CN109133090B - 一种由微晶纤维素调控制备的多级孔mtt结构分子筛、制备方法及用途 - Google Patents
一种由微晶纤维素调控制备的多级孔mtt结构分子筛、制备方法及用途 Download PDFInfo
- Publication number
- CN109133090B CN109133090B CN201811254113.9A CN201811254113A CN109133090B CN 109133090 B CN109133090 B CN 109133090B CN 201811254113 A CN201811254113 A CN 201811254113A CN 109133090 B CN109133090 B CN 109133090B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- pore
- mtt
- mtt structure
- microcrystalline cellulose
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 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 86
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 83
- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 29
- 229920000168 Microcrystalline cellulose Polymers 0.000 title claims abstract description 25
- 235000019813 microcrystalline cellulose Nutrition 0.000 title claims abstract description 25
- 239000008108 microcrystalline cellulose Substances 0.000 title claims abstract description 25
- 229940016286 microcrystalline cellulose Drugs 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000011148 porous material Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 150000004693 imidazolium salts Chemical class 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 8
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 44
- 238000006317 isomerization reaction Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002199 base oil Substances 0.000 description 9
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 239000000314 lubricant Substances 0.000 description 6
- 239000010687 lubricating oil Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000005336 cracking Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 235000010980 cellulose Nutrition 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010517 secondary reaction Methods 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229910021472 group 8 element Inorganic materials 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7046—MTT-type, e.g. ZSM-23, KZ-1, ISI-4 or EU-13
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7492—MTT-type, e.g. ZSM-23, KZ-1, ISI-4 or EU-13
-
- 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
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
-
- 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
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2767—Changing the number of side-chains
- C07C5/277—Catalytic processes
- C07C5/2775—Catalytic processes with crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/02—Well-defined hydrocarbons
- C10M105/04—Well-defined hydrocarbons aliphatic
-
- 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
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
- C07C2529/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing iron group metals, noble metals or copper
- C07C2529/74—Noble metals
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/02—Well-defined aliphatic compounds
- C10M2203/0206—Well-defined aliphatic compounds used as base material
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种多级孔MTT结构分子筛，其含有介孔和微孔，比表面积为400m2/g以上，所述介孔孔径为8‑30nm，所述微孔的孔道尺寸为0.52nm×0.45nm。本发明还公开了所述多级孔MTT结构分子筛的由微晶纤维素调控的制备方法及用于催化剂载体在正烷烃临氢异构反应提高产物中单支链异构产物收率的用途。
Description
技术领域
本发明属于催化剂技术领域，具体涉及一种由微晶纤维素调控制备的多级孔MTT结构分子筛、制备方法及用途。
背景技术
石油产品中，润滑油、喷气燃料等都是注重低温下的各种性质，尤其是凝点、冰点等。近年来，煤通过费托合成法得到的烃类产物更加洁净，具有无硫、无氮、低芳烃的特点，作为制造燃料、润滑油基础油等的原料油而受到瞩目。从润滑油在保持较高粘度指数的同时，并降低倾点来说，并不希望生成有很多支链的异构体，蜡的异构化希望生成少支链异构体，特别是在中央有一个支链的异构产物倾点较低。
对于润滑油基础油的异构脱蜡反应一般使用MTT结构分子筛负载金属活性组分Pt、Pd等第Ⅷ族元素制备的催化剂。长链正构烷烃(碳原子数＞15)的异构化反应主要发生在催化剂的孔口处，只有位于分子筛孔口附近的活性位才能起作用。因此，长链烷烃异构化的高活性催化剂要求所用的分子筛具有较多的孔口数目。MTT结构分子筛的孔道尺寸一般较小，其结构对多支链异构产物的生成和扩散进行限制，导致异构产物发生二次反应，即裂解反应，裂解产物促进积碳的生成，易堵塞催化剂孔道。
专利US7390763 B2公开了一种小晶粒MTT结构分子筛的制备方法及其在C10+正构烷烃的异构降凝中的应用，使用小晶粒MTT结构分子筛可以使目标产物收率提高7.14％。专利CN 103153860 A提出了一种不存在胺组分的情况下制备小晶粒分子筛，但是MTT结构分子筛的孔道结构对多支链异构产物的生成和扩散限制导致异构产物发生二次反应，即裂解反应；裂解产物促进积碳的生成，易堵塞催化剂孔道。
专利CN 105645428 A介绍了一种具有介孔-微孔分等级结构的SSZ-32分子筛的制备方法，该方法通过将原料均质化混合后加入淀粉，再经过老化、晶化、煅烧等过程制备得到分等级结构的SSZ-32分子筛，该分子筛在直链烷烃在临氢异构化反应中可以提高异构化产品中多支链异构体的含量，但单支链异构产物含量仍然较低。专利CN 105640607 A介绍了一种具有介孔-微孔分等级结构的SSZ-23分子筛的制备方法，该方法也是通过将原料均质化混合后加入淀粉，再经过老化、晶化、煅烧等过程制备得到分等级结构的SSZ-32分子筛，该分子筛在直链烷烃在临氢异构化反应中也是可以提高异构化产品中多支链异构体的含量，但单支链异构产物含量仍然较低。
上述的分子筛用着催化剂载体，在加氢异构反应中的活性、选择性和稳定性还不够理想，特别是分子筛的比表面积仍然较少；用于正烷烃临氢异构反应，产物中的单支链异构产物含量仍然较低。
微晶纤维素是一种纯化的、部分解聚的纤维素，是天然纤维素经稀酸水解至极限聚合度(LOOP)的可自由流动的极细微的短棒状或粉末状多孔状颗粒。颜色为白色或近白色，无臭、无味，极限聚合度(LODP)在15-375，不具纤维性而流动性极强。由于具有较低聚合度和较大的比表面积等特殊性质，微晶纤维素被广泛应用于医药、食品、化妆品以及轻化工行业。
本发明首次在微孔结构分子筛的基础上原位加入微晶纤维素制备晶体内和晶体间介孔，得到多级孔MTT结构分子筛。该多级孔MTT结构分子筛的比表面积较大，在400m2/g以上，用于正烷烃临氢异构反应，表现出优异的活性、选择性和稳定性，可以显著提高产物中单支链异构产物收率。
发明内容
本发明第一方面公开了一种多级孔MTT结构分子筛，其含有介孔和微孔，比表面积为400m2/g以上，所述介孔孔径为8-30nm，所述微孔的孔道尺寸为0.52nm×0.45nm。
本发明第二方面公开了所述的多级孔MTT结构分子筛的制备方法，包括如下步骤：
(1)将模板剂、碱液、硅源、铝源加入水中混合均匀；
(2)向步骤(1)得到的混合液中加入微晶纤维素，在一定温度下进行反应；
(3)将步骤(2)得到的固体产物洗涤至中性，干燥后煅烧，冷却至室温，即得到所述的多级孔MTT结构分子筛。
优选地，步骤(1)所述的模板剂为咪唑鎓盐、异丁胺、1,7-庚二胺中的一种或几种；所述铝源为十八水和硫酸铝、铝溶胶、硅铝溶胶中的一种或几种；所述硅源为硅溶胶；所述碱液为NaOH或KOH水溶液。
优选地，所述模板剂、碱液、硅源、铝源、微晶纤维素和水的加入量的摩尔比为：SiO2/Al2O3，15-100；模板剂/SiO2，0.01-0.3；H2O/SiO2，10-80；OH-/SiO2，0.05-0.7；微晶纤维素/SiO2，0.05-1.0。
优选地，步骤(2)所述反应条件为：温度为150-180℃，反应时间为3-10天。
优选地，步骤(3)所述煅烧条件为温度在600℃以上，煅烧时间为3-5小时。
本发明第三方面公开了所述多级孔MTT结构分子筛用于催化剂载体的用途。
优选地，所述多级孔MTT结构分子筛在正烷烃临氢异构反应提高产物中单支链异构产物的用途。
本发明的有益效果：
1、本发明的多级孔MTT结构分子筛是分等级孔结构分子筛，既有微孔又有介孔，具有较多的孔口数量、较高的比表面积和孔容、较大的活性位可接近性，作为催化剂载体负载金属活性组分Pt、Pd等第VIII族元素，能够优化多孔催化剂的孔性质和活性位的合理配置，在加氢异构等需要酸性位的反应中具有广阔的应用前景。特别是用于含蜡的长链正构烷烃的异构降凝反应中所需的催化剂，表现出更高的活性和异构选择性，可以显著提高产物中单支链异构产物收率。
2、本发明首次得到比表面积在400m2/g以上的分子筛，用于正烷烃临氢异构反应，表现出优异的活性和选择性，单支链产物与多支连产物摩尔比率在10以上，显著提高了润滑油的质量。
3、本发明的制备方法首次原位引入廉价易得的具有多孔状结构的微晶纤维素作为共模板剂，实现了一步法合成微孔-介孔分等级结构的MTT分子筛，在微孔结构的基础上原位制备出晶体内、晶体间丰富的介孔，具有较高的比表面积与孔容。微晶纤维素的引入一方面可以作为介孔导向剂在微孔基础上生成介孔，增加了分子筛的孔口数量和比表面积；二是可以减少有机模板剂的使用，减少环境污染，降低了催化剂的制备成本，有利于多级孔MTT分子筛的大规模应用。且通过调节微晶纤维素加入的比例，可以调控级孔分子筛中介微孔比例。而使用普通纤维素达不到本发明的效果。
附图说明
图1为对比例制得的微孔MTT结构分子筛和实施例1制得的多级孔MTT结构分子筛的XRD图；
图2为对比例制得的微孔MTT结构分子筛和实施例1制得的多级孔MTT结构分子筛的N2吸附-脱附等温曲线；
图3为对比例制得的微孔MTT结构分子筛和实施例1制得的多级孔MTT结构分子筛对正十六烷临氢异构选择性的对比图。
图4为对比例制得的微孔MTT结构分子筛和实施例1制得的多级孔MTT结构分子筛对正十六烷临氢异构产物中单支链异构产物与多支链异构产物摩尔比值的对比图。
具体实施方式
为了对本发明的技术特征、目的和有益效果更加清楚的理解，现对本发明的技术方案进行以下详细说明，下面的实施例体现了本发明描述的过程，但本发明并不局限于这些实例。
实施例1：多级孔MTT分子筛的制备。
称取1.0g咪唑鎓盐(1.0M)、21.3g去离子水、10.0g氢氧化钾溶液(1mol/L)加入到有聚四氟内衬的反应器中，搅拌均匀。再向上述的碱性溶液中加入硅铝摩尔比为50的7.6g硅溶胶和2.5g硅铝溶胶、0.9g异丁胺，搅拌均匀。最后再加入微晶纤维素，微晶纤维素的摩尔量为微晶纤维素/SiO2＝0.3，搅拌均匀后，将反应物凝胶装入带聚四氟乙烯内衬水热合成釜中，密封，在自生压力170℃下，晶化8天。
取出晶化产物，冷却，离心分离，并用去离子水洗至中性，在120℃烘箱中干燥；然后将其置于马弗炉中，650℃煅烧6h，即得到所述的多级孔MTT结构分子筛。
得到的多级孔MTT结构分子筛的XRD衍射图谱如图1中的曲线所示，N2吸附-脱附等温曲线如图2中的曲线所示。由图1可知，实施例1原位加入微晶纤维素后得到的分子筛产物晶型没有发生改变，仍然是MTT结构分子筛；由图2可知，实施例1得到的分子筛中有介孔存在。
得到的多级孔MTT分子筛比表面积为430m2/g，介孔孔径范围为8-30nm。
实施例2：多级孔MTT分子筛的制备。
具体合成条件类似于实施例1，但微晶纤维素加入的摩尔量为微晶纤维素/SiO2＝0.05。得到的多级孔MTT结构分子筛比表面积为420m2/g，介孔孔径范围为8-30nm。
实施例3：多级孔MTT分子筛的制备。
具体合成条件类似于实施例1，但微晶纤维素加入的摩尔量为微晶纤维素/SiO2＝1.0。得到的多级孔MTT结构分子筛比表面积为440m2/g，介孔孔径范围为8-30nm。
实施例4：多级孔MTT分子筛的制备。
具体合成条件同实施例1，煅烧温度为700℃。得到的多级孔MTT结构分子筛比表面积为410m2/g，介孔孔径范围为8-30nm。
对比例：微孔MTT结构分子筛的制备。
除了不加入微晶纤维素外，原料与合成条件均与实施例1相同。得到微孔MTT结构分子筛的XRD衍射图谱如图1中的曲线所示，N2吸附-脱附等温曲线如图2中的曲线所示。
实施例5：正十六烷烃临氢异构反应
将上述实施例1得到的多级孔MTT分子筛和对比例得到的微孔MTT结构分子筛分别作为载体，负载贵金属Pt，负载量为0.5wt％，应用到正十六烷的临氢异构反应中，反应压力5MPa，产物分析结果如表1所示。由表1可以看出，在相同的反应温度下，Pt/多级孔MTT结构分子筛(实施例1)催化剂的转化率和异构量比Pt/微孔MTT结构分子筛(对比例)催化剂的转化率和异构量均大幅提升，产物中单支链异构产物显著提高，单支链产物与多支链产物摩尔比率在270℃下，由3以下提高到10以上；说明本发明制得的多级孔MTT结构分子筛应用到正构烷烃的异构降凝反应中，可以高活性、高选择性地制得异构烷烃混合物，显著提高产物中单支链异构产物与多支链异构产物摩尔之比。
异构选择性如图3所示，异构产物中单支链异构产物与多支链异构产物的比值如图4所示。
表1催化性能结果比较
【备注】表1中的“≤C15/wt％”表示产物中碳原子数小于等于15的物质的总质量分数；“异构C16/wt％”表示产物中正十六烷异构体的总质量分数；“异构选择性/％”表示反应物选择性生成正十六烷异构体的百分数；单支链产物/多支连产物表示产物中单支链产物与多支链产物摩尔比。
实施例6：异构脱蜡制备III+润滑油基础油
将上述实施例1得到的多级孔MTT分子筛和对比例得到的微孔MTT结构分子筛分别作为载体，负载贵金属Pt，负载量为0.5wt％，应用到n-C20～n-C60混合正构烷烃的异构脱蜡制备润滑油基础油中。
结果为：实施例1得到多级孔MTT分子筛负载贵金属Pt催化得到的III类+润滑油基础油的收率在50％以上；而在相同条件下，对比例得到微孔MTT结构分子筛作为载体负载贵金属Pt得到的III类+润滑油基础油的收率为30％左右；且实施例1得到多级孔MTT分子筛负载贵金属Pt催化得到的III类+润滑油基础油的粘度指数可以达到140以上，在保持较高收率下，倾点比对比例得到微孔MTT结构分子筛作为载体负载贵金属Pt得到的III类+润滑油基础油的降低幅度可达15％以上。说明本发明制得的具有多级孔MTT结构分子筛负载贵金属Pt催化剂正构烷烃的异构脱蜡反应，可以高活性、高选择性地制得润滑油基础油。
Claims (3)
1.一种多级孔MTT结构分子筛的制备方法，其特征在于，所述多级孔MTT结构分子筛含有介孔和微孔，比表面积为400m2/g以上，所述介孔孔径为8-30nm，所述微孔的孔道尺寸为0.52nm×0.45nm；
所述多级孔MTT结构分子筛的制备方法包括如下步骤：
(1)称取1.0g咪唑鎓盐(1.0M)、21.3g去离子水、10.0g氢氧化钾溶液(1mol/L)加入到有聚四氟内衬的反应器中，搅拌均匀； 再向上述的碱性溶液中加入硅铝摩尔比为50的7.6g硅溶胶和2.5g硅铝溶胶、0.9g异丁胺，搅拌均匀；
(2)最后再加入微晶纤维素，微晶纤维素的摩尔量为微晶纤维素/SiO2＝0.3，搅拌均匀后，将反应物凝胶装入带聚四氟乙烯内衬水热合成釜中，密封，在自生压力170℃下，晶化8天；
(3)取出晶化产物，冷却，离心分离，并用去离子水洗至中性，在120℃烘箱中干燥；然后将其置于马弗炉中，650℃煅烧6h，即得到所述的多级孔MTT结构分子筛。
2.根据权利要求1所述制备方法得到的多级孔MTT结构分子筛用于催化剂载体的用途。
3.根据权利要求2所述的用途，其特征在于，所述多级孔MTT结构分子筛在正烷烃临氢异构反应中提高产物中单支链异构产物的收率。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811254113.9A CN109133090B (zh) | 2018-10-26 | 2018-10-26 | 一种由微晶纤维素调控制备的多级孔mtt结构分子筛、制备方法及用途 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811254113.9A CN109133090B (zh) | 2018-10-26 | 2018-10-26 | 一种由微晶纤维素调控制备的多级孔mtt结构分子筛、制备方法及用途 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109133090A CN109133090A (zh) | 2019-01-04 |
| CN109133090B true CN109133090B (zh) | 2021-09-10 |
Family
ID=64810097
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811254113.9A Active CN109133090B (zh) | 2018-10-26 | 2018-10-26 | 一种由微晶纤维素调控制备的多级孔mtt结构分子筛、制备方法及用途 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109133090B (zh) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110252391A (zh) * | 2019-07-02 | 2019-09-20 | 中国天辰工程有限公司 | 一种催化剂的制备方法及应用 |
| CN114956113B (zh) * | 2021-12-27 | 2023-10-27 | 昆明理工大学 | 一种由静电纺丝纳米纤维素调控制备多级孔分子筛的方法 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102294261A (zh) * | 2011-06-24 | 2011-12-28 | 卓润生 | 一种适用于二段催化裂化反应的催化剂及其制备方法和应用 |
| CN103553077A (zh) * | 2013-11-13 | 2014-02-05 | 黑龙江大学 | 一种具有多级孔的sapo-31分子筛的合成方法 |
| CN105540607A (zh) * | 2016-02-29 | 2016-05-04 | 中国科学院山西煤炭化学研究所 | 具有介孔-微孔分等级结构的zsm-23分子筛的制法 |
| CN106513035A (zh) * | 2016-11-16 | 2017-03-22 | 中国海洋石油总公司 | 一种介孔‑微孔复合加氢异构脱蜡催化剂的制备方法 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016500637A (ja) * | 2012-10-19 | 2016-01-14 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | 合成ガスからオレフィンへの変換のための触媒、およびその調製 |
-
2018
- 2018-10-26 CN CN201811254113.9A patent/CN109133090B/zh active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102294261A (zh) * | 2011-06-24 | 2011-12-28 | 卓润生 | 一种适用于二段催化裂化反应的催化剂及其制备方法和应用 |
| CN103553077A (zh) * | 2013-11-13 | 2014-02-05 | 黑龙江大学 | 一种具有多级孔的sapo-31分子筛的合成方法 |
| CN105540607A (zh) * | 2016-02-29 | 2016-05-04 | 中国科学院山西煤炭化学研究所 | 具有介孔-微孔分等级结构的zsm-23分子筛的制法 |
| CN106513035A (zh) * | 2016-11-16 | 2017-03-22 | 中国海洋石油总公司 | 一种介孔‑微孔复合加氢异构脱蜡催化剂的制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109133090A (zh) | 2019-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109336130B (zh) | 一种由葡聚糖调控制备的多级孔mtt结构分子筛、制备方法及用途 | |
| JP4693239B2 (ja) | 結晶性分子ふるい | |
| CN100587035C (zh) | 制备小晶粒ssz-32的方法及其在烃转化方法的应用 | |
| CN109133090B (zh) | 一种由微晶纤维素调控制备的多级孔mtt结构分子筛、制备方法及用途 | |
| CN112830499B (zh) | 一种单分散ssz-32分子筛、其制备方法和应用 | |
| US9518233B2 (en) | Catalyst for a hydrodgenation dewaxing process and method for manufacturing same | |
| JP2010506010A (ja) | 金属修飾小型結晶ｍｔｔ分子篩を用いる異性化方法 | |
| EP0581619A1 (fr) | Catalyseur à base de cobalt et procédé de conversion du gaz de synthèse en hydrocarbures | |
| CN106430238B (zh) | 以植物纤维素为模板剂制备多级孔道sapo-11分子筛的方法及应用 | |
| JP2011523619A (ja) | 結晶質メタロシリケートの製造方法 | |
| CN101508446B (zh) | 一种调控sapo-11分子筛孔径的制备方法 | |
| CN109110778B (zh) | 一种由脱碱木质素调控制备的多级孔mtt结构分子筛、制备方法及用途 | |
| WO2018192530A1 (zh) | 一种复合结构分子筛及其制备方法与应用 | |
| CN1792451A (zh) | 一种烷烃临氢异构化催化剂及其制备方法和应用 | |
| EP0894768B1 (fr) | Procédé de préparation d'une zéolithe de type ferrierite utilisable comme catalyseur d'isomérisation d'une oléfine linéaire en isooléfine ou comme catalyseur d'hydrocraquage et d'hydroisomérisation des paraffines | |
| NO335850B1 (no) | Fremgangsmåte for fremstilling av paraffiniske mellomdestillater | |
| CN107140657B (zh) | 一种izm-2分子筛的制备方法 | |
| CN112717995A (zh) | 一种mcm-41和ssz-32复合分子筛催化剂、其制备及用途 | |
| JP2004315338A (ja) | 微小粒子径ゼオライトおよびその製造方法 | |
| CN113333017B (zh) | 一种生物质炭辅助合成双功能催化剂的制备方法及应用 | |
| JP2019034879A (ja) | Ｍｆｉ型ゼオライト | |
| CN109665540A (zh) | 一种zsm-5/zsm-48共晶分子筛及其制备方法与应用 | |
| WO2021164135A1 (zh) | 一种用于气态烷烃低温等离子体催化转化的催化剂及其制备方法 | |
| EP4324556A1 (en) | Zeolite with improved hydroisomerization activity | |
| CN115055205A (zh) | 一种zsm-5/y复合分子筛的合成和重油催化裂化催化剂的制备方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder |
Address after: 300452 Binhai Industrial Research Institute Campus of Tianjin University, No. 48 Jialingjiang Road, Binhai New Area, Tianjin Patentee after: Tianjin University Address before: 300072 Tianjin City, Nankai District Wei Jin Road No. 92 Patentee before: Tianjin University |
|
| CP02 | Change in the address of a patent holder |