RU2725586C1 - Method of producing a composite based on microporous zeolite and silicon carbide - Google Patents
Method of producing a composite based on microporous zeolite and silicon carbide Download PDFInfo
- Publication number
- RU2725586C1 RU2725586C1 RU2020108036A RU2020108036A RU2725586C1 RU 2725586 C1 RU2725586 C1 RU 2725586C1 RU 2020108036 A RU2020108036 A RU 2020108036A RU 2020108036 A RU2020108036 A RU 2020108036A RU 2725586 C1 RU2725586 C1 RU 2725586C1
- Authority
- RU
- Russia
- Prior art keywords
- silicon carbide
- composite
- water
- product
- tetrapropylammonium hydroxide
- Prior art date
Links
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 239000010457 zeolite Substances 0.000 title claims abstract description 21
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 18
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 15
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002425 crystallisation Methods 0.000 claims abstract description 12
- 230000005855 radiation Effects 0.000 claims abstract description 12
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000000047 product Substances 0.000 claims abstract description 10
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- 239000000725 suspension Substances 0.000 claims abstract description 5
- 230000008025 crystallization Effects 0.000 claims description 9
- JJWLVOIRVHMVIS-UHFFFAOYSA-O isopropylaminium Chemical compound CC(C)[NH3+] JJWLVOIRVHMVIS-UHFFFAOYSA-O 0.000 claims 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 17
- 239000013078 crystal Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 3
- 238000005341 cation exchange Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000002808 molecular sieve Substances 0.000 abstract description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 230000008030 elimination Effects 0.000 abstract 1
- 238000003379 elimination reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000011148 porous material Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- -1 aluminum compound Chemical class 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000034655 secondary growth Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3234—Inorganic material layers
- B01J20/3238—Inorganic material layers containing any type of zeolite
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
-
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- 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
-
- 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
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
- C01B33/28—Base exchange silicates, e.g. zeolites
- C01B33/2807—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures
- C01B33/2869—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures of other types characterised by an X-ray spectrum and a definite composition
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
- C01B33/28—Base exchange silicates, e.g. zeolites
- C01B33/2807—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures
- C01B33/2876—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures from a reacting mixture containing an amine or an organic cation, e.g. a quaternary onium cation-ammonium, phosphonium, stibonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
- C01B33/28—Base exchange silicates, e.g. zeolites
- C01B33/2807—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures
- C01B33/2884—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures the aluminium or the silicon in the network being partly replaced
-
- 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
-
- 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
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Изобретение относится к области неорганической химии и химической технологии, а именно, к способам получения соединений со свойствами молекулярных сит, которые имеют катион-обменные свойства - микро-мезо-макропористым материалам, содержащим в своей структуре кристаллические фазы микропористого цеолита (в частности, структуры MFI) и мезо-макропористого карбида кремния (SiC).The invention relates to the field of inorganic chemistry and chemical technology, and in particular, to methods for producing compounds with molecular sieve properties that have cation-exchange properties — micro-meso-macroporous materials containing crystalline phases of microporous zeolite in their structure (in particular, MFI structures ) and meso-macroporous silicon carbide (SiC).
Цеолиты MFI находят широкое применение в различных процессах гетерогенного катализа. Однако вследствие того, что размер пор в структуре цеолита MFI не превышает 0,5-0,6 нм (микропоры), существует проблема диффузионного ограничения при проведении каталитических процессов, что обуславливает, в частности, быструю дезактивацию катализатора при закупорке пор углеродистыми отложениями (закоксовывание катализатора). Одним из решений данной проблемы может служить синтез и использование в катализе материалов, содержащих наряду с микропорами, и поры с большим размером (от 2 до 50 нм - мезопоры или более 50 нм - макропоры). Одним из таких материалов является композит на основе микропористого цеолита и мезо-макропористого карбида кремния - MFI/SiC. Большинство известных способовполучения данного материала представляют собой процедуру кристаллизации цеолита MFI на карбиде кремния SiC. Кроме этого, указанные способы получения данного композита позволяют получать композит в натриевой форме. В результате чего в ряде случаев необходимо переводить синтезированный композит в водородную форму путем ионного обмена, что является затратной по времени стадией.MFI zeolites are widely used in various heterogeneous catalysis processes. However, due to the fact that the pore size in the structure of the MFI zeolite does not exceed 0.5-0.6 nm (micropores), there is a problem of diffusion limitation during catalytic processes, which leads, in particular, to rapid deactivation of the catalyst during blockage of pores with carbon deposits (coking catalyst). One of the solutions to this problem can be the synthesis and use in catalysis of materials containing, along with micropores, pores with a large size (from 2 to 50 nm - mesopores or more than 50 nm - macropores). One such material is a composite based on microporous zeolite and meso-macroporous silicon carbide - MFI / SiC. Most of the known methods for the preparation of this material are the crystallization of MFI zeolite on silicon carbide SiC. In addition, these methods of obtaining this composite allow to obtain a composite in sodium form. As a result, in some cases it is necessary to convert the synthesized composite into the hydrogen form by ion exchange, which is a time-consuming stage.
Известен способ получения композита на основе цеолита и карбида кремния, в частности, ZSM-5/SiC (US 7179764, 2007), в котором наращивают кристаллы различных цеолитов на карбиде кремния. Для этого гидроксид тетра-н-пропиламмония и тетраэтилортосиликат растворяют в дистиллированной воде. Отдельно растворяют нонагидрат нитрата алюминия в дистиллированной воде. Затем раствор, содержащий соединение алюминия, добавляют к первому раствору и перемешивают 50 минут. После чего добавляют карбид кремния, который предварительно был прокален при 900°С в течение двух часов. Эту смесь заливают в автоклав, который помещают в печь и проводят кристаллизацию при 150°С в течение 7 часов. После синтеза материал промывают дистиллированной водой, сушат в печи при 100°С и прокаливают при 550°С в течение 10 часов для удаления темплата. Далее проводят обработку композита водным раствором хлорида аммония в течение 16 часов. После чего композит ZSM-5/SiC промывают дистиллированной водой, сушат и прокаливают при 550°С в течение 10 часов для получения водородной формы.A known method of producing a composite based on zeolite and silicon carbide, in particular, ZSM-5 / SiC (US 7179764, 2007), in which crystals of various zeolites are grown on silicon carbide. For this, tetra-n-propylammonium hydroxide and tetraethylorthosilicate are dissolved in distilled water. Separately dissolve the aluminum nitrate nonahydrate in distilled water. Then, the solution containing the aluminum compound is added to the first solution and stirred for 50 minutes. Then add silicon carbide, which was previously calcined at 900 ° C for two hours. This mixture is poured into an autoclave, which is placed in an oven and crystallized at 150 ° C. for 7 hours. After synthesis, the material is washed with distilled water, dried in an oven at 100 ° C and calcined at 550 ° C for 10 hours to remove the template. Next, the composite is treated with an aqueous solution of ammonium chloride for 16 hours. Then the ZSM-5 / SiC composite is washed with distilled water, dried and calcined at 550 ° C for 10 hours to obtain a hydrogen form.
Недостатком указанного способа являются продолжительная по времени стадия перевода композита в водородную форму, которая включают в себя длительный ионный обмен с раствором хлорида аммония и последующее прокаливание. Кроме этого, синтезную смесь готовят путем приготовления двух отдельных растворов, что, в свою очередь, увеличивает трудоемкость и продолжительность синтеза.The disadvantage of this method is the time-consuming step of converting the composite into a hydrogen form, which includes a prolonged ion exchange with a solution of ammonium chloride and subsequent calcination. In addition, the synthesis mixture is prepared by preparing two separate solutions, which, in turn, increases the complexity and duration of the synthesis.
Наиболее близким к изобретению является способ получения композита на основе микропористого цеолита MFI и карбида кремния с использованием микроволнового излучения, где на карбиде кремния SiC наращивают цеолит MFI. (Xiaoxia Ou, Shaojun Xu, Jason M. Warnett, Stuart M. Holmes, Amber Zaheer, Arthur A. Garforth, Mark A. Williams, Yilai Jiao, Xiaolei Fan. Creating hierarchies promptly: Microwave-accelerated synthesis of ZSM-5 zeolites on macrocellular silicon carbide (SiC) foams. // Chemical Engineering Journal. - 2017. - V. 312. - P. 1-9). При этом вначале проводят синтез затравочных кристаллов цеолита MFI в 2 стадии. Стадию зародышеобразования проводят вначале при 80°С, затем при 120°С при мощности 150 Вт. Общее время зародышеобразования составляет 3 часа. В результате получают зародыши силикалита размером 50-100 нм. Карбид кремния перед синтезом прокаливают при 900°С в течение 4 часов. Композит ZSM-5 на карбиде кремния получают гидротермальным и гидротермально-микроволновым методами. Синтезную смесь готовят при мольном соотношении компонентов: тетраэтилортосиликат: хлорид натрия: гидроксид тетра-н-пропиламмония: алюминат натрия: вода, равным 1:0,22:0,19:0,023:178 и подвергают старению при комнатной температуре в течение 24 часов. Карбид кремния смешивают с затравочными кристаллами силикалита в растворе этанола и сушат в печи при 160°С. Смесь карбида кремния с затравочными кристаллами вводят в полученную после старения синтезную смесь, содержащую тетраэтилортосиликат, хлорид натрия, гидроксид тетра-н-пропиламмония, алюминат натрия и воду, и заливают в автоклав для вторичного роста цеолита ZSM-5 из затравочных кристаллов силикалита. Гидротермальный синтез проводят в автоклаве объемом 50 мл (заливают описанную выше смесь объемом 25 мл), который помещают в печь и выдерживают при 150°С, в течение различного времени для роста кристаллов цеолита ZSM-5. Гидротермально-микроволновой синтез проводят в микроволновой установке СЕМ Discover SP-D, частота излучения 2,45 Ггц (в автоклавы объемом 35 мл загружают описанную выше смесь объемом 20 мл). Синтез ведут при мощности излучения 150 Вт, температуре 110-160°С, в течение 1-6 часов. После синтеза материал промывают дистиллированной водой в ультразвуковой бане в течение 15 минут, сушат в печи при 100°С и прокаливают при 550°С в течение 4 часов (нагрев от комнатной температуры до 550°С со скоростью 1°С/мин) для удаления темплата. В результате получают ZSM-5/SiC в Na-форме.Closest to the invention is a method of producing a composite based on microporous zeolite MFI and silicon carbide using microwave radiation, where MFI zeolite is grown on silicon carbide SiC. (Xiaoxia Ou, Shaojun Xu, Jason M. Warnett, Stuart M. Holmes, Amber Zaheer, Arthur A. Garforth, Mark A. Williams, Yilai Jiao, Xiaolei Fan. Creating hierarchies promptly: Microwave-accelerated synthesis of ZSM-5 zeolites on macrocellular silicon carbide (SiC) foams. // Chemical Engineering Journal. - 2017 .-- V. 312. - P. 1-9). In this case, first, the synthesis of seed crystals of MFI zeolite in 2 stages is carried out. The nucleation stage is carried out first at 80 ° C, then at 120 ° C at a power of 150 watts. The total nucleation time is 3 hours. The result is a silicalite nucleus with a size of 50-100 nm. Silicon carbide is baked before synthesis at 900 ° C for 4 hours. ZSM-5 composite on silicon carbide is prepared by hydrothermal and hydrothermal-microwave methods. The synthesis mixture is prepared at a molar ratio of components: tetraethylorthosilicate: sodium chloride: tetra-n-propylammonium hydroxide: sodium aluminate: water, equal to 1: 0.22: 0.19: 0.023: 178 and subjected to aging at room temperature for 24 hours. Silicon carbide is mixed with seed crystals of silicalite in an ethanol solution and dried in an oven at 160 ° C. A mixture of silicon carbide with seed crystals is introduced into the synthesis mixture obtained after aging, containing tetraethylorthosilicate, sodium chloride, tetra-n-propylammonium hydroxide, sodium aluminate and water, and poured into an autoclave for secondary growth of ZSM-5 zeolite from seed crystals of silicalite. Hydrothermal synthesis is carried out in a 50 ml autoclave (pour the above mixture with a volume of 25 ml), which is placed in an oven and incubated at 150 ° C for various times for the growth of ZSM-5 zeolite crystals. Hydrothermal-microwave synthesis is carried out in a CEM Discover SP-D microwave unit, the radiation frequency is 2.45 GHz (the above mixture with a volume of 20 ml is loaded into 35 ml autoclaves). The synthesis is carried out at a radiation power of 150 W, a temperature of 110-160 ° C, for 1-6 hours. After synthesis, the material is washed with distilled water in an ultrasonic bath for 15 minutes, dried in an oven at 100 ° C and calcined at 550 ° C for 4 hours (heating from room temperature to 550 ° C at a rate of 1 ° C / min) to remove template. The result is ZSM-5 / SiC in the Na form.
Недостатками данного способа являются длительное время и сложность стадии кристаллизации реакционной смеси, которую проводят, используя синтезированные отдельно затравочные кристаллы. Кроме того, приведенные в источнике рентгенограммы показывают, что, несмотря на длительное время кристаллизации, не удается добиться достижения высокой степени кристалличности цеолита, о чем свидетельствует отсутствие характеристических пиков в интервале 8-9°угла 2G. При этом, для использования описываемого в источнике композита ZSM-5/SiC в каталитических процессах, последний необходимо перевести в водородную форму, что приводит к дополнительному увеличению времени синтеза. При этом в качестве побочного продукта образуется раствор, содержащий ионы натрия, что приводит к необходимости его утилизации.The disadvantages of this method are the long time and complexity of the stage of crystallization of the reaction mixture, which is carried out using separately synthesized seed crystals. In addition, the X-ray patterns shown in the source show that, despite the long crystallization time, it is not possible to achieve a high degree of crystallinity of the zeolite, as evidenced by the absence of characteristic peaks in the range of 8–9 ° of the 2G angle. Moreover, in order to use the ZSM-5 / SiC composite described in the source in catalytic processes, the latter must be converted to the hydrogen form, which leads to an additional increase in the synthesis time. At the same time, a solution containing sodium ions is formed as a by-product, which leads to the need for its disposal.
Таким образом, данный способ недостаточно эффективен.Thus, this method is not effective enough.
Проблемой настоящего изобретения является повышение эффективности способа получения композита на основе микропористого цеолита и карбида кремния, а именно, упрощение технологии способа, сокращение времени синтеза, исключение необходимости утилизации побочных продуктов.The problem of the present invention is to increase the efficiency of the method for producing a composite based on microporous zeolite and silicon carbide, namely, simplifying the technology of the method, reducing the synthesis time, eliminating the need for disposal of by-products.
Указанная проблема решается описываемым способом получения композита на основе микропористого цеолита и карбида кремния, заключающимся в том, что готовят смесь, состоящую из тетраэтилортосиликата, воды, 1 М раствора гидроксида тетрапропиламмония, изопропоксида алюминия и карбида кремния в мольном соотношении тетраэтилортосиликат: вода: гидроксид тетрапропиламмония: изопропоксид алюминия: карбид кремния, равном 1: 35-39: 0,11-0,16: 0,013-0,015: 0,5-0,7, соответственно, полученную суспензию подвергают кристаллизации под воздействием микроволнового излучения при температуре 190-200°С, в течение 180-210 минут, с образованием продукта кристаллизации, после чего отделяют от продукта кристаллизации осадок, который промывают, сушат и прокаливают с получением целевого продукта.This problem is solved by the described method for producing a composite based on microporous zeolite and silicon carbide, which consists in preparing a mixture consisting of tetraethylorthosilicate, water, 1 M solution of tetrapropylammonium hydroxide, aluminum isopropoxide and silicon carbide in a molar ratio of tetraethylorthosilicate: water: hydroxy: aluminum isopropoxide: silicon carbide equal to 1: 35-39: 0.11-0.16: 0.013-0.015: 0.5-0.7, respectively, the resulting suspension is subjected to crystallization under the influence of microwave radiation at a temperature of 190-200 ° C , for 180-210 minutes, with the formation of the crystallization product, after which the precipitate is separated from the crystallization product, which is washed, dried and calcined to obtain the target product.
Достигаемый технический результат заключается в обеспечении получения композита непосредственно в водородной форме при одновременном исключении наличия в указанном композите ионов натрия, а также исключения использования затравочных кристаллов в ходе синтеза.Achievable technical result consists in providing the composite directly in hydrogen form while eliminating the presence of sodium ions in the composite, as well as eliminating the use of seed crystals during synthesis.
Сущность изобретения заключается в следующем.The invention consists in the following.
Готовят смесь, состоящую из тетраэтилортосиликата, воды, 1 М раствора гидроксида тетрапропиламмония, изопропоксида алюминия и карбида кремния, взятых в вышеоговоренном соотношении. Полученную суспензию помещают в герметичную емкость (автоклав) из инертного материала, например, в тефлоновый автоклав, выдерживающий максимально возможное давление 3,7 Мпа с целью поддержания герметичности автоклава на протяжении всего времени синтеза и подвергают кристаллизации под воздействием микроволнового излучения при температуре 190-200°С, в течение 180-210 минут. Мощность микроволнового излучения составляет 900 Вт, частота излучения 2,45 Ггц. Образовавшийся твердый осадок отделяют центрифугированием.A mixture is prepared consisting of tetraethylorthosilicate, water, 1 M solution of tetrapropylammonium hydroxide, aluminum isopropoxide and silicon carbide, taken in the above ratio. The resulting suspension is placed in a sealed container (autoclave) of inert material, for example, in a Teflon autoclave, which can withstand the maximum possible pressure of 3.7 MPa in order to maintain the integrity of the autoclave throughout the synthesis time and is crystallized by microwave radiation at a temperature of 190-200 ° C, for 180-210 minutes. The microwave radiation power is 900 W, the radiation frequency is 2.45 GHz. The solid precipitate formed is separated by centrifugation.
Полученный осадок промывают водой, сушат при температуре 180-200°С, в течение 1,5-2,0 ч. и прокаливают при температуре 500-600°С с получением целевого продукта.The resulting precipitate is washed with water, dried at a temperature of 180-200 ° C, for 1.5-2.0 hours and calcined at a temperature of 500-600 ° C to obtain the target product.
Ниже приведены примеры, иллюстрирующие изобретение, но не ограничивающие его. Описываемый способ иллюстрируют на примере получения композита на основе микропористого цеолита и макропористого карбида кремния - MFI/SiC.The following are examples illustrating the invention, but not limiting it. The described method is illustrated by the example of obtaining a composite based on microporous zeolite and macroporous silicon carbide - MFI / SiC.
Пример 1.Example 1
Приготовление смеси. В плоскодонную колбу с магнитной мешалкой заливают 59 мл дистиллированной воды. Затем в нее при перемешивании добавляют 0,25 г изопропоксида алюминия, 11,3 мл 20% водного раствора гидроксида тетрапропиламмония, медленно - 19,8 мл тетраэтилортосиликата и 2 г карбида кремния. Мольное соотношение компонентов в смеси тетраэтилортосиликат: вода: гидроксид тетрапропиламмония: изопропоксид алюминия: карбид кремния составляет 1:37,1:0,127:0,014:0,562. Перемешивание проводят до получения однородной смеси. Затем данную смесь помещают в тефлоновый автоклав с заданным предельным давлением 3,7 МПа и в микроволновой установке SpeedWave Berghof - 4 (мощность микроволнового излучения составляет 900 Вт, частота излучения 2,45 Ггц) подвергают воздействию микроволнового излучения, обеспечивающего температуру реакционной массы 200°С, в течение 210 минут.Preparation of the mixture. 59 ml of distilled water are poured into a flat-bottomed flask with a magnetic stirrer. Then, 0.25 g of aluminum isopropoxide, 11.3 ml of a 20% aqueous solution of tetrapropylammonium hydroxide, slowly added to 19.8 ml of tetraethylorthosilicate and 2 g of silicon carbide are added to it with stirring. The molar ratio of the components in the mixture tetraethylorthosilicate: water: tetrapropylammonium hydroxide: aluminum isopropoxide: silicon carbide is 1: 37.1: 0.127: 0.014: 0.562. Mixing is carried out until a homogeneous mixture is obtained. Then this mixture is placed in a Teflon autoclave with a predetermined limiting pressure of 3.7 MPa and in a SpeedWave Berghof - 4 microwave system (microwave power is 900 W, the radiation frequency is 2.45 GHz), it is exposed to microwave radiation, providing a reaction mass temperature of 200 ° C , for 210 minutes.
Образовавшуюся в автоклаве суспензию подвергают центрифугированию в ультрацентрифуге при частоте вращения 2000 об/мин. Затем сливают аликвоту, а твердый осадок промывают не менее 4-х раз дистиллированной водой. После этого проводят его сушку в муфельной печи при температуре 190°С в течение 2 часов. С целью удаления темплата (органических структурообразующих добавок) проводят прокаливание порошка при 550°С в течение 6 часов с получением целевого продукта.The suspension formed in the autoclave is subjected to centrifugation in an ultracentrifuge at a speed of 2000 rpm. An aliquot is then drained, and the solid precipitate is washed at least 4 times with distilled water. After that, it is dried in a muffle furnace at a temperature of 190 ° C for 2 hours. In order to remove the template (organic structure-forming additives), the powder is calcined at 550 ° C for 6 hours to obtain the target product.
На чертеже представлена рентгенограмма твердого продукта - композита, подтверждающая наличие в последнем фазы цеолита MFI и фазы карбида кремния.The drawing shows an x-ray of a solid product - a composite, confirming the presence in the last phase of the MFI zeolite and phase of silicon carbide.
Проведение способа при использовании компонентов смеси в иных мольных соотношениях, входящих в соответствующие вышеоговоренные соотношения, приводит к аналогичным результатам. Проведение способа при соотношениях, выходящих за рамки указанных интервалов не приводит к желаемым результатам. Аналогичная зависимость относится и к режимным условиям воздействия микроволнового излучения при проведении описываемого способа.The method when using the components of the mixture in other molar ratios included in the corresponding above ratios, leads to similar results. The implementation of the method with ratios beyond the specified intervals does not lead to the desired results. A similar dependence applies to the operating conditions of exposure to microwave radiation when carrying out the described method.
Таким образом, описываемый способ позволяет значительно упростить технологию получения целевого композита, снизить время проведения процесса его образования. Данный композит может быть использован в различных процессах кислотно-основного катализа, в частности, процессах крекинга, алкилирования, изомеризации, ароматизации алканов и спиртов.Thus, the described method can significantly simplify the technology of obtaining the target composite, reduce the time of the process of its formation. This composite can be used in various processes of acid-base catalysis, in particular, cracking, alkylation, isomerization, aromatization of alkanes and alcohols.
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
RU2020108036A RU2725586C1 (en) | 2020-02-25 | 2020-02-25 | Method of producing a composite based on microporous zeolite and silicon carbide |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
RU2020108036A RU2725586C1 (en) | 2020-02-25 | 2020-02-25 | Method of producing a composite based on microporous zeolite and silicon carbide |
Publications (1)
Publication Number | Publication Date |
---|---|
RU2725586C1 true RU2725586C1 (en) | 2020-07-02 |
Family
ID=71510377
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
RU2020108036A RU2725586C1 (en) | 2020-02-25 | 2020-02-25 | Method of producing a composite based on microporous zeolite and silicon carbide |
Country Status (1)
Country | Link |
---|---|
RU (1) | RU2725586C1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2787374C1 (en) * | 2022-03-24 | 2023-01-09 | Федеральное государственное бюджетное учреждение науки Ордена Трудового Красного Знамени Институт нефтехимического синтеза им. А.В. Топчиева Российской академии наук (ИНХС РАН) | Method for obtaining zsm-5 structural type nanoscale zeolite in proton form |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6849568B2 (en) * | 2000-03-23 | 2005-02-01 | Honeywell International Inc. | Hydrophilic zeolite coating |
US7179764B2 (en) * | 2002-01-17 | 2007-02-20 | Sicat | Zeolite/SiC composites and their use in catalysis |
-
2020
- 2020-02-25 RU RU2020108036A patent/RU2725586C1/en active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6849568B2 (en) * | 2000-03-23 | 2005-02-01 | Honeywell International Inc. | Hydrophilic zeolite coating |
US7179764B2 (en) * | 2002-01-17 | 2007-02-20 | Sicat | Zeolite/SiC composites and their use in catalysis |
Non-Patent Citations (5)
Title |
---|
GU L. et al., Template-synthesized porous silicon carbide as an effective host for zeolite catalysts, "Chemistry - A European Journal", 2009, Vol.15, No.48, pp 13449-13455. * |
GU L. et al., Template-synthesized porous silicon carbide as an effective host for zeolite catalysts, "Chemistry - A European Journal", 2009, Vol.15, No.48, pp 13449-13455. JUNG E. et al., Synthesis of ZSM-5 on the surface of foam type porous sic support, "Korean Chemical Engineering Research", 2015, Vol.53, No.4, pp 425-430. YILAI JIAO et al., MFI zeolite coating with intrazeolitic aluminum (acidic) gradient supported on SiC foams to improve the methanol-to-propylene (MTP) reaction, "Applied Catalysis A: General", 2018, Vol.559, pp 1-9. * |
JUNG E. et al., Synthesis of ZSM-5 on the surface of foam type porous sic support, "Korean Chemical Engineering Research", 2015, Vol.53, No.4, pp 425-430. * |
XIAOXIA OUA et al., Creating hierarchies promptly: Microwave-accelerated synthesis of ZSM-5 zeolites on macrocellular silicon carbide (SiC) foams, "Chemical Engineering Journal", 2017, Vol. 312, pp 1-9. * |
YILAI JIAO et al., MFI zeolite coating with intrazeolitic aluminum (acidic) gradient supported on SiC foams to improve the methanol-to-propylene (MTP) reaction, "Applied Catalysis A: General", 2018, Vol.559, pp 1-9. * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2787374C1 (en) * | 2022-03-24 | 2023-01-09 | Федеральное государственное бюджетное учреждение науки Ордена Трудового Красного Знамени Институт нефтехимического синтеза им. А.В. Топчиева Российской академии наук (ИНХС РАН) | Method for obtaining zsm-5 structural type nanoscale zeolite in proton form |
RU2799782C1 (en) * | 2022-06-17 | 2023-07-11 | Федеральное государственное бюджетное учреждение науки Ордена Трудового Красного Знамени Институт нефтехимического синтеза им. А.В. Топчиева Российской академии наук (ИНХС РАН) | Composite based on zsm-5 structural type nanosized zeolite in proton form and silicon carbide, and method for its production |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR101230026B1 (en) | Zeolite compositions and preparation and use thereof | |
JP4673379B2 (en) | Method for producing germanium zeolite | |
TWI490167B (en) | Method of preparing zsm-5 zeolite using nanocrystalline zsm-5 seeds | |
JP2002186849A (en) | Method for producing inorganic raw material and apparatus therefor | |
KR101743760B1 (en) | Method for manufacturing of SSZ-13 zeolite catalyst and the SSZ-13 zeolite catalyst thereby | |
EP2300160B1 (en) | Process for making crystalline metallosilicates | |
WO2012071889A1 (en) | Method for synthesizing sapo-34 molecular sieve with low silicon content | |
JP2014531981A (en) | Method for producing phosphorus-modified zeolite catalyst | |
WO2017188341A1 (en) | Mse-type zeolite production method | |
US20110190561A1 (en) | Process for Making Crystalline Metallosilicates | |
US6241960B1 (en) | Method for preparation of small zeotype crystals | |
US20040241072A1 (en) | Process for manufacture of molecular sieves | |
Cheong et al. | Rapid synthesis of nanocrystalline zeolite W with hierarchical mesoporosity as an efficient solid basic catalyst for nitroaldol Henry reaction of vanillin with nitroethane | |
RU2725586C1 (en) | Method of producing a composite based on microporous zeolite and silicon carbide | |
Zhang et al. | Progress in seed-assisted synthesis of (silico) aluminophosphate molecular sieves | |
JP6059068B2 (en) | Method for producing VET type zeolite | |
JP5813858B2 (en) | Process for producing molecular sieve material | |
Chokkalingam et al. | Optimized ultrafast flow synthesis of CON-type zeolite and improvement of its catalytic properties | |
US10207259B2 (en) | Hybrid SAPO-34/ZSM-5 catalyst, its preparation and its use | |
RU2807864C1 (en) | Method for producing zeolite with a ferrierite type structure | |
CN110065953B (en) | Preparation method of beta molecular sieve | |
RU2740476C1 (en) | Method of producing titanium-alumo-silicate zeolite of zsm-12 type | |
RU2740452C1 (en) | Microwave method of producing zsm-12 zeolite with mtw structure | |
RU2787374C1 (en) | Method for obtaining zsm-5 structural type nanoscale zeolite in proton form | |
CN109665540B (en) | ZSM-5/ZSM-48 eutectic molecular sieve and preparation method and application thereof |