CN109529921A - Hydrogen production by ethanol steam reforming multi-stage porous Beta molecular sieve, Ni type method for preparing catalyst - Google Patents
Hydrogen production by ethanol steam reforming multi-stage porous Beta molecular sieve, Ni type method for preparing catalyst Download PDFInfo
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- CN109529921A CN109529921A CN201811359977.7A CN201811359977A CN109529921A CN 109529921 A CN109529921 A CN 109529921A CN 201811359977 A CN201811359977 A CN 201811359977A CN 109529921 A CN109529921 A CN 109529921A
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- molecular sieve
- stage porous
- deionized water
- beta molecular
- catalyst
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- 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 97
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 95
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000001257 hydrogen Substances 0.000 title claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 19
- 238000001666 catalytic steam reforming of ethanol Methods 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000008367 deionised water Substances 0.000 claims abstract description 41
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 41
- 239000012265 solid product Substances 0.000 claims abstract description 26
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002425 crystallisation Methods 0.000 claims abstract description 22
- 230000008025 crystallization Effects 0.000 claims abstract description 22
- 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 abstract description 17
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 17
- 239000011734 sodium Substances 0.000 claims abstract description 17
- -1 nickelous carbonates Chemical class 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 11
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 11
- 229910021485 fumed silica Inorganic materials 0.000 claims abstract description 11
- 230000036571 hydration Effects 0.000 claims abstract description 11
- 238000006703 hydration reaction Methods 0.000 claims abstract description 11
- 229910001388 sodium aluminate Inorganic materials 0.000 claims abstract description 11
- 230000003068 static effect Effects 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 45
- MAUMSNABMVEOGP-UHFFFAOYSA-N (methyl-$l^{2}-azanyl)methane Chemical compound C[N]C MAUMSNABMVEOGP-UHFFFAOYSA-N 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 239000004094 surface-active agent Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 12
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 10
- 238000011017 operating method Methods 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 9
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 claims description 5
- 239000003957 anion exchange resin Substances 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 244000144992 flock Species 0.000 claims description 5
- 238000009415 formwork Methods 0.000 claims description 5
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexamethylene diamine Natural products NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 5
- 230000000171 quenching effect Effects 0.000 claims description 5
- 238000009738 saturating Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 3
- 210000003850 cellular structure Anatomy 0.000 abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 40
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 229960004756 ethanol Drugs 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000012429 reaction media Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 239000012071 phase Substances 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000002407 reforming Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 229910005108 Ni3Si2 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000006057 reforming reaction Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 235000007926 Craterellus fallax Nutrition 0.000 description 1
- 240000007175 Datura inoxia Species 0.000 description 1
- 229910021543 Nickel dioxide Inorganic materials 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 241000124033 Salix Species 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 210000003054 facial bone Anatomy 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- MSNOMDLPLDYDME-UHFFFAOYSA-N gold nickel Chemical compound [Ni].[Au] MSNOMDLPLDYDME-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/7007—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
- 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
-
- 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
-
- 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
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
-
- 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
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
-
- 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
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
-
- 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
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to multistage porous molecular sieves and the standby catalyst of the system with molecular sieve for preparing, specially multi-stage porous Beta molecular sieve and its Ni type method for preparing catalyst, it is single to solve cellular structure, utilization rate is low, fail complete opening, only play suction-operated, easy-sintering, which is reunited, to be inactivated, the problem of forming carbon distribution, scheme: deionized water, sodium metaaluminate NaAlO2, double template stir to obtain clear solution, fumed silica stirring is added, moves into polytetrafluoroethylcontainer container, it is cooling that reactor constant temperature heats static crystallization, after dry high-temperature calcination, take four hydration nickelous carbonates molten, ammonium chloride, ammonium hydroxide is stirred in deionized water, molecular sieve stirring is added, after a certain period of time, washing filters retains solid product to hydrothermal synthesis, dry.Prepared multi-stage porous Beta molecular sieve is rich in micro- mesoporous two-phase height connection cellular structure, and prepared catalyst is class catalyst with core-casing structure, obtains superior returns.
Description
Technical field
The present invention relates to the preparation methods of the standby catalyst of multistage porous molecular sieve and the system with molecular sieve for preparing, specially ethanol water
Vapour reforming hydrogen producing multi-stage porous Beta molecular sieve, Ni type method for preparing catalyst.
Background technique
Currently, the steam reformation technology (being substantially natural gas) of the non-renewable raw material based on fossil fuel is most
Common technology, but this has ignored the after-cost of environment influence.Hydrogen Energy is pollution-free and reproducibility " green " energy.Benefit
Become in recent years with advantages such as bio-ethanol vapor reforming hydrogen production possessing unit energy height, high, nontoxic, the easy storage and transportations of hydrogen content
The hot spot of concern.
Using base metal nickel as active metal for hydrogen production by ethanol steam reforming it is active higher, availability
Extensively, function admirable and feature at low cost.Usually there is easy-sintering and inactivate that this feature limits in existing nickel-base catalyst
The popularization of nickel load type catalyst is made.How to improve that nickel is anti-to be sintered into current urgent problem to be solved.By improving nickel gold
The anti-caking power of nickel-base catalyst can be improved in the dispersion degree of category and the granularity for reducing nickel metal, no matter however using which kind of catalysis
Agent carrier all inevitably by the way of dipping or active metal is supported on carrier surface by the mode of ion exchange, though
The purpose for improving nickel dispersity and reducing Nickel particle degree is so realized to a certain extent, but metallic nickel is always simply by electrostatic
Gravitation is combined with carrier, this just inevitably influences the service life of catalyst.On the other hand, carrier is in ethanol reformation system
Vital influence is also functioned in hydrogen reaction process, relates generally to active sites, the problem of surface area, mass-transfer efficiency.In recent years,
Multistage porous molecular sieve is since its hydrothermal stability is good, and cellular structure is abundant, and the big feature of surface area is concerned.But due to
Cellular structure is covered by Equilibrium cation and later period active metal in molecular sieve, influences the utilization rate in its duct.
Therefore, design prepares a kind of suitable template to synthesize the multistage porous molecular sieve of transgranular micro--meso-hole structure connection
And the duct of multistage porous molecular sieve is made full use of, while establishing active metal and being combined and be applied in a manner of chemical bond with carrier
Bio-ethanol vapor reforming hydrogen production, realize base metal type catalyst it is efficient using be very it is necessary to.
Summary of the invention
The present invention solves molecular sieve, and that there are cellular structures is single, and cellular structure utilization rate is not high, and duct fails complete opening,
Framework of molecular sieve is only capable of playing physical absorption reaction medium, and nickel-base catalyst easy-sintering, which is reunited, to be inactivated, and is easy in catalytic process logical
The problem of reaction medium migration causes carbon distribution is crossed, a kind of cellular structure multiplicity, the high multi-stage porous Beta of duct degree of opening are provided
Molecular sieve, and active metal is introduced into molecular sieve table in a manner of chemical bonded refractory resultant force using this molecular sieve as carrier hydro-thermal method
In facial bone frame, a kind of class catalyst with core-casing structure is prepared, realizes ethanol steam reforming superior returns.
The present invention is realized by following operating procedure: hydrogen production by ethanol steam reforming multi-stage porous Beta system with molecular sieve for preparing is standby
Method, including following operating procedure:
1) first for being 1:1 by the volume ratio that the 4-methyl hexamethylene diamine of the Dodecyl Bromide of 0.2mol and 0.1mol is dissolved in 50mL
In benzene and acetonitrile mixed solution, flow back 48h under the conditions of 70 DEG C of water bath；Be cooled to room temperature, solid product after filtering,
It is washed with cold diethyl ether solution, obtained white solid is in 50 DEG C of vacuum drying 5h, obtained white Gemini surface active agent
[C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25][Br]2 -Being dissolved under the conditions of mixture ratios of 100mL deionized water according to every 10g will
[C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25][Br]2 -It is dissolved in deionized water；By anion exchange resin, obtain saturating
Bright [C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25][OH]2 -Solution, by above-mentioned [C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25][OH]2 -Solution is by being freeze-dried to obtain white flock template [C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25]
[OH]2 -；
2) according to tetraethyl ammonium hydroxide: deionized water: template [C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25][OH-]2:
Sodium metaaluminate (NaAlO2)=10~20: 2~10:1~5:0.4~1 mass ratio measures tetraethyl ammonium hydroxide, deionization
Water, Gemini surface active agent [C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25][OH-]2, sodium metaaluminate (NaAlO2) stirred
It mixes to obtain clear solution；
3) fumed silica SiO is weighed2·nH2O is added in clear solution described in step 2, and room temperature continues stirring 10 minutes
Obtain white silica-alumina gel, wherein the mass ratio of the amount of weighing of fumed silica and sodium metaaluminate is 5~10:0.4~1；Room
Temperature continues stirring and obtains the uniformly white silica-alumina gel containing crystal seed in 10 minutes, prepared white silica-alumina gel is moved into poly-
It in tetrafluoroethene container, is then placed in reaction kettle, closed reactor, places it in airtight heating in insulating box, heating temperature
120~150 DEG C, constant temperature 72~120h of static crystallization becomes crystallization gel solution；
4) it after reaction, takes out reaction kettle to be placed in quenching slot, 20 DEG C is quickly cooled in 10 DEG C of deionized water；
5) reaction kettle is opened, takes out polytetrafluoroethylcontainer container, soaked overnight is washed with deionized in reaction product therein,
Filtering and washing finally discards filtrate, retains solid product to neutrality repeatedly；
6) solid product is put in surface plate, is placed in vacuum oven, 100 DEG C of condition is dry, and vacuum degree 10Pa is dry
Time is 5~12h, takes out desciccate；
7) desciccate is put in 500~550 DEG C of 5~7h of high-temperature calcination in Muffle furnace, removes organic formwork agent to get described in
Multi-stage porous Beta molecular sieve.
The present invention is using double template agent methods, and tetraethyl ammonium hydroxide is as micropore template agent for being oriented to synthesis Beta molecule
Sieve, and [C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25][OH]2 -There are following 3 functions: (1) conduct as the second template
Alkaline matter provides alkaline environment for silica-alumina gel.Often use the mode of addition inorganic salts for body in conventional molecular sieve synthesis
System provides alkaline condition, sieves aluminum-oxygen tetrahedron electronegativity by the final balance molecule of cation in inorganic salts, and uses [C12H25
(CH3)2N+(CH2)6N+(CH3)2C12H25][OH]2 -Afterwards, not only every mole of [C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25]
[OH]2 -2 moles of OH will be provided-, simultaneously because quaternary ammonium base itself can also be used as Zeolite synthesis directed agents and participate in molecule
In the synthesis process of sieve.Due to needing balance molecule sieve skeleton frame electronegativity, [C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25]
[OH]2 -It effectively will comprehensively participate in be formed in molecular sieve precursor liquid, effectively influence the skeleton structure that molecular sieve is formed；(2)
Cause to form class meso-hole structure in molecular sieve crystal as occupy-place agent, due to [C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25]
[OH]2 -Every molecular contains 2 moles of long hydrophobic chains after being dissolved in water, simultaneously because aluminum-oxygen tetrahedron and [C12H25(CH3)2N+
(CH2)6N+(CH3)2C12H25][OH]2 -Because charge conservation is combined closely, therefore long hydrophobic chain is by oriented control microporous molecular sieve hole
Road growth trend, this further ensures that intrinsic micropore canals crystallization around hydrophobic chain is grown, after the completion of crystallization, template
After roasting removes, with regard to the micro- mesoporous connection cellular structure (3) of Lock-in since framework of molecular sieve electronegativity is by N+Balance is gone,
After template removal, framework of molecular sieve shows electronegativity, increases in ethanol steam reforming reaction to electrophilic group
Absorption, further increase catalytic efficiency, purified product composition.
Multi-stage porous Beta molecular sieve Ni type method for preparing catalyst, including following operating procedure:
A) according to four hydration nickelous carbonates: ammonium chloride: the ammonium hydroxide that content is 28%: deionized water=1~2: 5~10:100~150:
500~1000 mass ratio measures four hydration nickelous carbonates, ammonium chloride, the ammonium hydroxide that content is 28%, deionized water and is stirred
To clear solution；
B) it weighs multi-stage porous Beta molecular sieve to be added in step a) in solution obtained, ultrasound 30~60 minutes will prepare
Mixture move into polytetrafluoroethylcontainer container in, be then placed in reaction kettle, closed reactor, place it in closed in insulating box
Heating, becomes crystallization gel solution, multi-stage porous Beta molecular sieve by 100~140 DEG C of heating temperature, constant temperature 1~10h of static crystallization
Mass ratio with deionized water is 1~5:500~1000；
C) reaction kettle is opened, takes out polytetrafluoroethylcontainer container, reaction product deionized water therein and dehydrated alcohol is anti-
Multiple filtering and washing finally discards filtrate, retains solid product to neutrality；
D) solid product is put in surface plate, is placed in vacuum oven, 60 DEG C of condition is dry, and vacuum degree 10Pa is dry
Time is 5~12h, takes out desciccate；
Above-mentioned steps a) ~ d) e) is operated to 1-5 times repeatedly to obtain the multi-stage porous that Ni load capacity accounts for 7~22wt% of catalyst weight
Beta molecular sieve Ni type catalyst.
By active metal by the silicon in hydro-thermal method and framework of molecular sieve in the present invention, oxygen occurs chemical reaction and generates
Ni3Si2O5(OH)4, so that active metal is secured firmly on carrier, high-temperature roasting is needed not move through when as catalyst and is formed
NiO2.This just effectively prevents making active metal because of high-temperature roasting that there is a phenomenon where agglomerations.Simultaneously in hydrogen from ethanol reforming
The carbon deposition phenomenon occurred by active metal migration is decreased during gas.Secondly, in former multi-stage porous molecular sieve carrier surface shape
At the structure of similar petal, carrier surface area is effectively increased, reaction medium and active metal contact frequency are increased, makes to live
Property metal utilization improve.Entire catalyst constitutes the catalyst of a similar core-shell structure.Nucleoid phase structure is multi-stage porous
Beta molecular sieve, since it is with cellular structure complicated and changeable, so that reaction medium mass transfer rate improves, and because it has one
Determine electronegativity, to reaction medium other than the effect of absorption screening, also improve product purity, is conveyed convenient for reaction medium.Class
Shell is the special construction that active metal is effectively fixed, and such nucleocapsid, which plays synergistic effect in catalysis reaction, carries out reaction
It is more thorough, extend catalyst service life.
The present invention is with [C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25][OH-]2It is template with tetraethyl ammonium hydroxide,
Multi-stage porous Beta molecular sieve is synthesized using one step hydro thermal method.Adopt this method the standby catalysis of multi-stage porous Beta system with molecular sieve for preparing of preparation
Agent have it is abundant transgranular mesoporous, simultaneously because be free of Na+, all cellular structures have sufficiently been opened, multi-stage porous point is enhanced
Advantage of the son sieve as carrier, further improves mass-transfer efficiency, increases the surface area of carrier.And in multistage porous molecular sieve
On the basis of further hydro-thermal reaction by base metal active component Ni in a manner of chemical bond in conjunction with framework of molecular sieve, make
Ethanol steam reforming reacting catalytic performance is obtained to increase substantially.
The invention has the following advantages that there is 1, synthesized multi-stage porous molecular sieve the transgranular and intergranular of high-sequential to be situated between
Hole has surface area big, the big excellent physicochemical property of pore volume；And due to addition sodium hydroxide no in synthesis process, institute
Elecrtonegativity with framework of molecular sieve structure is not to pass through Na+It is balanced, therefore after all templates are roasted and removed, duct quilt
Being opened to for maximum possible comes, and molecular sieve shows elecrtonegativity, is conducive to combining closely between active metal and carrier, while advantageous
Suction-operated during ethanol steam reforming to intermediate product；2, multi-stage porous Beta molecular sieve Ni type catalyst of the present invention
It is a kind of containing high degree of dispersion active metal Ni, active metal and multi-stage porous point as hydrogen production by ethanol steam reforming catalyst
Son sieve carrier is combined in a manner of chemical bond, is not only changed the pattern of multistage porous molecular sieve originally, is further improved catalysis
The surface area of agent realizes the raising of the mass-transfer efficiency of reaction medium, also increases the contact frequency of reaction medium and active metal,
To show higher ethanol conversion and hydrogen selective, carbon monoxide, methane, acetaldehyde, Crude products.deep process is greatly reduced
Selectivity, improve product purity.
Detailed description of the invention
Fig. 1 is the XRD spectra comparison of multi-stage porous Beta molecular sieve synthesized by the embodiment of the present invention 1 and Beta molecular sieve
Figure；As shown in the figure: in obtained multi-stage porous Beta sieve sample, the characteristic diffraction peak position of Beta is embodied,
7.6 ° and 22.4 ° have the obvious and higher appearance of crystallinity, and occur without the characteristic diffraction peak of other crystal phases, card
Bright synthesized sample has single Beta zeolite phase, meanwhile, in low angle diffraction locations, synthesized Beta sieve sample
There is Bao Feng at 2 °~3 ° or so, illustrate wherein there is meso-hole structure, and without there is complete meso-hole structure diffraction maximum image,
The not simple composite molecular screen of multi-stage porous Beta molecular sieve for illustrating synthesis, the Beta molecular sieve with meso-hole structure,
Its is mesoporous to be present in molecular sieve crystal phase；Secondly 22.4 or so characteristic diffraction peak has an apparent left side compared to traditional Beta zeolite
It moves, illustrates synthesized multi-stage porous Beta molecular sieve more horn of plenty containing aluminium；
Fig. 2 is the SEM figure of multi-stage porous Beta molecular sieve synthesized by the embodiment of the present invention 1；As shown in Figure 2, synthesized multistage
Hole Beta molecular sieve has shape characteristic abundant, there is the pattern of similar pine tree, absolutely proves, the homemade template of addition
Effectively take part in the synthesis and growth of crystal phase；
Fig. 3 is the figure of multi-stage porous Beta molecular sieve TEM synthesized by the embodiment of the present invention 1；From the figure 3, it may be seen that synthesized multi-stage porous
Beta molecular sieve has apparent Beta molecular sieve lattice fringe, and there are transgranular mesoporous, transgranular mesoporous no destruction molecules
Sieve inherent structure and height connection micropore canals structure and mesopore orbit structure；
Fig. 4 is the N of multi-stage porous Beta molecular sieve and Beta molecular sieve synthesized by the embodiment of the present invention 12Adsorption/desorption curve figure
Comparison diagram；It is as shown in the figure: by N2Adsorption/desorption curve can be seen that multi-stage porous Beta molecular sieve and combine I type, IV type thermoisopleth,
In 0.4 < P/P0< 1.0, there is apparent desorption hysteresis loop, this is that the Beta molecular sieve of the single microcellular structure of tradition does not have
Have, this is because mesoporous presence, has occurred capillary condensation phenomenon, while also illustrating synthesized multi-stage porous Beta points
Mesoporous in son sieve is not that simple intergranular is mesoporous, while adsorbance significantly increases, and illustrate under sodium free system, effective liberation
Cellular structure；
Fig. 5 is the graph of pore diameter distribution of multi-stage porous Beta molecular sieve synthesized by the embodiment of the present invention 1；It is as shown in the figure: by pore
Holding distribution curve can be seen that mesoporous pore size is widely distributed, illustrate synthesized multi-stage porous Beta molecular sieve rich in meso-hole structure；
Fig. 6 is the infrared spectrum comparison diagram of multi-stage porous Beta molecular sieve and Beta molecular sieve synthesized by the embodiment of the present invention 1；By
Figure is it is found that multi-stage porous Beta molecular sieve has and the consistent infrared spectrum of Beta molecular sieve；Absolutely prove synthesized multi-stage porous
Beta molecular sieve is pure BEA zeolite phase；
Fig. 7 is the XRD spectra of multi-stage porous Beta molecular sieve Ni type catalyst synthesized by the embodiment of the present invention 1；As shown, institute
In multi-stage porous Beta molecular sieve Ni type catalyst sample obtained, the not only intact feature diffraction for showing Beta molecular sieve
Also there is Ni in peak3Si2O5(OH)4Characteristic diffraction peak, 34.1 °, 36.7 ° and 60.5 ° have apparent diffraction maximum, and do not have
The characteristic diffraction peak of other crystal phases occurs, especially the characteristic diffraction peak of nickel oxide；Illustrate synthesized multi-stage porous Beta molecule
The intact inherent structure for remaining multi-stage porous Beta molecular sieve of Ni type catalyst is sieved, by active metal also in a manner of chemical bond
Ni dispersion has been fixed in framework of molecular sieve structure；
Fig. 8 is the SEM spectrogram of multi-stage porous Beta molecular sieve Ni type catalyst synthesized by the embodiment of the present invention 1；As shown, institute
The multi-stage porous Beta molecular sieve Ni type catalyst of synthesis has similar petal-like pattern, absolutely proves that Ni is uniformly dispersed in
On framework of molecular sieve, while expanding the contact area of reaction medium and carrier；
Fig. 9 is the TEM spectrogram of multi-stage porous Beta molecular sieve Ni type catalyst synthesized by the embodiment of the present invention 1；As shown, institute
The multi-stage porous Beta molecular sieve Ni type catalyst-rich of synthesis contains Ni3Si2O5(OH)4Structure, and Ni3Si2O5(OH)4Similar willow leaf
Shape, while being observed that catalyst has apparent nuclear phase and shell structurre by TEM spectrogram.
Specific embodiment
Embodiment 1: hydrogen production by ethanol steam reforming multi-stage porous Beta molecular sieve preparation method, including following operating procedure:
1) first for being 1:1 by the volume ratio that the 4-methyl hexamethylene diamine of the Dodecyl Bromide of 0.2mol and 0.1mol is dissolved in 50mL
In benzene and acetonitrile mixed solution, flow back 48h under the conditions of 70 DEG C of water bath；Be cooled to room temperature, solid product after filtering,
It is washed with cold diethyl ether solution, obtained white solid is in 50 DEG C of vacuum drying 5h, obtained white Gemini surface active agent
[C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25][Br]2 -Being dissolved under the conditions of mixture ratios of 100mL deionized water according to every 10g will
[C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25][Br]2 -It is dissolved in deionized water；By anion exchange resin, obtain saturating
Bright [C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25][OH]2 -Solution, by above-mentioned [C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25][OH]2 -Solution is by being freeze-dried to obtain white flock template [C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25]
[OH]2 -；
2) according to tetraethyl ammonium hydroxide: deionized water: Gemini surface active agent [C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25][OH-]2: sodium metaaluminate (NaAlO2): the mass ratio of=10:5:3:1, measure tetraethyl ammonium hydroxide, deionized water,
Gemini surface active agent [C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25][OH-]2, sodium metaaluminate (NaAlO2) be stirred
To clear solution；
3) fumed silica (SiO is weighed2·nH2O it) is added in clear solution described in step 1, room temperature continues 10 points of stirring
Clock obtains white silica-alumina gel, wherein the mass ratio of the amount of weighing of fumed silica and sodium metaaluminate is 10:1；Room temperature continues
Stirring obtains the uniformly white silica-alumina gel containing crystal seed in 10 minutes, and prepared white silica-alumina gel is moved into polytetrafluoroethyl-ne
It in alkene container, is then placed in reaction kettle, closed reactor, places it in airtight heating in insulating box, 150 DEG C of heating temperature,
Constant temperature static crystallization 72h, becomes crystallization gel solution；
4) it after reaction, takes out reaction kettle to be placed in quenching slot, 20 DEG C is quickly cooled in 10 DEG C of deionized water；
5) reaction kettle is opened, takes out polytetrafluoroethylcontainer container, soaked overnight is washed with deionized in reaction product therein,
Filtering and washing finally discards filtrate, retains solid product to neutrality repeatedly；
6) solid product is put in surface plate, is placed in vacuum oven, 100 DEG C of condition is dry, and vacuum degree 10Pa is dry
Time is 5h, takes out desciccate；
7) desciccate is put in 550 DEG C of high-temperature calcination 5h in Muffle furnace, removes organic formwork agent to get the multi-stage porous is arrived
Beta molecular sieve.
Multi-stage porous Beta molecular sieve Ni type method for preparing catalyst, including following operating procedure:
A) according to four hydration nickelous carbonates: ammonium chloride: the ammonium hydroxide that content is 28%: deionized water=1: the quality of 5:100:500
Than measuring four hydration nickelous carbonates, ammonium chloride, the ammonium hydroxide that content is 28%, deionized water and being stirred to obtain clear solution；
B) the multi-stage porous Beta molecular sieve for weighing above-mentioned preparation is added in step 1 in solution obtained, and ultrasound 60 minutes will match
The mixture made moves into polytetrafluoroethylcontainer container, is then placed in reaction kettle, closed reactor places it in insulating box
Airtight heating, becomes crystallization gel solution by 140 DEG C of heating temperature, constant temperature static crystallization 1h, multi-stage porous Beta molecular sieve and go from
The mass ratio of sub- water is 1:500；
C) reaction kettle is opened, takes out polytetrafluoroethylcontainer container, reaction product deionized water therein and dehydrated alcohol is anti-
Multiple filtering and washing finally discards filtrate, retains solid product to neutrality；
D) solid product is put in surface plate, is placed in vacuum oven, 60 DEG C of condition is dry, and vacuum degree 10Pa is dry
Time is 12h, takes out desciccate；
Above-mentioned steps a) ~ d) e) is operated to 5 times repeatedly to obtain the multi-stage porous Beta point that Ni load capacity accounts for catalyst weight 22wt%
Son sieve Ni type catalyst.
Ethanol steam is carried out to above-mentioned catalyst using atmospheric fixed bed micro-reactor (internal diameter 10mm, length 60cm)
Reforming reaction evaluation.By above-mentioned catalyst tabletting, it is crushed, is sized to 60 mesh, 0 .1g of amount of fill.Reaction is in 500 DEG C, normal pressure, liquid
Phase feed ethanol and water quality air speed (WHSV) 15h-1Under the conditions of carry out.
Reaction result is ethanol conversion up to 90.5%, and the selectivity of hydrogen is up to 67.7%.
Embodiment 2: hydrogen production by ethanol steam reforming multi-stage porous Beta molecular sieve preparation method, including following operating procedure:
1) first for being 1:1 by the volume ratio that the 4-methyl hexamethylene diamine of the Dodecyl Bromide of 0.2mol and 0.1mol is dissolved in 50mL
In benzene and acetonitrile mixed solution, flow back 48h under the conditions of 70 DEG C of water bath；Be cooled to room temperature, solid product after filtering,
It is washed with cold diethyl ether solution, obtained white solid is in 50 DEG C of vacuum drying 5h, obtained white Gemini surface active agent
[C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25][Br]2 -Being dissolved under the conditions of mixture ratios of 100mL deionized water according to every 10g will
[C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25][Br]2 -It is dissolved in deionized water；By anion exchange resin, obtain saturating
Bright [C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25][OH]2 -Solution, by above-mentioned [C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25][OH]2 -Solution is by being freeze-dried to obtain white flock template [C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25]
[OH]2 -；
2) according to tetraethyl ammonium hydroxide: deionized water: Gemini surface active agent [C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25][OH-]2): sodium metaaluminate NaAlO2:=20: 10:5:0.4 mass ratio measures tetraethyl ammonium hydroxide, deionization
Water, Gemini surface active agent [C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25][OH-]2, sodium metaaluminate NaAlO2It is stirred
Obtain clear solution；
3) fumed silica SiO is weighed2·nH2O is added in clear solution described in step 1, and room temperature continues stirring 10 minutes
Obtain white silica-alumina gel, wherein the mass ratio of the amount of weighing of fumed silica and sodium metaaluminate is 5:0.4；Room temperature continues
Stirring obtains the uniformly white silica-alumina gel containing crystal seed in 10 minutes, and prepared white silica-alumina gel is moved into polytetrafluoroethyl-ne
It in alkene container, is then placed in reaction kettle, closed reactor, places it in airtight heating in insulating box, 120 DEG C of heating temperature,
Constant temperature static crystallization 120h, becomes crystallization gel solution；
4) it after reaction, takes out reaction kettle to be placed in quenching slot, 20 DEG C is quickly cooled in 10 DEG C of deionized water；
5) reaction kettle is opened, takes out polytetrafluoroethylcontainer container, soaked overnight is washed with deionized in reaction product therein,
Filtering and washing finally discards filtrate, retains solid product to neutrality repeatedly；
6) solid product is put in surface plate, is placed in vacuum oven, 100 DEG C of condition is dry, and vacuum degree 10Pa is dry
Time is 10h, takes out desciccate；
7) desciccate is put in 500 DEG C of high-temperature calcination 7h in Muffle furnace, removes organic formwork agent to get the multi-stage porous is arrived
Beta molecular sieve.
Multi-stage porous Beta molecular sieve Ni type method for preparing catalyst, including following operating procedure:
A) according to four hydration nickelous carbonates: ammonium chloride: the ammonium hydroxide that content is 28%: deionized water=2: the quality of 10:150:1000
Than measuring four hydration nickelous carbonates, ammonium chloride, the ammonium hydroxide that content is 28%, deionized water and being stirred to obtain clear solution；
B) the multi-stage porous Beta molecular sieve for weighing above-mentioned preparation is added in step 1 in solution obtained, and ultrasound 30 minutes will match
The mixture made moves into polytetrafluoroethylcontainer container, is then placed in reaction kettle, closed reactor places it in insulating box
Airtight heating, becomes crystallization gel solution by 100 DEG C of heating temperature, constant temperature static crystallization 10h, grade hole Beta molecular sieve and go from
The mass ratio of sub- water is 5:1000；
C) reaction kettle is opened, takes out polytetrafluoroethylcontainer container, reaction product deionized water therein and dehydrated alcohol is anti-
Multiple filtering and washing finally discards filtrate, retains solid product to neutrality；
D) solid product is put in surface plate, is placed in vacuum oven, 60 DEG C of condition is dry, and vacuum degree 10Pa is dry
Time is 5h, takes out desciccate；
Above-mentioned steps a) ~ d) e) is operated to 3 times repeatedly to obtain the multi-stage porous Beta point that Ni load capacity accounts for catalyst weight 10wt%
Son sieve Ni type catalyst.
Ethanol steam is carried out to above-mentioned catalyst using atmospheric fixed bed micro-reactor (internal diameter 10mm, length 60cm)
Reforming reaction evaluation.By above-mentioned catalyst tabletting, it is crushed, is sized to 60 mesh, 0 .1g of amount of fill.Reaction is in 550 DEG C, normal pressure, liquid
Phase feed ethanol and water quality air speed (WHSV) 20h-1Under the conditions of carry out.
Reaction result is ethanol conversion up to 95 .1%, and the selectivity of hydrogen is up to 70.7%.
Embodiment 3: hydrogen production by ethanol steam reforming multi-stage porous Beta molecular sieve preparation method, including following operating procedure:
1) first for being 1:1 by the volume ratio that the 4-methyl hexamethylene diamine of the Dodecyl Bromide of 0.2mol and 0.1mol is dissolved in 50mL
In benzene and acetonitrile mixed solution, flow back 48h under the conditions of 70 DEG C of water bath；Be cooled to room temperature, solid product after filtering,
It is washed with cold diethyl ether solution, obtained white solid is in 50 DEG C of vacuum drying 5h, obtained white Gemini surface active agent
[C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25][Br]2 -Being dissolved under the conditions of mixture ratios of 100mL deionized water according to every 10g will
[C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25][Br]2 -It is dissolved in deionized water；By anion exchange resin, obtain saturating
Bright [C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25][OH]2 -Solution, by above-mentioned [C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25][OH]2 -Solution is by being freeze-dried to obtain white flock template [C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25]
[OH]2 -；
2) according to tetraethyl ammonium hydroxide: deionized water: Gemini surface active agent [C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25][OH-]2: sodium metaaluminate NaAlO2The mass ratio of :=15:2:1:0.6, measure tetraethyl ammonium hydroxide, deionized water,
Gemini surface active agent [C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25][OH-]2, sodium metaaluminate NaAlO2It is stirred to obtain
Clear solution；
3) fumed silica SiO is weighed2·nH2O is added in clear solution described in step 1, and room temperature continues stirring 10 minutes
Obtain white silica-alumina gel, wherein the mass ratio of the amount of weighing of fumed silica and sodium metaaluminate is 6:0.6；Room temperature continues
Stirring obtains the uniformly white silica-alumina gel containing crystal seed in 10 minutes, and prepared white silica-alumina gel is moved into polytetrafluoroethyl-ne
It in alkene container, is then placed in reaction kettle, closed reactor, places it in airtight heating in insulating box, 140 DEG C of heating temperature,
Constant temperature static crystallization 96h, becomes crystallization gel solution；
4) it after reaction, takes out reaction kettle to be placed in quenching slot, 20 DEG C is quickly cooled in 10 DEG C of deionized water；
5) reaction kettle is opened, takes out polytetrafluoroethylcontainer container, soaked overnight is washed with deionized in reaction product therein,
Filtering and washing finally discards filtrate, retains solid product to neutrality repeatedly；
6) solid product is put in surface plate, is placed in vacuum oven, 100 DEG C of condition is dry, and vacuum degree 10Pa is dry
Time is 12h, takes out desciccate；
7) desciccate is put in 550 DEG C of high-temperature calcination 6h in Muffle furnace, removes organic formwork agent to get the multi-stage porous is arrived
Beta molecular sieve.
Multi-stage porous Beta molecular sieve Ni type method for preparing catalyst, including following operating procedure:
A) according to four hydration nickelous carbonates: ammonium chloride: the ammonium hydroxide that content is 28%: deionized water=1: the mass ratio of 7:120:700,
Four hydration nickelous carbonates, ammonium chloride, the ammonium hydroxide that content is 28%, deionized water is measured to be stirred to obtain clear solution；
B) the multi-stage porous Beta molecular sieve for weighing above-mentioned preparation is added in step 1 in solution obtained, and ultrasound 50 minutes will match
The mixture made moves into polytetrafluoroethylcontainer container, is then placed in reaction kettle, closed reactor places it in insulating box
Airtight heating, becomes crystallization gel solution, grade hole Beta molecular sieve and deionization by 120 DEG C of heating temperature, constant temperature static crystallization 7h
The mass ratio of water is 3:600；
C) reaction kettle is opened, takes out polytetrafluoroethylcontainer container, reaction product deionized water therein and dehydrated alcohol is anti-
Multiple filtering and washing finally discards filtrate, retains solid product to neutrality；
D) solid product is put in surface plate, is placed in vacuum oven, 60 DEG C of condition is dry, and vacuum degree 10Pa is dry
Time is 10h, takes out desciccate；
Above-mentioned steps a) ~ d) e) is operated to 1 time repeatedly to obtain the multi-stage porous Beta point that Ni load capacity accounts for catalyst weight 7wt%
Son sieve Ni type catalyst.
Ethanol steam is carried out to above-mentioned catalyst using atmospheric fixed bed micro-reactor (internal diameter 10mm, length 60cm)
Reforming reaction evaluation.By above-mentioned catalyst tabletting, it is crushed, is sized to 60 mesh, amount of fill 0.1g.Reaction is in 600 DEG C, normal pressure, liquid
Phase feed ethanol and water quality air speed (WHSV) 28.5h-1Under the conditions of carry out.
Reaction result is ethanol conversion up to 92.5%, and the selectivity of hydrogen is up to 73.0%.
Claims (2)
1. a kind of hydrogen production by ethanol steam reforming multi-stage porous Beta molecular sieve preparation method, it is characterised in that: including following operation
Step:
It 1) is, 1:1's by the volume ratio that the 4-methyl hexamethylene diamine of the Dodecyl Bromide of 0.2mol and 0.1mol is dissolved in 50mL
In toluene and acetonitrile mixed solution, flow back 48h under the conditions of 70 DEG C of water bath；It is cooled to room temperature, solid product is through filtering
Afterwards, it is washed with cold diethyl ether solution, obtained white solid is in 50 DEG C of vacuum drying 5h, obtained white Gemini surface active agent
[C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25][Br]2 -Being dissolved under the conditions of mixture ratios of 100mL deionized water according to every 10g will
[C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25][Br]2 -It is dissolved in deionized water；By anion exchange resin, obtain saturating
Bright [C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25][OH]2 -Solution, by above-mentioned [C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25][OH]2 -Solution is by being freeze-dried to obtain white flock template [C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25]
[OH]2 -；
2), according to tetraethyl ammonium hydroxide: deionized water: template [C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25]
[OH-]2: sodium metaaluminate NaAlO2=10~20: 2~10:1~5:0.4~1 mass ratio measures tetraethyl ammonium hydroxide, goes
Ionized water, Gemini surface active agent [C12H25(CH3)2N+(CH2)6N+(CH3)2C12H25][OH-]2, sodium metaaluminate NaAlO2It carries out
Stir to get clear solution；
3) fumed silica SiO, is weighed2·nH2O is added in clear solution described in step 2, and room temperature continues stirring 10 minutes
Obtain white silica-alumina gel, wherein the mass ratio of the amount of weighing of fumed silica and sodium metaaluminate is 5~10:0.4~1；Room
Temperature continues stirring and obtains the uniformly white silica-alumina gel containing crystal seed in 10 minutes, prepared white silica-alumina gel is moved into poly-
It in tetrafluoroethene container, is then placed in reaction kettle, closed reactor, places it in airtight heating in insulating box, heating temperature
120~150 DEG C, constant temperature 72~120h of static crystallization becomes crystallization gel solution；
4) it, after reaction, takes out reaction kettle to be placed in quenching slot, 20 DEG C is quickly cooled in 10 DEG C of deionized water；
5), reaction kettle is opened, polytetrafluoroethylcontainer container is taken out, reaction product therein is washed with deionized and was impregnated
At night, filtering and washing to neutrality, finally discards filtrate repeatedly, retains solid product；
6), solid product is put in surface plate, is placed in vacuum oven, 100 DEG C of condition is dry, and vacuum degree 10Pa is done
The dry time is 5~12h, takes out desciccate；
7) desciccate, is put in 500~550 DEG C of 5~7h of high-temperature calcination in Muffle furnace, removes organic formwork agent to get institute is arrived
The multi-stage porous Beta molecular sieve stated.
2. a kind of multi-stage porous Beta molecular sieve Ni type method for preparing catalyst, it is characterised in that: including following operating procedure:
A), according to four hydration nickelous carbonates: ammonium chloride: the ammonium hydroxide that content is 28%: deionized water=1~2: 5~10:100~
The mass ratio of 150:500~1000 measures four hydration nickelous carbonates, ammonium chloride, the ammonium hydroxide that content is 28%, deionized water and is stirred
It mixes to obtain clear solution；
B), the multi-stage porous Beta molecular sieve for weighing method preparation as described in claim 1 is added to solution obtained in step a)
In, prepared mixture is moved into polytetrafluoroethylcontainer container, is then placed in reaction kettle by ultrasound 30~60 minutes, closed
Reaction kettle places it in airtight heating in insulating box, 100~140 DEG C of heating temperature, constant temperature 1~10h of static crystallization, becomes brilliant
The mass ratio of change gel solution, multi-stage porous Beta molecular sieve and deionized water is 1~5:500~1000；
C), reaction kettle is opened, takes out polytetrafluoroethylcontainer container, reaction product deionized water therein and dehydrated alcohol is anti-
Multiple filtering and washing finally discards filtrate, retains solid product to neutrality；
D), solid product is put in surface plate, is placed in vacuum oven, 60 DEG C of condition is dry, and vacuum degree 10Pa is dry
Time is 5~12h, takes out desciccate；
E), above-mentioned steps a) ~ d) is operated to 1-5 times repeatedly to obtain the multi-stage porous that Ni load capacity accounts for 7~22wt% of catalyst weight
Beta molecular sieve Ni type catalyst.
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