CN116237030A - Nickel-ruthenium-zirconium/attapulgite-based molecular sieve catalyst and application thereof - Google Patents
Nickel-ruthenium-zirconium/attapulgite-based molecular sieve catalyst and application thereof Download PDFInfo
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- CN116237030A CN116237030A CN202211678225.3A CN202211678225A CN116237030A CN 116237030 A CN116237030 A CN 116237030A CN 202211678225 A CN202211678225 A CN 202211678225A CN 116237030 A CN116237030 A CN 116237030A
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- attapulgite
- molecular sieve
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- ruthenium
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- 229960000892 attapulgite Drugs 0.000 title claims abstract description 92
- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 92
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 70
- 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 70
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- -1 Nickel-ruthenium-zirconium Chemical compound 0.000 title claims abstract description 46
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 33
- 239000001257 hydrogen Substances 0.000 claims abstract description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 19
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 19
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000002407 reforming Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000007634 remodeling Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 23
- 238000000227 grinding Methods 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 16
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000003921 oil Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000012075 bio-oil Substances 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000012071 phase Substances 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 229920000428 triblock copolymer Polymers 0.000 claims description 8
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 6
- 239000008247 solid mixture Substances 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 238000000508 aqueous-phase reforming Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 4
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 4
- 230000002572 peristaltic effect Effects 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 125000003916 ethylene diamine group Chemical group 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 15
- 230000008901 benefit Effects 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000007789 gas Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 26
- 239000007787 solid Substances 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 10
- 230000003068 static effect Effects 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 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 description 5
- 238000005303 weighing Methods 0.000 description 5
- WXKDNDQLOWPOBY-UHFFFAOYSA-N zirconium(4+);tetranitrate;pentahydrate Chemical compound O.O.O.O.O.[Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WXKDNDQLOWPOBY-UHFFFAOYSA-N 0.000 description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 239000004927 clay Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000004913 activation Effects 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
- 238000004873 anchoring Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- 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
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- 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
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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- 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
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
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- 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
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- C01B2203/1041—Composition of the catalyst
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- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
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- C01B2203/1229—Ethanol
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Abstract
The invention discloses a nickel-ruthenium-zirconium/attapulgite-based molecular sieve catalyst and application thereof, wherein the catalyst comprises a carrier and an active component loaded on the carrier, the carrier is an attapulgite-based molecular sieve prepared by structural remodeling of attapulgite, and the attapulgite-based molecular sieve is subjected to desilication treatment; the active components are nickel, ruthenium and zirconium. The nickel-ruthenium-zirconium/attapulgite-based porous catalyst used in the invention has excellent conversion rate, hydrogen yield/selectivity and higher stability in the water phase reforming hydrogen production of biological oil and model compounds thereof, the conversion rate of raw materials such as biological oil reaches 100%, the hydrogen yield is more than 80%, the purity of hydrogen in product gas is more than 70%, good stability is maintained in the reaction for 200 hours, the method has the advantages of green and economy, the industrial requirement of the water phase reforming hydrogen production of biological oil is met, and the method has good industrial application prospect.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a nickel-ruthenium-zirconium/attapulgite-based molecular sieve catalyst and application thereof.
Background
With the greenhouse gases (CO) 2 /CH 4 ) The emission amount rises year by year, and the research and development of the green hydrogen production technology has important significance for relieving environmental problems, guaranteeing energy supply and realizing a double-carbon target. In recent years, research has been made into converting renewable, carbon-neutral biomass resources into bio-oil by using a thermal cracking technology, and then producing hydrogen by using an aqueous phase reforming technology, so that low-energy-density biomass can be subjected to energy enrichment, thereby reducing transportation cost and energy consumption. The process is considered to have the advantages of process economy, low reaction temperature, zero carbon emission in the hydrogen production process and the like. Therefore, the biological oil steam reforming hydrogen production is a promising green hydrogen production technology.
However, there are a number of parallel reactions that are affected by catalyst structure and performance in the bio-oil aqueous phase reforming hydrogen production process. The research and development of economic and green catalysts are key to realizing the hydrogen production by the water phase reforming of the high-efficiency biological oil. In the research of the bio-oil water phase and the model catalytic reforming hydrogen production catalyst thereof, the noble metal catalyst (such as Rh and the like) shows high catalytic conversion activity and hydrogen selectivity, because d orbitals of noble metal atoms which are not filled with electrons have strong adsorption capacity on bio-oil molecules, and reactant molecules can be activated to form intermediate species with high reactivity. However, the high cost and low reserves of noble metals limit their industrial application. At present, the scholars at home and abroad mainly focus on the research of the low-cost nickel metal-based catalyst. However, the structural composition characteristics of the bio-oil and the carbon affinity of Ni metal lead to the easy occurrence of sintering and carbon deposition of the nickel-based catalyst, resulting in short service life of the catalyst.
Therefore, how to prepare a carrier with large specific surface area and pore volume and excellent hydrothermal stability, selectively load nickel-based composite active components, realize selective bond breaking on bio-oil molecules, improve the carbon deposit removal capacity of the catalyst surface, inhibit active nickel metal sintering and enhance hydrogen yield, and is a key for solving the deactivation of the current nickel-based steam reforming hydrogen production catalyst.
Disclosure of Invention
The invention mainly aims to provide a nickel-ruthenium-zirconium/attapulgite-based molecular sieve catalyst with high conversion rate and hydrogen yield and long service life and application thereof.
The invention provides a nickel-ruthenium-zirconium/attapulgite-based molecular sieve catalyst, which comprises a carrier and an active component loaded on the carrier, wherein the carrier is an attapulgite-based molecular sieve prepared by structural remodeling of attapulgite, and the attapulgite-based molecular sieve is subjected to desilication treatment to construct a surface silicon-aluminum cavity; the active components are nickel, ruthenium and zirconium.
Further, the content of nickel is 3-5 wt%, the content of ruthenium is 0.1-3 wt%, the content of zirconium is 5-10 wt%, and the balance is attapulgite-based molecular sieve.
Further, the attapulgite-based molecular sieve is prepared by structurally remolding attapulgite by an ammonia vapor induced recrystallization method, and the specific preparation method comprises the following steps:
mixing attapulgite with NH 4 F. Mixing and grinding NaOH, a template agent and a structure directing agent to obtain a mixture I, transferring the mixture I into a synthesis kettle, adding ammonia water solution, then carrying out constant temperature treatment at 160-200 ℃ for 48-72 h to obtain a solid mixture II, collecting the mixture II for grinding, and then carrying out constant temperature calcination at 500-700 ℃ in an air atmosphere for 4-8 h to obtain the attapulgite-based molecular sieve.
Further, the template agent is a mixture of tetrapropylammonium bromide and triblock copolymer P123 mixed according to the mass ratio of 1:1 or a mixture of tetraethylammonium bromide and triblock copolymer P123 mixed according to the mass ratio of 1:1, the structure directing agent is ethylenediamine, attapulgite and NH 4 F. The mass ratio of NaOH to template agent to structure guiding agent is 1:0.2-0.5:0.2-0.5:0.5-1:0.1～0.5。
further, the specific preparation method for carrying out the desilication treatment on the attapulgite-based molecular sieve comprises the following steps:
sequentially treating the attapulgite-based molecular sieve with an acid solution and an alkali solution in a hydrothermal synthesis kettle at 180 ℃ for 4-6 hours, performing centrifugal separation, filtering and drying after each treatment, and finally calcining.
Further, the acid solution is 3.5mol/L oxalic acid solution or 3.5mol/L hydrochloric acid solution, and the alkali solution is 3.5mol/L NH 4 The ratio of the attapulgite-based molecular sieve to the acid solution or the alkali solution is 1 g:20-30 mL.
Further, the specific preparation method for loading nickel, ruthenium and zirconium on the attapulgite-based molecular sieve comprises the following steps:
mixing a nickel precursor, a ruthenium precursor, a zirconium precursor and a surfactant in absolute ethyl alcohol uniformly, adding an attapulgite molecular sieve with surface silicon-aluminum cavities, stirring at a constant temperature of 80 ℃ until the ethanol is completely evaporated, filtering and collecting a solid product, drying and grinding, and calcining at a constant temperature of 500-700 ℃ and an air atmosphere of 30mL/min for 4-8 hours to realize the loading of nickel, ruthenium and zirconium on the attapulgite molecular sieve, thereby preparing the nickel-ruthenium-zirconium/attapulgite molecular sieve catalyst.
Further, the surfactant is any one of sodium dodecyl benzene sulfonate, CTAB and zwitterionic polyacrylamide.
The invention also provides application of the nickel-ruthenium-zirconium/attapulgite-based molecular sieve catalyst in preparing hydrogen by reforming biological oil and a model object thereof in water phase.
The invention also provides a method for preparing hydrogen by reforming the biological oil and the model water phase thereof, which comprises the following steps: the raw materials, the nickel-ruthenium-zirconium/attapulgite-based molecular sieve catalyst and water are added into a reactor for reaction, the catalyst dosage is 0.1-0.5 g, the raw material feeding rate is 0.001-0.01 g/min, the water is injected into the reactor through a peristaltic pump, the S/C ratio of the water and the reactant in the feeding is 1.5-10, and the reaction temperature is 200-400 ℃.
Attapulgite is a natural cheap clay with a 2:1 type phyllosilicate structure, i.e. a [ Mg/AlO ] 6 ]Octahedron connects two inversed [ SiO ] through Mg/Al-O-Si bond 4 ]Tetrahedra extend to infinity to form a hollow fiber structure having a nano-size. And [ SiO ] in attapulgite 4 ]Tetrahedra and [ AlO ] 6 ]The octahedral structure is similar to zeolite. Therefore, based on the composition and structural characteristics of the natural attapulgite clay, the porous carrier with a specific structure can be prepared by remolding the structure of the natural attapulgite clay. And then carrying out local desilication and aluminum treatment on the active component to construct a porous carrier with specific defect positions, namely silicon-aluminum holes, and then carrying out loading on the active component by using the defect positions, so that the anchoring of the carrier to the active component can be increased, and the sintering resistance of the active component can be improved. In addition, the specific porous structure of the carrier can improve the heat and mass transfer effect in the reaction process and improve the reaction efficiency.
The active metals of ruthenium and zirconium are compounded with nickel components, and nickel-ruthenium-zirconium can be organically combined to form a mixed metal oxide solid solution with a specific structure by utilizing a specific treatment process in the preparation process, so that the sintering resistance of the active nickel metal is enhanced. In addition, the ruthenium active metal has excellent C-C bond rupture and dehydrogenation functions on biological oil/model compounds, and can obviously improve the hydrogen yield and reduce the reaction temperature; the zirconium component is introduced into the catalyst and mainly exists in the form of oxide, and nickel and ruthenium can mutually cause zirconium oxide lattice distortion with zirconium, so that oxygen holes on the surface of the catalyst are increased, and the removal of carbon-related deposition species on the surface of the catalyst is improved. The composite structure of the active component can simultaneously improve the sintering resistance and the carbon deposit resistance of the catalytic active component.
The beneficial effects of the invention are as follows:
the catalyst of the invention adopts nickel-ruthenium-zirconium as an active component, can enhance the capability of the catalyst on the C-C, C-H, C-O bond of biological oil molecules, and can achieve relatively higher activity by loading low-content nickel-ruthenium-zirconium with an attapulgite-based porous carrier. Compared with other nickel-based catalysts, the catalyst disclosed by the invention has the advantages that through constructing the surface holes of the attapulgite-based porous carrier and the interaction between nickel-ruthenium-zirconium components, the active components are effectively introduced into the silicon-aluminum holes on the surface of the carrier by using a surfactant-assisted impregnation method, so that the carbon deposition resistance and sintering resistance of the catalyst are obviously improved.
The nickel-ruthenium-zirconium/attapulgite-based porous catalyst used in the invention has excellent conversion rate, hydrogen yield/selectivity and higher stability in the water phase reforming hydrogen production of biological oil and model compounds thereof, the conversion rate of raw materials such as biological oil reaches 100%, the hydrogen yield is more than 80%, the purity of hydrogen in product gas is more than 70%, good stability is maintained in the reaction for 200 hours, the method has the advantages of green and economy, the industrial requirement of the water phase reforming hydrogen production of biological oil is met, and the method has good industrial application prospect.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The various materials used in the examples below, unless otherwise specified, are commercially available products known in the art.
Example 1
Preparing an attapulgite-based molecular sieve carrier with surface silicon-aluminum cavities:
mixing 1g of attapulgite with 0.2g of NH 4 F. A mixture I was formed by physical mortar for 2 hours from 0.2g NaOH, 0.5g tetrapropylammonium bromide+triblock copolymer P123 (mass ratio 1:1) and 0.1g ethylenediamine. Transferring the mixture I onto a fixed support, placing the support into a polytetrafluoroethylene lining stainless steel synthesis kettle, adding 10ml of ammonia water solution at the bottom of the kettle, performing constant temperature treatment at 160 ℃ for 48 hours to obtain a solid mixture II, collecting and grinding the mixture II, and performing constant temperature calcination at 500 ℃ in a static air atmosphere for 4 hours to obtain the attapulgite-based molecular sieve carrier.
Weighing 1g of attapulgite-based molecular sieve carrier, mixing with 20mL of 3.5mol/L oxalic acid solution, placing in a hydrothermal synthesis kettle, treating for 4 hours at 180 ℃, and obtaining solid III after centrifugal separation, filtration, drying and grinding; then the solid III is mixed with 20mL of 3.5mol/L NH 4 Mixing OH solutions, placing the mixture in a hydrothermal synthesis kettle, treating the mixture at 180 ℃ for 4 hours, and obtaining solid IV after centrifugal separation, filtration, drying and grinding; calcining the solid IV at a constant temperature of 500 ℃ for 4 hours in a static air atmosphere to obtain the attapulgite-based molecular sieve carrier with surface silicon-aluminum holes, which is denoted as S1.
Example 2
Preparing an attapulgite-based molecular sieve carrier with surface silicon-aluminum cavities:
mixing 1.0g of attapulgite with 0.5g of NH 4 F. A mixture I was formed by physical mortar for 2 hours from 0.5g NaOH, 1.0g tetraethylammonium bromide+triblock copolymer P123 (mass ratio 1:1) and 0.5g ethylenediamine. Transferring the mixture I onto a fixed support, placing the support into a polytetrafluoroethylene lining stainless steel synthesis kettle, adding 10ml of ammonia water solution at the bottom of the kettle, performing constant temperature treatment at 200 ℃ for 72 hours to obtain a solid mixture II, collecting and grinding the mixture II, and performing constant temperature calcination at 700 ℃ in a static air atmosphere for 8 hours to obtain the attapulgite-based molecular sieve carrier.
Weighing 1g of attapulgite-based molecular sieve carrier, mixing with 30mL of 3.5mol/L hydrochloric acid solution, placing in a hydrothermal synthesis kettle, treating for 4 hours at 180 ℃, and obtaining solid III after centrifugal separation, filtration, drying and grinding; mixing the solid III with 30mL of 3.5mol/L NaOH solution, placing the mixture in a hydrothermal synthesis kettle, treating the mixture at 180 ℃ for 4 hours, and obtaining a solid IV after centrifugal separation, filtration, drying and grinding; calcining the solid IV at the constant temperature of 700 ℃ for 8 hours in a static air atmosphere to obtain the attapulgite-based molecular sieve carrier with surface silicon-aluminum holes, which is denoted as S2.
Example 3
Preparing an attapulgite-based molecular sieve carrier with surface silicon-aluminum cavities:
mixing 1.0g of attapulgite with 0.3g of NH 4 F. 0.3g of NaOH, 0.8g of tetraethylammonium bromide and triblock copolymer P123 (mass ratio is 1:1) and 0.4g of ethylenediamine are formed after being physically ground for 2 hoursMixture I. Transferring the mixture I onto a fixed support, placing the support into a polytetrafluoroethylene lining stainless steel synthesis kettle, adding 10ml of ammonia water solution at the bottom of the kettle, performing constant temperature treatment at 180 ℃ for 60 hours to obtain a solid mixture II, collecting and grinding the mixture II, and performing constant temperature calcination at 600 ℃ in a static air atmosphere for 6 hours to obtain the attapulgite-based molecular sieve carrier.
Weighing 1g of attapulgite-based molecular sieve carrier, mixing with 25mL of 3.5mol/L hydrochloric acid solution, placing in a hydrothermal synthesis kettle, treating for 4 hours at 180 ℃, and obtaining solid III after centrifugal separation, filtration, drying and grinding; then the solid III is mixed with 25mL of 3.5mol/L NH 4 Mixing OH solutions, placing the mixture in a hydrothermal synthesis kettle, treating the mixture at 180 ℃ for 4 hours, and obtaining solid IV after centrifugal separation, filtration, drying and grinding; calcining the solid IV at a constant temperature of 600 ℃ for 6 hours in a static air atmosphere to obtain the attapulgite-based molecular sieve carrier with surface silicon-aluminum holes, which is denoted as S3.
Example 4
Preparing an attapulgite-based molecular sieve carrier with surface silicon-aluminum cavities:
mixing 1.0g of attapulgite with 0.4g of NH 4 F. A mixture I was formed by physical mortar for 2 hours from 0.4g NaOH, 0.8g tetrapropylammonium bromide+triblock copolymer P123 (mass ratio 1:1) and 0.3g ethylenediamine. Transferring the mixture I onto a fixed support, placing the support into a polytetrafluoroethylene lining stainless steel synthesis kettle, adding 10ml of ammonia water solution at the bottom of the kettle, performing constant temperature treatment at 180 ℃ for 54 hours to obtain a solid mixture II, collecting and grinding the mixture II, and performing constant temperature calcination at 650 ℃ in a static air atmosphere for 7 hours to obtain the attapulgite-based molecular sieve carrier.
Weighing 1g of attapulgite-based molecular sieve carrier, mixing with 24mL of 3.5mol/L oxalic acid solution, placing in a hydrothermal synthesis kettle, treating for 4 hours at 180 ℃, and obtaining solid III after centrifugal separation, filtration, drying and grinding; mixing the solid III with 24mL of 3.5mol/L NaOH solution, placing the mixture in a hydrothermal synthesis kettle, treating the mixture at 180 ℃ for 4 hours, and obtaining a solid IV after centrifugal separation, filtration, drying and grinding; calcining the solid IV at 650 ℃ for 5 hours under the static air atmosphere to obtain the attapulgite-based molecular sieve carrier with surface silicon-aluminum holes, which is marked as S4.
Example 5
The preparation method of the nickel-ruthenium-zirconium/attapulgite-based molecular sieve based catalyst comprises the following steps:
with nickel nitrate hexahydrate (NiNO) 3 ·6H 2 O), ammonium ruthenium (IV) hexachloride hydrate (H) 8 Cl 6 N 2 Ru), zirconium nitrate pentahydrate (Zr (NO) 3 ) 2 ·6H 2 O) is precursor salt of nickel, ruthenium and zirconium.
0.3179g of nickel nitrate hexahydrate, 0.0759g of ammonium ruthenium (IV) chloride hydrate, 0.5167g of zirconium nitrate pentahydrate and 1.0000g of sodium dodecyl benzene sulfonate surfactant are weighed and uniformly mixed in absolute ethyl alcohol; then adding 2.0000g of S1 carrier for stirring and mixing, and stirring at a constant temperature of 80 ℃ until the ethanol solution is completely evaporated; and then filtering and collecting a solid product, drying and grinding, and then calcining for 4 hours at constant temperature under the air atmosphere of 30mL/min at the temperature of 500 ℃ to prepare the nickel-ruthenium-zirconium/attapulgite-based molecular sieve catalyst containing 3wt% of nickel, 1wt% of ruthenium and 5wt% of zirconium, which is denoted as 3Ni1Ru5Zr.
Example 6
The preparation method of the nickel-ruthenium-zirconium/attapulgite-based molecular sieve based catalyst comprises the following steps:
0.4557g of nickel nitrate hexahydrate, 0.1593g of ammonium ruthenium (IV) chloride hydrate, 0.7573g of zirconium nitrate pentahydrate and 1.5000g of sodium dodecyl benzene sulfonate surfactant are weighed and uniformly mixed in absolute ethyl alcohol; then adding 2.0000g of S2 carrier for stirring and mixing, and stirring at a constant temperature of 80 ℃ until the ethanol solution is completely evaporated; and then filtering and collecting a solid product, drying and grinding, and then calcining for 8 hours at a constant temperature of 700 ℃ and under an air atmosphere of 30mL/min to prepare the nickel-ruthenium-zirconium/attapulgite-based molecular sieve catalyst containing 4wt% of nickel, 2wt% of ruthenium and 7wt% of zirconium, which is denoted as 4Ni2Ru7Zr.
Example 7
The preparation method of the nickel-ruthenium-zirconium/attapulgite-based molecular sieve based catalyst comprises the following steps:
weighing 0.5976g of nickel nitrate hexahydrate, 0.3653g of ammonium ruthenium (IV) chloride hydrate, 0.9102g of zirconium nitrate pentahydrate and 2.0000g of sodium dodecyl benzene sulfonate surfactant, and uniformly mixing in absolute ethanol; then adding 2.0000g of S3 carrier for stirring and mixing, and stirring at a constant temperature of 80 ℃ until the ethanol solution is completely evaporated; and then filtering and collecting a solid product, drying and grinding, and then calcining for 6 hours at the constant temperature of 600 ℃ under the air atmosphere of 30mL/min to prepare the nickel-ruthenium-zirconium/attapulgite-based molecular sieve catalyst containing 5wt% of nickel, 3wt% of ruthenium and 8wt% of zirconium, which is marked as 5Ni3Ru8Zr.
Example 8
The preparation method of the nickel-ruthenium-zirconium/attapulgite-based molecular sieve based catalyst comprises the following steps:
0.6157g of nickel nitrate hexahydrate, 0.3768g of ammonium ruthenium (IV) chloride hydrate, 1.2335g of zirconium nitrate pentahydrate and 1.0000g of sodium dodecyl benzene sulfonate surfactant are weighed and uniformly mixed in absolute ethyl alcohol; then adding 2.0000g of S4 carrier for stirring and mixing, and stirring at a constant temperature of 80 ℃ until the ethanol solution is completely evaporated; and then filtering and collecting a solid product, drying, grinding, and then calcining at the constant temperature of 650 ℃ and under the air atmosphere of 30mL/min for 7 hours to realize the loading of the nickel-ruthenium-zirconium active component on the silicon-aluminum cavity on the surface of the attapulgite-based porous carrier, namely preparing the nickel-ruthenium-zirconium/attapulgite-based molecular sieve catalyst containing 5wt% of nickel, 3wt% of ruthenium and 10wt% of zirconium, which is marked as 5Ni3Ru10Zr.
Example 9
Test of Hydrogen production performance by aqueous phase reforming of Nickel-ruthenium-zirconium/Attapulgite-based molecular sieve catalyst:
the nickel-ruthenium-zirconium/attapulgite-based molecular sieve catalyst can be used for preparing hydrogen by carrying out biological oil and model water phase reforming in a fixed bed reactor without the traditional reduction and activation steps; the reaction conditions are as follows: the catalyst dosage is 0.1-0.5 g, the feed rate of the biological oil and the model thereof is 0.001-0.01 g/min, water is injected into the reactor through a peristaltic pump, the water injection speed of the pump is adjusted to change the water-carbon ratio (S/C), the S/C ratio of the water and the reactant in the feed is 1.5-10, and the reaction temperature is 200-400 ℃. Specific reaction conditions and experimental results are shown in table 1.
Table 1 laboratory bio-oil and its model aqueous phase reforming hydrogen production performance test
From the results, the conversion rate of raw materials such as bio-oil reaches 100%, the hydrogen yield is more than 80%, the purity of hydrogen in the product gas is more than 70%, and good stability is maintained in 200h reaction in the water phase reforming hydrogen production performance test process of the bio-oil and the model thereof.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. The nickel-ruthenium-zirconium/attapulgite-based molecular sieve catalyst is characterized by comprising a carrier and an active component loaded on the carrier, wherein the carrier is an attapulgite-based molecular sieve prepared by performing structural remodeling on attapulgite, and the attapulgite-based molecular sieve is subjected to desilication treatment; the active components are nickel, ruthenium and zirconium.
2. The nickel-ruthenium-zirconium/attapulgite-based molecular sieve catalyst according to claim 1, wherein the nickel content is 3-5 wt%, the ruthenium content is 0.1-3 wt%, the zirconium content is 5-10 wt%, and the balance is attapulgite-based molecular sieve.
3. The nickel-ruthenium-zirconium/attapulgite-based molecular sieve catalyst according to claim 1 or 2, wherein the attapulgite-based molecular sieve is prepared by structurally remolding attapulgite by an ammonia vapor induced recrystallization method, and the specific preparation method comprises the following steps:
mixing attapulgite with NH 4 F. Mixing and grinding NaOH, a template agent and a structure directing agent to obtain a mixture I, transferring the mixture I into a synthesis kettle, adding ammonia water solution, then carrying out constant temperature treatment at 160-200 ℃ for 48-72 h to obtain a solid mixture II, collecting the mixture II for grinding, and then carrying out constant temperature calcination at 500-700 ℃ in an air atmosphere for 4-8 h to obtain the productThe attapulgite-based molecular sieve.
4. The nickel-ruthenium-zirconium/attapulgite-based molecular sieve catalyst according to claim 3, wherein the template agent is a mixture of tetrapropylammonium bromide and triblock copolymer P123 mixed according to a mass ratio of 1:1 or a mixture of tetraethylammonium bromide and triblock copolymer P123 mixed according to a mass ratio of 1:1, the structure directing agent is ethylenediamine, and the attapulgite and NH are mixed according to a mass ratio of 1:1 4 F. The mass ratio of NaOH to template agent to structure guiding agent is 1:0.2-0.5:0.2-0.5:0.5-1:0.1-0.5.
5. The nickel-ruthenium-zirconium/attapulgite-based molecular sieve catalyst according to claim 1 or 2, wherein the specific preparation method for the dealumination treatment of the attapulgite-based molecular sieve comprises the following steps:
sequentially treating the attapulgite-based molecular sieve with an acid solution and an alkali solution in a hydrothermal synthesis kettle at 180 ℃ for 4-6 hours, performing centrifugal separation, filtering and drying after each treatment, and finally calcining.
6. The nickel-ruthenium-zirconium/attapulgite-based molecular sieve catalyst according to claim 5, wherein the acid solution is 3.5mol/L oxalic acid solution or 3.5mol/L hydrochloric acid solution, and the alkali solution is 3.5mol/L NH 4 The ratio of the attapulgite-based molecular sieve to the acid solution or the alkali solution is 1 g:20-30 mL.
7. The nickel-ruthenium-zirconium/attapulgite-based molecular sieve catalyst according to claim 1 or 2, wherein the specific preparation method for loading nickel, ruthenium and zirconium on the attapulgite-based molecular sieve comprises the following steps:
mixing a nickel precursor, a ruthenium precursor, a zirconium precursor and a surfactant in absolute ethyl alcohol uniformly, adding an attapulgite molecular sieve with surface silicon-aluminum cavities, stirring at a constant temperature of 80 ℃ until the ethanol is completely evaporated, filtering and collecting a solid product, drying and grinding, and calcining at a constant temperature of 500-700 ℃ and an air atmosphere of 30mL/min for 4-8 hours to realize the loading of nickel, ruthenium and zirconium on the attapulgite molecular sieve, thereby preparing the nickel-ruthenium-zirconium/attapulgite molecular sieve catalyst.
8. The nickel-ruthenium-zirconium/attapulgite-based molecular sieve catalyst according to claim 1 or 2, wherein the surfactant is any one of sodium dodecyl benzene sulfonate, CTAB, and zwitterionic polyacrylamide.
9. Use of the nickel-ruthenium-zirconium/attapulgite-based molecular sieve catalyst according to any one of claims 1 to 8 for the preparation of hydrogen by aqueous phase reforming of bio-oil and its model.
10. The method for preparing hydrogen by reforming the biological oil and the model water phase thereof is characterized by comprising the following steps: raw materials, the nickel-ruthenium-zirconium/attapulgite-based molecular sieve catalyst according to any one of claims 1 to 8 and water are added into a reactor for reaction, the catalyst dosage is 0.1 to 0.5g, the raw material feeding rate is 0.001 to 0.01g/min, the water is injected into the reactor through a peristaltic pump, the S/C ratio of the water and the reactant in the feeding is 1.5 to 10, and the reaction temperature is 200 to 400 ℃.
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