CN109231232A - Micro--meso-hole structure Beta molecular sieve, micro--mesoporous Beta molecular sieve catalyst of Ni base and preparation method thereof - Google Patents
Micro--meso-hole structure Beta molecular sieve, micro--mesoporous Beta molecular sieve catalyst of Ni base and preparation method thereof Download PDFInfo
- Publication number
- CN109231232A CN109231232A CN201811320142.0A CN201811320142A CN109231232A CN 109231232 A CN109231232 A CN 109231232A CN 201811320142 A CN201811320142 A CN 201811320142A CN 109231232 A CN109231232 A CN 109231232A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- micro
- beta molecular
- mesoporous
- mesoporous beta
- 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.)
- Pending
Links
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 107
- 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 107
- 239000003054 catalyst Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- WSULSMOGMLRGKU-UHFFFAOYSA-N 1-bromooctadecane Chemical compound CCCCCCCCCCCCCCCCCCBr WSULSMOGMLRGKU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims abstract description 8
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims description 31
- 238000002425 crystallisation Methods 0.000 claims description 24
- 230000008025 crystallization Effects 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 230000032683 aging Effects 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 14
- 238000011017 operating method Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 229910001868 water Inorganic materials 0.000 claims description 8
- MAUMSNABMVEOGP-UHFFFAOYSA-N (methyl-$l^{2}-azanyl)methane Chemical compound C[N]C MAUMSNABMVEOGP-UHFFFAOYSA-N 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000009415 formwork Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- 238000010791 quenching Methods 0.000 claims description 7
- 230000000171 quenching effect Effects 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 7
- 239000012265 solid product Substances 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000003643 water by type Substances 0.000 claims description 7
- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 33
- 239000001257 hydrogen Substances 0.000 abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 22
- 238000003786 synthesis reaction Methods 0.000 abstract description 12
- 230000015572 biosynthetic process Effects 0.000 abstract description 11
- 239000011148 porous material Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 abstract 1
- 150000004985 diamines Chemical class 0.000 abstract 1
- 238000009792 diffusion process Methods 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 23
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 15
- 235000019441 ethanol Nutrition 0.000 description 13
- 239000004094 surface-active agent Substances 0.000 description 13
- 239000013078 crystal Substances 0.000 description 9
- 238000001666 catalytic steam reforming of ethanol Methods 0.000 description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 8
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000002407 reforming Methods 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 description 3
- 239000006071 cream Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 210000003850 cellular structure Anatomy 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000004966 Carbon aerogel Substances 0.000 description 1
- 201000001376 Familial Combined Hyperlipidemia Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 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
- 238000003795 desorption Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000012690 zeolite precursor Substances 0.000 description 1
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
- B01J29/72—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
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
-
- 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
- B01J35/66—Pore distribution
- B01J35/69—Pore distribution bimodal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1217—Alcohols
- C01B2203/1229—Ethanol
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
本发明涉及分子筛、催化剂，具体为微‑介孔Beta分子筛、Ni基微介孔Beta分子筛催化剂及其制备方法，解决现有微孔Beta分子筛孔道狭窄、比表面积小和Ni基分子筛催化剂扩散限制问题，步骤：在乙腈和甲苯（1:1 v/v）中，以摩尔比为2:1的溴代十八烷和N,N,N’,N’‑四甲基‑1,6‑己二胺反应制得模板剂C18‑6‑18Br2；然后以四乙基氢氧化铵水溶液和上述模板剂及其它化学原料水热合成微介孔Beta分子筛；再将六水合硝酸镍负载于上述分子筛，即得Ni基微介孔Beta分子筛催化剂。优点：以自制模板剂合成微‑介孔Beta分子筛，成本低；所合成的微介孔Beta分子筛孔道连通性好；所制备的Ni基微介孔Beta分子筛催化剂，使乙醇转化率和氢气选择性明显提高。
The invention relates to molecular sieves and catalysts, in particular to micro-mesoporous Beta molecular sieves, Ni-based micro-mesoporous Beta molecular sieve catalysts and preparation methods thereof, and solves the problems of narrow pores, small specific surface area and diffusion limitation of Ni-based molecular sieve catalysts in the existing microporous Beta molecular sieves , step: in acetonitrile and toluene (1:1 v/v), in a molar ratio of 2:1 bromooctadecane and N,N,N',N'-tetramethyl-1,6-hexane The template agent C 18-6-18 Br 2 is prepared by the reaction of diamine; then the micro-mesoporous Beta molecular sieve is hydrothermally synthesized with tetraethylammonium hydroxide aqueous solution, the above-mentioned template agent and other chemical raw materials; then nickel nitrate hexahydrate is loaded on Above-mentioned molecular sieve, namely obtains Ni-based micro-mesoporous Beta molecular sieve catalyst. Advantages: Synthesis of micro-mesoporous Beta molecular sieve with self-made template, low cost; The synthesized micro-mesoporous Beta molecular sieve has good channel connectivity; The prepared Ni-based micro-mesoporous Beta molecular sieve catalyst improves the ethanol conversion rate and hydrogen selectivity Significantly improved.
Description
Technical field
The present invention relates to molecular sieve, catalyst, specially micro--meso-hole structure Beta molecular sieve, micro--mesoporous Beta of Ni base point
Sub- sieve catalyst and preparation method thereof.
Background technique
In recent years, the non-renewable energy resources such as coal, petroleum, natural gas are largely consumed, the serious energy danger of facing mankind
Machine and environmental problem find the problem of new alternative energy source is urgent need to resolve.Hydrogen Energy, with its reproducibility, burning is pollution-free, comes
The advantages that source is extensive and obtained extensive concern.Wherein, the indirect hydrogen manufacturing of wood-based composites is considered as most economical feasible side
Formula.Therefore, it selects suitable catalyst carrier and has stronger C-C key and the transition metal of c h bond fracture energy to be to improve second
The key of alcohol conversion and hydrogen selective.Beta molecular sieve is unique silica-rich zeolite with three-dimensional twelve-ring duct, along a
Direction and the direction b have twelve-ring straight hole, have the twelve-ring cellular structure slightly distorted along the direction c.Its unique hole
Road structure, stronger acid, good thermal stability, become research hotspot in recent years, are widely used in catalysis, ion
The fields such as exchange and absorption.But due to its cellular structure relative narrowness, especially when the size of reactant molecule is more than molecular sieve
When internal aperture size, reactant is easily caused to be blocked in duct, active site can not be reached, limits it in production and living
Using.Narrow for molecular sieve bore diameter, bottom-to-top method can solve the problems, such as this.Bottom-to-top method, which refers to, to be synthesized
Mesoporous directed agents are introduced in the process, generate secondary apertures using the effect of its structure directing.Relative to prepare composite molecular screen and from
The upper and lower method for carrying out subsequent dealuminzation or desiliconization, this method for introducing template can realize the accurate control to duct, most
The big possible intrinsic skeleton structure for retaining molecular sieve.Therefore, this method is widely used for synthesizing micro- meso-hole structure molecular sieve.
In bottom-to-top method, hard template method and soft template method are related generally to.Hard template method is primarily referred to as utilizing some relative stiffnesses
Material as template is synthesising mesoporous or multistage porous molecular sieve, such as carbon nanotube, porous carbon, carbon aerogels.For example,
The dense HCl and dense H such as Tang2SO4Mixture handle multi-walled carbon nanotube, then synthesized nanometer in hydrothermal synthesis system
ZSM-5 the and NaA type molecular sieve of grade.But hard mould agent, for synthesizing micro- meso-hole structure molecular sieve, expensive, yield is low,
So that method application is limited.And soft template method is a kind of relatively good method, used quaternary ammonium salt cationic surface-active
Agent not only has multiple positively charged nitrogenous polar head groups, also has long alkyl chain symmetrically or non-symmetrically, can form a setting
The micella of shape, so that electrostatic interaction occur with electronegative alumino-silicate species, guiding generates micro--meso-hole structure.For example,
Six ammonium cation type quaternary surfactants are used to synthesize simultaneously in 102826564 A of patent CN as template
Contain micropore and mesoporous multi-stage porous Beta molecular sieve.Therefore, prepare first generated time is short, yield is high quaternary ammonium salt sun from
Then sub- surfactant synthesizes the good micro- mesoporous Beta molecular sieve of large specific surface area, hole link using soft template method
The problem of being urgent need to resolve.In addition to this, Ni base catalyst is cheap, has stronger C-C key fracture energy, by W metal
Active component is supported on micro- mesoporous Beta molecular sieve, and is applied to hydrogen production by ethanol steam reforming catalysis reaction, is to solve mesh
The effective way of preceding hydrogen energy fuel problem.
Therefore, it designs a kind of simple, the easy to operate, at low cost micro--meso-hole structure Beta molecular sieve of synthesis condition and urges
The preparation method of agent is highly beneficial to improve catalytic efficiency of the catalyst in hydrogen production by ethanol steam reforming reaction.
Summary of the invention
The existing micropore Beta molecular sieve pore passage structure of present invention solution is single, specific surface area is small and catalyst activity component point
The problem that cloth is uneven, catalytic efficiency is low provides a kind of crystallinity height, large specific surface area, hole link good micro--mesoporous Beta
Molecular sieve and preparation method thereof, unique skeleton structure and excellent physicochemical characteristic, when making it as carrier and active component
Between there are stronger active forces；It provides simultaneously a kind of using synthesized micro--mesoporous Beta molecular sieve as carrier, utilizes isometric leaching
Stain method carrying transition metal nickel, micro--mesoporous Beta molecular sieve catalyst of Ni base for hydrogen production by ethanol steam reforming gas and its
The selectivity of preparation method, the conversion ratio and hydrogen that make ethyl alcohol greatly improves.
The present invention is realized by following operating procedure: micro--mesoporous Beta molecular sieve preparation method, including following operation
Step:
One, by the tetraethyl ammonium hydroxide C of content 25%8H21NO aqueous solution 23.50ml ± 0.50ml, deionized water 19ml ±
0.50ml, sodium hydroxide solution 3.00ml ± 0.50ml that concentration is 8mol/L are sequentially added, and are stirred evenly；
Two, at 25-30 DEG C, the mixture of acetonitrile and toluene that volume ratio is 1:1 is added in three-necked flask, reaction is heated to
70-75 DEG C, respectively measure 0.005mol bromo-octadecane and 0.0025mol N, N, N ', N '-tetramethyl -1,6- hexamethylene diamine according to
It is secondary to be added drop-wise in mixed solution, continue return stirring 15 hours at the temperature disclosed above；After reaction, round-bottomed flask is taken out,
It is rapidly cooled to 25-30 DEG C, after the organic solvent in flask has rotated, the reaction product in flask is dissolved in ethyl acetate
In, by washing suction filtration repeatedly, finally place the product in being dried overnight in 40-50 DEG C of vacuum oven, dry gained after grinding
Product is template [C18H37(CH3)2N+(CH2)6N+(CH3)2C18H37][Br-]2(hereinafter it is abbreviated as C18-6-18Br2)；
Three, by template C18-6-18Br2 With sodium metaaluminate NaAlO21.200g ± 0.100g is added to step 1 acquired solution
In, continue to stir evenly；
Four, ethyl orthosilicate C is measured8H20O4Si 47.00ml ± 1.00ml is dissolved in step 3 acquired solution, 25-30 DEG C of stirring
30-60min obtains milky silica-alumina gel；
Five, at 30-80 DEG C, white silica-alumina gel constant temperature aging 30-50h obtained by step 4 turns the silica-alumina gel of aging
It moves in the stainless steel cauldron that liner is polytetrafluoroethylene (PTFE), is heated in insulating box under air-proof condition, crystallization temperature 100-
150 DEG C, crystallization time 80-120h；
Six, reaction kettle after the reaction was completed, is taken out, carries out quenching processing with 10 DEG C of deionized waters, the temperature to reaction kettle drops to
At 20 DEG C, crystallization product is taken out, product is washed repeatedly with deionized water to neutrality；
Seven, the solid product washed is put into clean surface plate, in 80-100 DEG C of vacuum drying oven, drying
10-20h, vacuum degree 20Pa；
Eight, desciccate is placed in Muffle furnace, 450-550 DEG C of high-temperature roasting, removes organic formwork agent, last gained is
Containing micro--mesoporous Beta molecular sieve.
Micro--mesoporous Beta molecular sieve catalyst preparation method of Ni base, including following operating procedure:
One, at 25-30 DEG C, the Nickelous nitrate hexahydrate of 10wt% ~ 15wt% is carried on 0.500- using equi-volume impregnating
Above-mentioned micro--mesoporous Beta molecular sieve of 1.000g；
Two, the sample after load is ground into fine powder, be placed in tube furnace, in N2In 500-550 DEG C of high-temperature roasting in atmosphere
2-3h；
Three, after the completion of roasting, powdered samples is subjected to tabletting sieving, obtain micro--mesoporous Beta molecular sieve of Ni base of 40-60 mesh
Catalyst.
The invention has the following advantages: organic mould that the 1, present invention is synthesized using inorganic raw material cheap and easy to get and certainly
Plate agent has synthesized while having had micropore, mesoporous Beta molecular sieve by a step hydrothermal crystallization method, greatly reduce synthesis at
This, provides new method for the excellent multi-stage porous Beta molecular sieve of synthesis performance；2, the present invention in suitable crystallization temperature and
Under crystallization time, micro--mesoporous Beta molecular sieve is provided using double-template method one-step synthesis, had both maintained the hole of micropore itself
Road structure and good hydrothermal stability, and the structure of micropore and the interconnection of mesoporous height in crystal phase is realized, operating procedure is simple,
Be easy to get target product；3, the Bis-quaternary Ammonium Surfactants synthesized by the present invention are dredged by two nitrogenous polar head groups, two
What the long alkane chain of water and a methylene linking group were constituted, electronegative sial in positively charged polar head group and gel
Hydrochlorate can occur closely to interact；Long chain hydrophobic group " C18H37" micellar structure to form meso-scale can be assembled, it can lead
It is crystallized to Beta zeolite precursor body；It is avoided the thermal and hydric environment break key the problem of by the linking group that six methylene are constituted,
Two hydrophilic head groups are closely connected by chemical bond, to weaken the repulsive interaction between hydrophilic head base, are made
Surfactant monomer molecule forms closer connection；4, the Bis-quaternary Ammonium Surfactants synthesized by the present invention, with biography
Single-stranded quaternary surfactant of uniting is compared, and distinctive connection type keeps the molecular structure of surfactant more stable, right
Claiming the quaternary ammonium group of distribution also makes the binding force of alumino-silicate and template stronger, and two long alkyl chains make its hydrophobic effect more
Obviously, to keep its opening hole effect more obvious；5, the present invention synthesized by micro--mesoporous Beta molecular sieve, why mesoporous phase
The degree of order it is very high, mainly used in template C18-6-18Br2Caused by, surfactant C18-6-18Br2Between molecule
Interaction will limit the growth of crystal, and hydrophobic long alkyl chain can form vermiform micellar structure, may participate in aluminosilicate
In the growth of salt precursor body, make its growth that there is certain direction, therefore the degree of order of mesoporous phase is improved significantly；6, this hair
Bright synthesized micro--mesoporous Beta molecular sieve catalyst of Ni base, by the way that active metal Ni is supported on micro--mesoporous Beta molecular sieve
In the surface or duct of carrier, the higher activity of transition metal Ni itself and stronger C-C key fracture energy are not only maintained,
The sintering for also contributing to inhibit W metal itself, keeps more active site；7, the Ni base synthesized by the present invention
Micro--mesoporous Beta molecular sieve catalyst has the characteristics that preparation process is simple, non-noble metal Ni is at low cost, while turn of ethyl alcohol
Rate and the selectivity of hydrogen are improved significantly.
Detailed description of the invention
Fig. 1 is the surfactant C of embodiment synthesis18-6-18Br2Infrared absorpting light spectra；As seen from the figure: it mainly contains
There are the characteristic absorption peak of alkanes and the stretching vibration peak 2918cm of quaternary ammonium salt group C-N-1、2835cm-1For the flexible vibration of C-H
Dynamic peak, 1468cm-1For-CH2、-CH3Antisymmetry bending vibration absorption peak, 717cm-1For-(CH2)nCharacteristic absorption peak,
900cm-1For the characteristic absorption peak of quaternary ammonium salt (C-N), therefore, this product is synthesized surfactant C18-6-18Br2；
Fig. 2 is micro--meso-hole structure Beta molecular sieve of embodiment synthesis and the X ray diffraction intensity of pure phase Beta molecular sieve
Spectrogram comparison diagram；As seen from the figure, in the diffraction region of 2 θ=5-40 °, there are 7.8 ° and 22.5 ° of the two characteristic diffraction peaks occur,
Illustrate that synthesized sample is Beta zeolite crystal, and mutually occurs without any stray crystal；It is micro--mesoporous relative to micropore Beta
The diffracted intensity of Beta molecular sieve characteristic peak slightly reduces, and illustrates that its crystallinity is slightly decreased；In the diffraction region of 2 θ=0-5 °,
There is apparent small-angle diffraction peak at 2.47 ° in micro--mesoporous Beta molecular sieve, illustrates inside crystal phase containing orderly mesoporous knot
Structure；
Fig. 3 is the transmission electron microscope photo of micro--meso-hole structure Beta molecular sieve of embodiment synthesis；As seen from the figure:
Synthesized micro--meso-hole structure Beta molecular sieve is arbitrarily to be accumulated to constitute by sheet-like particle not of uniform size, illustrates mould
Plate agent C18-6-18Br2Addition influence is produced on the pattern of molecular sieve, and participated in the forming process of Beta molecular sieve
In.C18-6-18Br2Long hydrophobic chain can be self-assembly of micella, on the one hand can hinder the continued growth of microcellular structure, on the other hand
The pore-foaming agent of meso-scale can be served as.
Fig. 4 is micro--meso-hole structure Beta molecular sieve of embodiment synthesis and the nitrogen adsorption-of pure phase Beta molecular sieve
Desorption isotherm comparison diagram；It as seen from the figure, is 0.0 < P/P in relative pressure0< 0.1 area of low pressure, both molecular sieves N2's
Adsorbance sharply increases, this is micropore caused by a large amount of fillings；It is 0.2 < P/P in relative pressure0< 1.0 mesohigh area
There is the hysteresis loop of apparent H1 type in domain, micro--mesoporous Beta molecular sieve, this is because mesoporous middle N2Capillary condensation draw
Rise, show micropore, it is mesoporous coexist in synthesized sample, meanwhile, N2Adsorbance be apparently higher than micropore Beta；And micro-
The N of hole Beta2It is this type hysteresis loop do not occur in adsorption desorption curve, only occurs being situated between by the intergranular accumulated in high-pressure area
Hysteresis loop caused by hole；Micro--mesoporous Beta molecular sieve combines I type familial combined hyperlipidemia thermoisopleth, shows to wrap in synthesized sample
Micropore and interconnected mesoporous is contained；
Fig. 5 is that micro--meso-hole structure Beta molecular sieve of embodiment synthesis and pure phase Beta molecular sieve are calculated according to NLDFT model
Obtained pore size distribution curve comparison diagram；As seen from the figure, the micropore size of the two concentrates on 0.526nm and 0.831nm, synthesized
Micro--mesoporous Beta microporous molecular sieve aperture when being 0.526nm micropore pore volume to be significantly lower than the micropore hole body of micropore Beta
Product, when aperture is 0.831nm, pore volume is higher than the pore volume of micropore Beta, this illustrates that used second template is effective
The crystallization process for taking part in micropore；The mesoporous pore size of micro--mesoporous Beta molecular sieve concentrates on 3.5nm, and this is mainly due to seasons
The addition of ammonium surfactant is so that transgranular mesoporous appear in zeolite phase；The two is mesoporous by the intergranular that particle packing is formed
It is existing；
Fig. 6 be the 10wt%Ni base of embodiment synthesis it is micro--the X ray diffraction intensity of meso-hole structure Beta molecular sieve catalyst spectrum
Figure；As seen from the figure, the sample after load has the characteristic diffraction peak of BEA after tube furnace roasts at 2 θ=7.8 ° and 22.5 °,
Illustrate that Beta zeolite crystal is retained after load；Meanwhile the intensity of diffraction maximum is not decreased obviously, the Beta after illustrating load
Molecular sieve crystallinity keeps good；There is the diffraction maximum of NiO at 2 θ=37.1 °, 43.2 ° and 62.8 °, be respectively belonging to 111,
200,220 crystal face illustrates that NiO has been dispersed in the outer surface or duct of Beta molecular sieve carrier；
Fig. 7 is micro--meso-hole structure Beta molecular sieve of embodiment synthesis and the texture property contrast table of pure phase Beta molecular sieve；By
Biao Ke get: in specific surface area, the specific surface area of micro--mesoporous Beta molecular sieve is higher than the specific surface area of micropore Beta molecular sieve,
The S of the twoMicroporeIt is close, but SIt is mesoporousAnd SIt is mesoporous/SBETThe former is significantly larger than the latter, illustrate it is mesoporous be present in it is synthesized micro--mesoporous
In Beta molecular sieve, and it will not influence the micropore in duct；On Kong Rong, the average V of the twoMicroporeIt is identical, VIt is mesoporousWith
VIt is mesoporous/VAlwaysIt is clearly present in micro--mesoporous Beta molecular sieve, this illustrates it is containing Jie in micro--mesoporous Beta crystal phase closed
Hole, this is because used quaternary surfactant enters in Beta zeolite crystal phase and plays the role of opening hole；From
In table it is also seen that aperture has similar trend with hole；In conclusion createing and in micro--mesoporous Beta molecular sieve
The mesoporous presence for having no effect on micropore.
Specific embodiment
Embodiment 1: micro--mesoporous Beta molecular sieve preparation method, including following operating procedure:
One, by the tetraethyl ammonium hydroxide C of content 25%8H21NO aqueous solution 23.50ml, deionized water 19ml, concentration 8mol/L
Sodium hydroxide solution 3ml sequentially add, stir evenly；
Two, at 25 DEG C, the mixture of acetonitrile and toluene that volume ratio is 1:1 is added in three-necked flask, reaction is heated to 75 DEG C,
The bromo-octadecane and 0.0025mol N, N, N of 0.005mol are measured respectively ', N '-tetramethyl -1,6- hexamethylene diamine is successively added drop-wise to
In mixed solution, continue return stirring 15 hours at the temperature disclosed above；After reaction, round-bottomed flask is taken out, it is cooling rapidly
To 28 DEG C, after the organic solvent in flask has rotated, the reaction product in flask is dissolved in ethyl acetate, by washing repeatedly
Suction filtration is washed, finally place the product in being dried overnight in 48 DEG C of vacuum ovens, products therefrom is template after drying grinding
[C18H37(CH3)2N+(CH2)6N+(CH3)2C18H37][Br-]2(hereinafter it is abbreviated as C18-6-18Br2)；
Three, by template C18-6-18Br2 With sodium metaaluminate NaAlO21.25g is added in step 1 acquired solution, continues to stir
Uniformly；
Four, ethyl orthosilicate C is measured8H20O4Si 47.00ml is dissolved in step 3 acquired solution, and 25 DEG C of stirring 60min obtain cream
White silica-alumina gel；
Five, at 55 DEG C, the silica-alumina gel of aging is transferred to interior by white silica-alumina gel constant temperature aging 48h obtained by step 4
Lining is to heat in insulating box under air-proof condition in the stainless steel cauldron of polytetrafluoroethylene (PTFE), and crystallization temperature is 120 DEG C, crystallization
Time is 100h；
Six, reaction kettle after the reaction was completed, is taken out, carries out quenching processing with 10 DEG C of deionized waters, the temperature to reaction kettle drops to
At 20 DEG C, crystallization product is taken out, product is washed repeatedly with deionized water to neutrality；
Seven, the solid product washed is put into clean surface plate, in 100 DEG C of vacuum drying ovens, dries 20h,
Vacuum degree is 20Pa；
Eight, desciccate is placed in Muffle furnace, 550 DEG C of high-temperature roastings, removes organic formwork agent, last gained be containing it is micro--
Mesoporous Beta molecular sieve.
Micro--mesoporous Beta molecular sieve catalyst preparation method of hydrogen production by ethanol steam reforming Ni base, including following operation step
It is rapid:
One, at 25 DEG C, it is above-mentioned micro--mesoporous that the Nickelous nitrate hexahydrate of 10wt% is carried on 0.500g using equi-volume impregnating
Beta molecular sieve；
Two, the sample after load is ground into fine powder, be placed in tube furnace, in N2In 500 DEG C of high-temperature roasting 2h in atmosphere；
Three, after the completion of roasting, powdered samples are subjected to tabletting sieving, micro--mesoporous Beta molecular sieve of Ni base for obtaining 50 mesh is urged
Agent.
Micro--mesoporous Beta molecular sieve catalyst of gained Ni base, for atmospheric fixed bed micro-reaction device in 450 DEG C of progress second
When alcohol vapor reforming hydrogen production Catalysis experiments, the conversion ratio of ethyl alcohol is 76.598%, and the selectivity of hydrogen is 56.89%.
Embodiment 2: micro--mesoporous Beta molecular sieve preparation method, including following operating procedure:
One, by the tetraethyl ammonium hydroxide C of content 25%8H21NO aqueous solution 23.00ml, deionized water 18.5ml, concentration are
The sodium hydroxide solution 3.20ml of 8mol/L is sequentially added, and is stirred evenly；
Two, at 30 DEG C, the mixture of acetonitrile and toluene that volume ratio is 1:1 is added in three-necked flask, reaction is heated to 70 DEG C,
The bromo-octadecane and 0.0025mol N, N, N of 0.005mol are measured respectively ', N '-tetramethyl -1,6- hexamethylene diamine is successively added drop-wise to
In mixed solution, continue return stirring 15 hours at the temperature disclosed above；After reaction, round-bottomed flask is taken out, it is cooling rapidly
To 30 DEG C, after the organic solvent in flask has rotated, the reaction product in flask is dissolved in ethyl acetate, by washing repeatedly
Suction filtration is washed, finally place the product in being dried overnight in 40 DEG C of vacuum ovens, products therefrom is template after drying grinding
[C18H37(CH3)2N+(CH2)6N+(CH3)2C18H37][Br-]2(hereinafter it is abbreviated as C18-6-18Br2)；
Three, by template C18-6-18Br2 With sodium metaaluminate NaAlO21.240g is added in step 1 acquired solution, continues to stir
Uniformly；
Four, ethyl orthosilicate C is measured8H20O4Si 46.00ml is dissolved in step 3 acquired solution, and 30 DEG C of stirring 45min obtain cream
White silica-alumina gel；
Five, at 75 DEG C, the silica-alumina gel of aging is transferred to interior by white silica-alumina gel constant temperature aging 40h obtained by step 4
Lining is to heat in insulating box under air-proof condition in the stainless steel cauldron of polytetrafluoroethylene (PTFE), and crystallization temperature is 110 DEG C, crystallization
Time is 90h；
Six, reaction kettle after the reaction was completed, is taken out, carries out quenching processing with 10 DEG C of deionized waters, the temperature to reaction kettle drops to
At 20 DEG C, crystallization product is taken out, product is washed repeatedly with deionized water to neutrality；
Seven, the solid product washed is put into clean surface plate, in 90 DEG C of vacuum drying ovens, dries 15h, very
Reciprocal of duty cycle is 20Pa；
Eight, desciccate is placed in Muffle furnace, 480 DEG C of high-temperature roastings, removes organic formwork agent, last gained be containing it is micro--
Mesoporous Beta molecular sieve.
Micro--mesoporous Beta molecular sieve catalyst preparation method of hydrogen production by ethanol steam reforming Ni base, including following operation step
It is rapid:
One, at 30 DEG C, it is above-mentioned micro--mesoporous that the Nickelous nitrate hexahydrate of 12wt% is carried on 1.000g using equi-volume impregnating
Beta molecular sieve；
Two, the sample after load is ground into fine powder, be placed in tube furnace, in N2In 520 DEG C of high-temperature roasting 2.5h in atmosphere；
Three, after the completion of roasting, powdered samples are subjected to tabletting sieving, micro--mesoporous Beta molecular sieve of Ni base for obtaining 40 mesh is urged
Agent.
Micro--mesoporous Beta molecular sieve catalyst of gained Ni base, for atmospheric fixed bed micro-reaction device in 500 DEG C of progress second
When alcohol vapor reforming hydrogen production Catalysis experiments, the conversion ratio of ethyl alcohol is 62.38%, and the selectivity of hydrogen is 62.4%.
Embodiment 3: micro--mesoporous Beta molecular sieve preparation method, including following operating procedure:
One, by the tetraethyl ammonium hydroxide C of content 25%8H21NO aqueous solution 24.0ml, deionized water 19.5ml, concentration 8mol/
The sodium hydroxide solution 2.8ml of L is sequentially added, and is stirred evenly；
Two, at 28 DEG C, the mixture of acetonitrile and toluene that volume ratio is 1:1 is added in three-necked flask, reaction is heated to 72 DEG C,
The bromo-octadecane and 0.0025mol N, N, N of 0.005mol are measured respectively ', N '-tetramethyl -1,6- hexamethylene diamine is successively added drop-wise to
In mixed solution, continue return stirring 15 hours at the temperature disclosed above；After reaction, round-bottomed flask is taken out, it is cooling rapidly
To 25 DEG C, after the organic solvent in flask has rotated, the reaction product in flask is dissolved in ethyl acetate, by washing repeatedly
Suction filtration is washed, finally place the product in being dried overnight in 50 DEG C of vacuum ovens, products therefrom is template after drying grinding
[C18H37(CH3)2N+(CH2)6N+(CH3)2C18H37][Br-]2(hereinafter it is abbreviated as C18-6-18Br2)；
Three, by template C18-6-18Br2With sodium metaaluminate NaAlO21.2g is added in step 1 acquired solution, and it is equal to continue stirring
It is even；
Four, ethyl orthosilicate C is measured8H20O4Si 48.00ml is dissolved in step 3 acquired solution, and 28 DEG C of stirring 30min obtain cream
White silica-alumina gel；
Five, at 80 DEG C, the silica-alumina gel of aging is transferred to interior by white silica-alumina gel constant temperature aging 50h obtained by step 4
Lining is to heat in insulating box under air-proof condition in the stainless steel cauldron of polytetrafluoroethylene (PTFE), and crystallization temperature is 150 DEG C, crystallization
Time is 80h；
Six, reaction kettle after the reaction was completed, is taken out, carries out quenching processing with 10 DEG C of deionized waters, the temperature to reaction kettle drops to
At 20 DEG C, crystallization product is taken out, product is washed repeatedly with deionized water to neutrality；
Seven, the solid product washed is put into clean surface plate, in 80 DEG C of vacuum drying ovens, dries 10h, very
Reciprocal of duty cycle is 20Pa；
Eight, desciccate is placed in Muffle furnace, 450 DEG C of high-temperature roastings, removes organic formwork agent, last gained be containing it is micro--
Mesoporous Beta molecular sieve.
Micro--mesoporous Beta molecular sieve catalyst preparation method of hydrogen production by ethanol steam reforming Ni base, including following operation step
It is rapid:
One, at 27 DEG C, it is above-mentioned micro--mesoporous that the Nickelous nitrate hexahydrate of 15wt% is carried on 0.75g using equi-volume impregnating
Beta molecular sieve；
Two, the sample after load is ground into fine powder, be placed in tube furnace, in N2In 550 DEG C of high-temperature roasting 3h in atmosphere；
Three, after the completion of roasting, powdered samples are subjected to tabletting sieving, micro--mesoporous Beta molecular sieve of Ni base for obtaining 60 mesh is urged
Agent.
Micro--mesoporous Beta molecular sieve catalyst of gained Ni base, for atmospheric fixed bed micro-reaction device in 550 DEG C of progress second
When alcohol vapor reforming hydrogen production Catalysis experiments, the conversion ratio of ethyl alcohol is 84.99%, and the selectivity of hydrogen is 68.87%.
Embodiment 4: micro--mesoporous Beta molecular sieve preparation method, including following operating procedure:
One, by the tetraethyl ammonium hydroxide C of content 25%8H21NO aqueous solution 23.75ml, deionized water 18.75ml, concentration are
The sodium hydroxide solution 3.5ml of 8mol/L is sequentially added, and is stirred evenly；
Two, at 26 DEG C, the mixture of acetonitrile and toluene that volume ratio is 1:1 is added in three-necked flask, reaction is heated to 74 DEG C,
The bromo-octadecane and 0.0025mol N, N, N of 0.005mol are measured respectively ', N '-tetramethyl -1,6- hexamethylene diamine is successively added drop-wise to
In mixed solution, continue return stirring 15 hours at the temperature disclosed above；After reaction, round-bottomed flask is taken out, it is cooling rapidly
To 27 DEG C, after the organic solvent in flask has rotated, the reaction product in flask is dissolved in ethyl acetate, by washing repeatedly
Suction filtration is washed, finally place the product in being dried overnight in 44 DEG C of vacuum ovens, products therefrom is template after drying grinding
[C18H37(CH3)2N+(CH2)6N+(CH3)2C18H37][Br-]2(hereinafter it is abbreviated as C18-6-18Br2)；
Three, by template C18-6-18Br2 With sodium metaaluminate NaAlO21.10g is added in step 1 acquired solution, continues to stir
Uniformly；
Four, ethyl orthosilicate C is measured8H20O4Si 46.5ml is dissolved in step 3 acquired solution, and 27 DEG C of stirring 50min are obtained milky white
Color silica-alumina gel；
Five, at 30 DEG C, the silica-alumina gel of aging is transferred to interior by white silica-alumina gel constant temperature aging 30h obtained by step 4
Lining is to heat in insulating box under air-proof condition in the stainless steel cauldron of polytetrafluoroethylene (PTFE), and crystallization temperature is 100 DEG C, crystallization
Time is 120h；
Six, reaction kettle after the reaction was completed, is taken out, carries out quenching processing with 10 DEG C of deionized waters, the temperature to reaction kettle drops to
At 20 DEG C, crystallization product is taken out, product is washed repeatedly with deionized water to neutrality；
Seven, the solid product washed is put into clean surface plate, in 85 DEG C of vacuum drying ovens, dries 18h, very
Reciprocal of duty cycle is 20Pa；
Eight, desciccate is placed in Muffle furnace, 500 DEG C of high-temperature roastings, removes organic formwork agent, last gained be containing it is micro--
Mesoporous Beta molecular sieve.
Micro--mesoporous Beta molecular sieve catalyst preparation method of hydrogen production by ethanol steam reforming Ni base, including following operation step
It is rapid:
One, at 29 DEG C, it is above-mentioned micro--mesoporous that the Nickelous nitrate hexahydrate of 14wt% is carried on 0.9g using equi-volume impregnating
Beta molecular sieve；
Two, the sample after load is ground into fine powder, be placed in tube furnace, in N2In 530 DEG C of high-temperature roasting 3h in atmosphere；
Three, after the completion of roasting, powdered samples are subjected to tabletting sieving, micro--mesoporous Beta molecular sieve of Ni base for obtaining 40 mesh is urged
Agent.
Micro--mesoporous Beta molecular sieve catalyst of gained Ni base, for atmospheric fixed bed micro-reaction device in 500 DEG C of progress second
When alcohol vapor reforming hydrogen production Catalysis experiments, the conversion ratio of ethyl alcohol is 99.76%, and the selectivity of hydrogen is 83.9%.
Embodiment 5: micro--mesoporous Beta molecular sieve preparation method, including following operating procedure:
One, by the tetraethyl ammonium hydroxide C of content 25%8H21NO aqueous solution 23.25ml, deionized water 19.25ml, concentration are
The sodium hydroxide solution 2.5ml of 8mol/L is sequentially added, and is stirred evenly；
Two, at 30 DEG C, the mixture of acetonitrile and toluene that volume ratio is 1:1 is added in three-necked flask, reaction is heated to 70 DEG C,
The bromo-octadecane and 0.0025mol N, N, N of 0.005mol are measured respectively ', N '-tetramethyl -1,6- hexamethylene diamine is successively added drop-wise to
In mixed solution, continue return stirring 15 hours at the temperature disclosed above；After reaction, round-bottomed flask is taken out, it is cooling rapidly
To 25 DEG C, after the organic solvent in flask has rotated, the reaction product in flask is dissolved in ethyl acetate, by washing repeatedly
Suction filtration is washed, finally place the product in being dried overnight in 40 DEG C of vacuum ovens, products therefrom is template after drying grinding
[C18H37(CH3)2N+(CH2)6N+(CH3)2C18H37][Br-]2(hereinafter it is abbreviated as C18-6-18Br2)；
Three, by template C18-6-18Br2 With sodium metaaluminate NaAlO21.3g is added in step 1 acquired solution, continues to stir
Uniformly；
Four, ethyl orthosilicate C is measured8H20O4Si 48ml is dissolved in step 3 acquired solution, and 30 DEG C of stirring 40min obtain milky
Silica-alumina gel；
Five, at 45 DEG C, the silica-alumina gel of aging is transferred to interior by white silica-alumina gel constant temperature aging 50h obtained by step 4
Lining is to heat in insulating box under air-proof condition in the stainless steel cauldron of polytetrafluoroethylene (PTFE), and crystallization temperature is 150 DEG C, crystallization
Time is 100h；
Six, reaction kettle after the reaction was completed, is taken out, carries out quenching processing with 10 DEG C of deionized waters, the temperature to reaction kettle drops to
At 20 DEG C, crystallization product is taken out, product is washed repeatedly with deionized water to neutrality；
Seven, the solid product washed is put into clean surface plate, in 95 DEG C of vacuum drying ovens, dries 20h, very
Reciprocal of duty cycle is 20Pa；
Eight, desciccate is placed in Muffle furnace, 450 DEG C of high-temperature roastings, removes organic formwork agent, last gained be containing it is micro--
Mesoporous Beta molecular sieve.
Micro--mesoporous Beta molecular sieve catalyst preparation method of hydrogen production by ethanol steam reforming Ni base, including following operation step
It is rapid:
One, at 30 DEG C, it is above-mentioned micro--mesoporous that the Nickelous nitrate hexahydrate of 10wt% is carried on 1.0g using equi-volume impregnating
Beta molecular sieve；
Two, the sample after load is ground into fine powder, be placed in tube furnace, in N2In 500 DEG C of high-temperature roasting 2h in atmosphere；
Three, after the completion of roasting, powdered samples are subjected to tabletting sieving, micro--mesoporous Beta molecular sieve of Ni base for obtaining 60 mesh is urged
Agent.
Micro--mesoporous Beta molecular sieve catalyst of gained Ni base, for atmospheric fixed bed micro-reaction device in 500 DEG C of progress second
When alcohol vapor reforming hydrogen production Catalysis experiments, the conversion ratio of ethyl alcohol is 97.28%, and the selectivity of hydrogen is 79.58%.
Claims (2)
1. a kind of micro--mesoporous Beta molecular sieve preparation method, it is characterised in that: including following operating procedure:
One, by the tetraethyl ammonium hydroxide C of content 25%8H21NO aqueous solution 23.50ml ± 0.50ml, deionized water 19ml ±
0.50ml, sodium hydroxide solution 3.00ml ± 0.50ml that concentration is 8mol/L are sequentially added, and are stirred evenly；
Two, at 25-30 DEG C, the mixture of acetonitrile and toluene that volume ratio is 1:1 is added in three-necked flask, reaction is heated to
70-75 DEG C, respectively measure 0.005mol bromo-octadecane and 0.0025mol N, N, N ', N '-tetramethyl -1,6- hexamethylene diamine according to
It is secondary to be added drop-wise in mixed solution, continue return stirring 15 hours at the temperature disclosed above；After reaction, round-bottomed flask is taken out,
It is rapidly cooled to 25-30 DEG C, after the organic solvent in flask has rotated, the reaction product in flask is dissolved in ethyl acetate
In, by washing suction filtration repeatedly, finally place the product in being dried overnight in 40-50 DEG C of vacuum oven, dry gained after grinding
Product is template [C18H37(CH3)2N+(CH2)6N+(CH3)2C18H37][Br-]2；
Three, by template C18-6-18Br2 With sodium metaaluminate NaAlO21.200g ± 0.100g is added in step 1 acquired solution,
Continue to stir evenly；
Four, ethyl orthosilicate C is measured8H20O4Si 47.00ml ± 1.00ml is dissolved in step 3 acquired solution, 25-30 DEG C of stirring 30-
60min obtains milky silica-alumina gel；
Five, at 30-80 DEG C, white silica-alumina gel constant temperature aging 30-50h obtained by step 4 turns the silica-alumina gel of aging
It moves in the stainless steel cauldron that liner is polytetrafluoroethylene (PTFE), is heated in insulating box under air-proof condition, crystallization temperature 100-
150 DEG C, crystallization time 80-120h；
Six, reaction kettle after the reaction was completed, is taken out, carries out quenching processing with 10 DEG C of deionized waters, the temperature to reaction kettle drops to
At 20 DEG C, crystallization product is taken out, product is washed repeatedly with deionized water to neutrality；
Seven, the solid product washed is put into clean surface plate, in 80-100 DEG C of vacuum drying oven, drying
10-20h, vacuum degree 20Pa；
Eight, desciccate is placed in Muffle furnace, 450-550 DEG C of high-temperature roasting, removes organic formwork agent, last gained is to contain
Micro--mesoporous Beta molecular sieve.
2. a kind of micro--mesoporous Beta molecular sieve catalyst preparation method of Ni base, it is characterised in that: including following operating procedure:
One, at 25-30 DEG C, the Nickelous nitrate hexahydrate of 10wt% ~ 15wt% is carried on 0.500- using equi-volume impregnating
Micro--mesoporous Beta molecular sieve that 1.000g is prepared according to claim 1 method；
Two, the sample after load is ground into fine powder, be placed in tube furnace, in N2In 500-550 DEG C of high-temperature roasting 2- in atmosphere
3h；
Three, after the completion of roasting, powdered samples is subjected to tabletting sieving, obtain micro--mesoporous Beta molecular sieve of Ni base of 40-60 mesh
Catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811320142.0A CN109231232A (en) | 2018-11-07 | 2018-11-07 | Micro--meso-hole structure Beta molecular sieve, micro--mesoporous Beta molecular sieve catalyst of Ni base and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811320142.0A CN109231232A (en) | 2018-11-07 | 2018-11-07 | Micro--meso-hole structure Beta molecular sieve, micro--mesoporous Beta molecular sieve catalyst of Ni base and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109231232A true CN109231232A (en) | 2019-01-18 |
Family
ID=65077228
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811320142.0A Pending CN109231232A (en) | 2018-11-07 | 2018-11-07 | Micro--meso-hole structure Beta molecular sieve, micro--mesoporous Beta molecular sieve catalyst of Ni base and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109231232A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110038626A (en) * | 2019-05-28 | 2019-07-23 | 河南师范大学 | A kind of preparation method for the multistage porous molecular sieve HP-ZSM-5 preparing propylene for efficient catalytic chloromethane reaction |
| CN113636566A (en) * | 2021-08-05 | 2021-11-12 | 肯特催化材料股份有限公司 | All-silicon Beta molecular sieve synthesis process and all-silicon Beta molecular sieve prepared by same |
| CN113813987A (en) * | 2021-09-30 | 2021-12-21 | 太原理工大学 | Preparation method and application of chain Ni/ZSM-5-V catalyst |
| CN114917950A (en) * | 2022-06-01 | 2022-08-19 | 山东理工大学 | Catalyst for preparing synthesis gas from methanol, preparation method and application thereof |
| CN116178181A (en) * | 2023-02-27 | 2023-05-30 | 安徽东至广信农化有限公司 | A kind of p-aminophenol production process |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1217058A1 (en) * | 2000-12-21 | 2002-06-26 | Techspace Aero S.A. | Thermally protective composition |
| CN1528853A (en) * | 2003-10-09 | 2004-09-15 | 西南石油学院 | Cationic Gemini Surfactants as Oil Displacing Agents |
| CN102351718A (en) * | 2011-08-09 | 2012-02-15 | 太原理工大学 | Gemini cationic surfactant and preparation method thereof |
| CN106185972A (en) * | 2016-07-12 | 2016-12-07 | 太原理工大学 | The preparation method of micro-meso-hole structure Beta molecular sieve |
| CN106276945A (en) * | 2015-06-10 | 2017-01-04 | 中国科学院大连化学物理研究所 | A kind of have in, micropore be combined the RHO-SAPO molecular sieve of pore passage structure |
| US20170114157A1 (en) * | 2015-10-21 | 2017-04-27 | Saudi Arabian Oil Company | Cationic polymers and porous materials |
| CN106904636A (en) * | 2017-03-17 | 2017-06-30 | 中触媒新材料股份有限公司 | It is a kind of with the molecular sieves of SSZ 13 and its synthetic method of microporous mesoporous multi-stage artery structure and application |
-
2018
- 2018-11-07 CN CN201811320142.0A patent/CN109231232A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1217058A1 (en) * | 2000-12-21 | 2002-06-26 | Techspace Aero S.A. | Thermally protective composition |
| CN1528853A (en) * | 2003-10-09 | 2004-09-15 | 西南石油学院 | Cationic Gemini Surfactants as Oil Displacing Agents |
| CN102351718A (en) * | 2011-08-09 | 2012-02-15 | 太原理工大学 | Gemini cationic surfactant and preparation method thereof |
| CN106276945A (en) * | 2015-06-10 | 2017-01-04 | 中国科学院大连化学物理研究所 | A kind of have in, micropore be combined the RHO-SAPO molecular sieve of pore passage structure |
| US20170114157A1 (en) * | 2015-10-21 | 2017-04-27 | Saudi Arabian Oil Company | Cationic polymers and porous materials |
| CN106185972A (en) * | 2016-07-12 | 2016-12-07 | 太原理工大学 | The preparation method of micro-meso-hole structure Beta molecular sieve |
| CN106904636A (en) * | 2017-03-17 | 2017-06-30 | 中触媒新材料股份有限公司 | It is a kind of with the molecular sieves of SSZ 13 and its synthetic method of microporous mesoporous multi-stage artery structure and application |
Non-Patent Citations (4)
| Title |
|---|
| WANG SHIYAO ET AL.: "Gemini quaternary ammonium salt cationic surfactant‐assisted hydrothermal synthesis: An effective way to tune the textural properties of zeolite and the acidity of Beta molecular sieves", 《APPLIED ORGANOMETALLIC CHEMISTRY》 * |
| 李超: "多级孔分子筛的设计制备、传质扩散及催化性能研究", 《中国博士学位论文全文数据库·工程科技Ⅰ辑》 * |
| 赵燕凌等: "Cu /Ni 负载型 Beta 分子筛催化剂的乙醇水蒸气重整制氢催化性能研究", 《燃料化学学报》 * |
| 陈培培: "多级孔道ZSM-5分子筛的合成及其吸附脱硫性能的研究", 《中国优秀硕士学位论文全文数据库·工程科技Ⅰ辑》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110038626A (en) * | 2019-05-28 | 2019-07-23 | 河南师范大学 | A kind of preparation method for the multistage porous molecular sieve HP-ZSM-5 preparing propylene for efficient catalytic chloromethane reaction |
| CN113636566A (en) * | 2021-08-05 | 2021-11-12 | 肯特催化材料股份有限公司 | All-silicon Beta molecular sieve synthesis process and all-silicon Beta molecular sieve prepared by same |
| CN113813987A (en) * | 2021-09-30 | 2021-12-21 | 太原理工大学 | Preparation method and application of chain Ni/ZSM-5-V catalyst |
| CN113813987B (en) * | 2021-09-30 | 2023-05-05 | 太原理工大学 | Preparation method and application of chain-shaped Ni/ZSM-5-V catalyst |
| CN114917950A (en) * | 2022-06-01 | 2022-08-19 | 山东理工大学 | Catalyst for preparing synthesis gas from methanol, preparation method and application thereof |
| CN114917950B (en) * | 2022-06-01 | 2024-05-03 | 山东理工大学 | Methanol to synthesis gas catalyst and its preparation method and application |
| CN116178181A (en) * | 2023-02-27 | 2023-05-30 | 安徽东至广信农化有限公司 | A kind of p-aminophenol production process |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109231232A (en) | Micro--meso-hole structure Beta molecular sieve, micro--mesoporous Beta molecular sieve catalyst of Ni base and preparation method thereof | |
| Zhang et al. | Synthesis of Ni/mesoporous ZSM-5 for direct catalytic conversion of cellulose to hexitols: modulating the pore structure and acidic sites via a nanocrystalline cellulose template | |
| CN114558612B (en) | Hierarchical pore ZSM-5 molecular sieve encapsulated Pt-Ni bimetallic catalyst and its preparation method and application | |
| CN104058423B (en) | A kind of method of the synthesizing ordered foramen magnum-mesoporous-micropore multi-stage porous molecular sieve TS-1 of hard template | |
| CN104043477B (en) | ZSM-5/MCM-48 composite molecular sieve, preparation method and application thereof | |
| CN104069886B (en) | A kind of preparation method and applications of the catalyst for aqueous phase furfural hydrogenation Ketocyclopentane | |
| CN106185972B (en) | The preparation method of micro--meso-hole structure Beta molecular sieves | |
| CN102039201A (en) | Double microporous-mesoporous composite molecular sieve and preparation method thereof | |
| CN109399660B (en) | Hierarchical Pore Beta Molecular Sieve, Hierarchical Pore Beta Molecular Sieve Ca-Ni Catalyst and Preparation Method | |
| Hou et al. | Activated carbon aerogel supported copper catalysts for the hydrogenation of methyl acetate to ethanol: effect of KOH activation | |
| Liu et al. | Synthesis of hierarchically porous silicate-1 and ZSM-5 by hydrothermal transformation of SiO2 colloid crystal/carbon composites | |
| CN113842918A (en) | High-activity anti-sintering methane steam reforming catalyst and preparation method and application thereof | |
| CN116809112A (en) | A molecular sieve supported bimetallic catalyst and its preparation method and use | |
| CN108441245B (en) | A kind of modified composite molecular sieve and its preparation method and use | |
| Yu et al. | Synthesis of novel nanotubular mesoporous nickel phosphates with high performance in epoxidation | |
| CN112850741B (en) | Method for synthesizing small-grain NaY molecular sieve with intracrystalline mesopores | |
| CN109529921A (en) | Hydrogen production by ethanol steam reforming multi-stage porous Beta molecular sieve, Ni type method for preparing catalyst | |
| CN109534358A (en) | A kind of hollow multi-stage porous Beta molecular sieve and its preparation method and application | |
| CN106423262B (en) | A kind of SAPO-34 molecular sieve catalyst with ordered mesopores and preparation method thereof | |
| CN111001433B (en) | Mesoporous zeolite loaded with palladium-copper alloy nanoparticles and preparation method and application thereof | |
| CN104402020A (en) | Micro-mesoporous beta molecular sieve and preparation method and application thereof | |
| CN112279268A (en) | Preparation method and application of hierarchical pore ZSM-5 nano lamellar zeolite | |
| WO2024011905A1 (en) | Metal-supported spinel nickel manganite nanosphere aerogel, preparation method therefor and use thereof | |
| CN109675600B (en) | Preparation method of heterojunction with special exposed surface | |
| Jermy et al. | Optimization, synthesis and characterization of vanadium-substituted thick-walled three-dimensional SBA-16 |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190118 |
|
| RJ01 | Rejection of invention patent application after publication |