost.
Drawings
FIG. 1 is an XRD diffractogram of the product synthesized in example 1 of the present invention.
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of a synthesized product of example 3 of the present invention.
FIG. 3 is an XRD diffraction pattern of a synthesized product of comparative example 1 of the present invention.
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but it should be noted that the scope of the present invention is not limited by the embodiments.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.
When the specification concludes with claims with the heading "known to those skilled in the art", "prior art", or the like, deriving materials, substances, methods, steps, etc., the subject matter that is derived from the heading encompasses those conventionally used in the art as proposed in the present application, but also includes those that are not currently in use, but would become known in the art to be suitable for a similar purpose.
The X-ray diffraction pattern in the embodiment is measured by an X' Pert Powder X-ray diffractometer in the Paronaceae, the Netherlands. The operating conditions were: cuK alpha target, tube current of 40 mA, tube voltage of 40 kV, and scanning range of 3-80 o At a scanning speed of 5 o /min。
Scanning Electron microscopy in this example was carried out on a QUNATA200 FEG field emission electron scanning electron microscope, manufactured by KANTA, USA. Fixing the sample on a copper table by conductive adhesive, and using N 2 And blowing and performing evacuation measurement.
Example 1
Aluminum sheet, potassium hydroxide, silica sol (26.5% SiO) 2 ) SiO and water according to a molar ratio 2 ：Al 2 O 3 ：KOH：H 2 O =16.5, 1. The reaction kettle is taken out and then is rapidly cooled to room temperature by cold water, and the obtained mixture is filtered and separated. And drying the obtained solid sample at 110 ℃ for 24 hours to obtain the SUZ-4 molecular sieve which does not contain mixed crystals and has relative crystallinity of 96%.
Example 2
Example 1 was repeated, but with white carbon black as the silicon source and with a reduced amount of deionized water. In this example, aluminum flake, potassium hydroxide, silica sol and water were mixed in a molar ratio of SiO 2 ：Al 2 O 3 ：KOH：H 2 O=275.5. Taking out the reaction kettle, rapidly cooling to room temperature with cold water, filtering and separating the obtained mixture, and drying at 110 ℃ for 24 hours to obtain the solid SUZ-4 molecular sieve which does not contain mixed crystals and has relative crystallinity of 98%.
Example 3
Example 1 was repeated, but using alumina as the aluminium source, alumina, potassium hydroxide, silica sol (26.5% SiO) 2 ) SiO and water according to a molar ratio 2 ：Al 2 O 3 ：KOH：H 2 O =18.8, 1.8, i.e., 1.5, 500.0, in a beaker, the amount of the HZSM-5 type molecular sieve added is 14% of the total mass of the initial gel mixture for synthesizing the SUZ-4 molecular sieve, the mixture is stirred for 2 hours, the solution is in a uniform state, and after the solution is placed in a reaction kettle, the mixture is dynamically crystallized at 160 ℃ for 3 days (the rotation speed is 20 r/min), so that the SUZ-4 molecular sieve free of the mixed crystals is obtained, and the relative crystallinity is 96%.
Example 4
Example 1 was repeated, but using silica as the silicon source and alumina as the aluminum source. In this example, alumina, potassium hydroxide, silica and water are in molar ratio SiO 2 ：Al 2 O 3 ：KOH：H 2 Adding O = 20.0.
Example 5
Aluminum sheet, potassium hydroxide, white carbon black and water are mixed according to the mol ratio SiO 2 ：Al 2 O 3 ：KOH：H 2 O =20.6And (4) crystallizing for 7 days to obtain the SUZ-4 molecular sieve without mixed crystals, wherein the relative crystallinity is 86%.
Comparative example 1
Example 1 was repeated, but dynamic crystallization was carried out for 7 days without adding HZSM-5 type molecular sieve. The resulting product was amorphous.
Comparative example 2
Example 1 was repeated, 12.68g of template tetraethylammonium hydroxide was added instead of the HZSM-5 type molecular sieve, dynamic crystallization was carried out for 4 days, and the obtained product was the SUZ-4 molecular sieve, containing no mixed crystals, and having a crystallinity of 98%.
Comparative example 3
Example 1 was repeated to change potassium hydroxide to sodium hydroxide, aluminum flake, sodium hydroxide, white carbon black and water to SiO in molar ratio 2 ：Al 2 O 3 ：NaOH：H 2 O = 21.2.
Claims (4)
1. A preparation method of SUZ-4 type molecular sieve is characterized by comprising the following steps: weighing a proper amount of alkali source, dissolving in water, adding an aluminum source for dissolving, weighing an HZSM-5 type molecular sieve, putting the HZSM-5 type molecular sieve into the mixed solution, stirring, adding a silicon source after stirring uniformly, stirring for 1-2 hours, crystallizing for 2-4 days at 140-180 ℃ under a sealed condition, filtering the obtained mixture after crystallization, washing and drying the obtained white solid to obtain the SUZ-4 molecular sieve, wherein the aluminum source is Al 2 O 3 The silicon source is SiO 2 Calculated as H, deionized water 2 Calculated by O, the alkali source is calculated by potassium hydroxide, and the molar ratio of the raw materials is SiO 2 ：Al 2 O 3 ：KOH：H 2 O = 15-30, 0.8-1.8.
2. The method of claim 1, wherein: the silicon source is one or more of silica sol, water glass, white carbon black and silicon dioxide; the aluminum source is one or more of aluminum sheet, aluminum oxide, aluminum hydroxide, pseudo-boehmite and aluminate; the alkali source is at least potassium hydroxide.
3. The method of claim 2, wherein: the silicon source is silica sol; the aluminum source is a metal aluminum sheet or aluminum oxide; the alkali source is KOH.
4. The method of claim 1, wherein: the crystallization process is dynamic crystallization or static crystallization.
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| CN102241407A (en) * | 2011-04-29 | 2011-11-16 | 大连理工大学 | Preparation method of SUZ-4 molecular sieve |
| CN104370295A (en) * | 2013-08-14 | 2015-02-25 | 中国科学院大连化学物理研究所 | ZSM-35 molecular sieve and Me-ZSM-35 synthesis methods |
| CN107285340A (en) * | 2017-08-02 | 2017-10-24 | 南京大学连云港高新技术研究院 | A kind of preparation method of the zeolite molecular sieves of SUZ 4 |
| CN108408735A (en) * | 2018-05-21 | 2018-08-17 | 太原理工大学 | A method of preparing SUZ-4 molecular sieves using silicon ash |
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| US9404045B2 (en) * | 2011-02-17 | 2016-08-02 | AMG Chemistry and Catalysis Consulting, LLC | Alloyed zeolite catalyst component, method for making and catalytic application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102241407A (en) * | 2011-04-29 | 2011-11-16 | 大连理工大学 | Preparation method of SUZ-4 molecular sieve |
| CN104370295A (en) * | 2013-08-14 | 2015-02-25 | 中国科学院大连化学物理研究所 | ZSM-35 molecular sieve and Me-ZSM-35 synthesis methods |
| CN107285340A (en) * | 2017-08-02 | 2017-10-24 | 南京大学连云港高新技术研究院 | A kind of preparation method of the zeolite molecular sieves of SUZ 4 |
| CN108408735A (en) * | 2018-05-21 | 2018-08-17 | 太原理工大学 | A method of preparing SUZ-4 molecular sieves using silicon ash |
Non-Patent Citations (1)
| Title |
|---|
| Organotemplate-free Hydrothermal Synthesis of SUZ-4 Zeolite: Influence of Synthesis Conditions;Zhou Hualan et al.;《Chinese Journal of Chemical Engineering》;20140131;第22卷(第1期);第121页左栏第1段 * |
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Effective date of registration: 20231109 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |