CN116422366A - Nickel-titanium layer lamellar mesoporous catalyst derived from attapulgite as well as preparation method and application thereof - Google Patents
Nickel-titanium layer lamellar mesoporous catalyst derived from attapulgite as well as preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 229960000892 attapulgite Drugs 0.000 title claims abstract description 75
- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 75
- HZEWFHLRYVTOIW-UHFFFAOYSA-N [Ti].[Ni] Chemical compound [Ti].[Ni] HZEWFHLRYVTOIW-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910001000 nickel titanium Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000010936 titanium Substances 0.000 claims abstract description 37
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 23
- 239000010703 silicon Substances 0.000 claims abstract description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000011541 reaction mixture Substances 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 13
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 13
- 239000010457 zeolite Substances 0.000 claims abstract description 13
- 239000002028 Biomass Substances 0.000 claims abstract description 11
- 238000000629 steam reforming Methods 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000005216 hydrothermal crystallization Methods 0.000 claims abstract description 8
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- 238000005470 impregnation Methods 0.000 claims abstract description 6
- 238000011068 loading method Methods 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical group [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
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- 238000003786 synthesis reaction Methods 0.000 abstract description 3
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- 238000010438 heat treatment Methods 0.000 description 16
- 238000005303 weighing Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- -1 alkali metal cation Chemical class 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 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
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000001193 catalytic steam reforming Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 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
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- 230000009849 deactivation Effects 0.000 description 1
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- 238000006062 fragmentation reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 238000010348 incorporation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 230000002572 peristaltic effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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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
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention discloses an attapulgite-derived nickel-titanium layer flaky mesoporous catalyst and a preparation method and application thereof, wherein the preparation method comprises the following steps: s1, dispersing attapulgite in a hydrochloric acid solution, and performing hydrothermal treatment to obtain an attapulgite-based silicon source; s2, reacting an attapulgite-based silicon source with a titanium source to obtain a reaction mixture containing Si-O-Ti polymer; s3, adding a template agent into the reaction mixture, and performing hydrothermal crystallization treatment to obtain a lamellar mesoporous zeolite carrier derived from attapulgite; s4, loading nickel on the carrier by an impregnation method to obtain the attapulgite-derived nickel-titanium layer lamellar mesoporous catalyst. The catalyst is applied to catalyzing biomass tar and a model object thereof to prepare hydrogen-rich gas by steam reforming, can realize the conversion rate of more than 95%, the hydrogen yield in the synthesis gas of more than 65%, the hydrogen selectivity of more than 70%, and the reaction for 30 hours still keeps higher activity, and has the advantages of environmental protection, high stability and low price.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to an attapulgite-derived nickel-titanium layer lamellar mesoporous catalyst, and a preparation method and application thereof.
Background
Catalytic steam reforming is of increasing interest because it allows tar conversion at low temperatures (500-900 ℃) to produce high value synthesis gas and hydrogen-rich gas. The most important catalyst in the catalytic steam reforming technology is that various transition metals are used as the catalyst, and the Ni-based catalyst has low cost and strong capability of breaking C-C bonds and C-H and O-H bonds, so that the catalyst can promote the WGS reaction and is widely applied to catalytic steam reforming.
However, since Ni-based catalysts are susceptible to deactivation by carbon deposition and sintering of metallic nickel particles at high temperatures, many researchers have been devoted to exploring nickel-based catalysts having improved resistance to carbon deposition and sintering. Different promoters and supports are one of the solutions for improving the catalyst life, for example Yufei Zhao et al reported that a metal oxide catalyst using titanium modified Attapulgite (ATP) as a support realizes alkali-resistant NOx catalytic reduction, and by ion exchange, alkali metal cation impurities in ATP are removed without damaging the initial layered chain structure of ATP, ti modified ATP is obtained, the octahedral center of Ti and the Si-OH site rich in ATP after modification can anchor alkali metal through coordination bond or ion exchange without damaging active substances, and thus the high NOx catalytic reduction capability of the catalyst is improved. However, the catalytic ability of the catalyst is still not ideal, and how to improve the catalytic effect of the catalyst has yet to be studied.
Disclosure of Invention
The invention mainly aims to provide an attapulgite-derived nickel-titanium layer lamellar mesoporous catalyst with better catalytic performance, and a preparation method and application thereof.
In order to achieve the above purpose, the invention provides a preparation method of an attapulgite-derived nickel-titanium layer lamellar mesoporous catalyst, which comprises the following steps:
s1, dispersing attapulgite in a hydrochloric acid solution, performing hydrothermal treatment at 150-200 ℃ for 10-15 hours, and filtering, washing and drying to obtain an attapulgite-based silicon source;
s2, adding an attapulgite-based silicon source into ethylene glycol, uniformly mixing, adding a titanium source, and then reacting for 1-4 hours at the temperature of 100-200 ℃ to obtain a reaction mixture containing Si-O-Ti polymer;
s3, adding a template agent into the reaction mixture, uniformly mixing, performing hydrothermal crystallization treatment at 150-200 ℃ for 24-36 hours, and centrifuging, washing, drying and calcining the obtained product to obtain the attapulgite-derived lamellar mesoporous zeolite carrier;
s4, loading nickel on the attapulgite-derived lamellar mesoporous zeolite carrier by an impregnation method, and drying and calcining to obtain the attapulgite-derived nickel-titanium lamellar mesoporous catalyst.
Further, in the catalyst, the content of nickel is 5-20wt% and the content of titanium is 1.0-3.5wt%.
Further, in the step S1, the concentration of the hydrochloric acid solution is 4mol/L, and the dosage ratio of the attapulgite to the hydrochloric acid solution is 1g: 5-10 mL.
In step S2, the titanium source is tetrabutyl titanate, the attapulgite-based silicon source, the tetrabutyl titanate titanium source and the ethylene glycol with the dosage ratio of 2-2.2 g: 0.45-0.5 mL: 10-10.2 mL.
Further, in the step S3, the template agent is tetrapropylammonium hydroxide, and the mass ratio of the template agent to the attapulgite-based silicon source is 2.5-7.5 g: 1-3 g, wherein the calcination treatment conditions are as follows: air atmosphere, temperature 550 ℃ and time 6-8 h.
Further, nickel nitrate hexahydrate is used as the precursor salt of nickel.
Further, in step S4, the operation procedure of the impregnation method is as follows: dissolving nickel precursor salt in water and ethanol according to the volume ratio of 2-3: 1, then aging for 8-12 h at normal temperature, and stirring for 5-8 h at 60-80 ℃.
Further, in step S4, the drying process conditions are: the temperature is 100-120 ℃ and the time is 8-12 h; the calcination treatment conditions are as follows: air atmosphere, temperature 500-600 deg.c and time 4-6 hr.
The invention also provides an attapulgite-derived nickel-titanium layer lamellar mesoporous catalyst which is prepared by the preparation method.
The invention also provides application of the attapulgite-derived nickel-titanium layer flaky mesoporous catalyst in preparing hydrogen-rich gas by steam reforming of biomass tar and a model thereof.
The invention also provides a method for preparing hydrogen-rich gas by steam reforming of biomass tar and a model thereof, which comprises the following steps: the biomass tar or the model thereof is used as a reaction raw material, and the catalyst as defined in claim 8 is added for reaction under the following reaction conditions: the dosage of the catalyst is 0.1-0.5 g, and the water-carbon ratio in the feed is 1:1.5 to 3, and the weight hourly space velocity is 0.0047 to 0.008min -1 The reaction temperature is 600-800 ℃; the catalyst reduction conditions were: at 100-150 mL/min, 10-15 vol% H 2 /N 2 Treating in the flow at 600-800 deg.c for 1-3 hr.
The beneficial effects of the invention are as follows:
the catalyst of the invention has the advantages that titanium is introduced into the attapulgite framework, the prepared nickel-titanium lamellar zeolite catalyst has very high specific surface area, the dispersibility of metal is enhanced, the catalytic performance is further improved, the catalyst adopts nickel and titanium as active components, and the catalyst can achieve relatively high activity by loading low-content nickel on the attapulgite-derived lamellar mesoporous zeolite carrier. Compared with other nickel-based catalysts, the catalyst provided by the invention has the advantages that attapulgite is used as a silicon source, tetrabutyl titanate is used as a titanium source, glycol is used as a solution to perform transesterification polymerization, then hydrothermal crystallization is performed in the presence of a template agent to synthesize a layered lamellar mesoporous zeolite carrier, nickel is loaded by an impregnation method, and the obtained attapulgite-derived nickel-titanium lamellar catalyst improves the carbon deposition resistance and sintering resistance of the catalyst.
The catalyst is applied to biomass tar and model steam reforming for preparing hydrogen-rich gas, can realize the conversion rate of more than 95%, the hydrogen yield in the synthesis gas of more than 65%, the hydrogen selectivity of more than 70%, and the reaction for 30 hours still keeps higher activity, has the advantages of environmental protection, high stability and low price, meets the industrialization requirement of biomass tar and model steam reforming for preparing hydrogen-rich gas, can obviously improve the capability of the catalyst for adsorbing and activating water vapor, improves the catalyst activity, and has good industrial application prospect.
Drawings
FIG. 1 is an SEM image of a carrier obtained in example 1 of the present invention;
FIG. 2 is an SEM image of a carrier obtained in example 1 of the present invention;
FIG. 3 is a TEM image of the catalyst # 1 prepared in example 1 of the present invention;
FIG. 4 is a TEM image of the catalyst # 1 prepared in example 1 of the present invention;
FIG. 5 is N of the catalyst # 1 prepared in example 1 of the present invention 2 Adsorption-desorption curves and pore size distribution plots;
FIG. 6 is an XRD pattern of catalyst # 1 prepared in example 1 of the present invention: N/TS (R) is a reduced catalyst; N-TS (C) is a calcined catalyst;
FIG. 7 is a US-Vis spectrum of the catalyst # 1 prepared in example 1 of the present invention: N/TS (R) is a reduced catalyst; N-TS (C) is a calcined catalyst; TS, carrier.
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
The active ingredient nickel (Ni) content in the attapulgite-derived nickel-titanium layer flaky mesoporous catalyst prepared in the embodiment is 5 weight percent, and the titanium (Ti) content is 2.7 weight percent, and the preparation method comprises the following steps:
s1, weighing 20g of mechanically ground attapulgite clay, dispersing in 120mL of 4mol/L hydrochloric acid solution to form suspension I, stirring on a stirring table for 2h, transferring the suspension I into a 200mL polytetrafluoroethylene-lined hydrothermal kettle, performing hydrothermal treatment at 160 ℃ for 10h, cooling to room temperature, filtering with deionized water, washing to neutrality, drying in a 100 ℃ oven for 10h, and grinding with a mortar to obtain the attapulgite-based silicon source.
S2, putting 10ml of ethylene glycol into a beaker, weighing 2g of attapulgite-based silicon source, pouring the mixture into a stirring table, stirring the mixture until the mixture is uniformly mixed, adding 0.5ml of tetrabutyl titanate, uniformly mixing the mixture, and reacting the mixture at 150 ℃ for 2.5 hours to enable the silicon source and the titanium source to complete polymerization reaction, thus obtaining a reaction mixture containing Si-O-Ti polymer;
s3, adding 4.6g of tetrapropylammonium hydroxide into the reaction mixture, uniformly mixing, transferring into a polytetrafluoroethylene lining hydrothermal reaction kettle, performing hydrothermal crystallization at 180 ℃ for 36 hours, centrifuging, washing, drying at 100 ℃ for 10 hours, and heating to 550 ℃ at a heating rate of 4 ℃/min in an air atmosphere to calcine for 6 hours to obtain the attapulgite-derived lamellar mesoporous zeolite carrier;
s4, weighing 0.132g of nickel nitrate hexahydrate, dissolving in 80ml of solution with the volume ratio of deionized water to ethanol being 2:1, adding 0.5g of the carrier, aging for 10 hours at normal temperature, placing on a stirring table, stirring for 5 hours at 60 ℃, placing in a 100 ℃ oven, drying for 10 hours, and heating to 550 ℃ at the heating rate of 4 ℃/min under the air atmosphere, thus obtaining the attapulgite-derived nickel-titanium lamellar mesoporous catalyst with the number of 1#.
Example 2
The active ingredient nickel (Ni) content in the attapulgite-derived nickel-titanium layer flaky mesoporous catalyst prepared in the embodiment is 10wt% and the titanium (Ti) content is 1.9wt%, and the preparation method is as follows:
s1, weighing 20g of mechanically ground attapulgite clay, dispersing in 100mL of 4mol/L hydrochloric acid solution to form suspension I, stirring on a stirring table for 2h, transferring the suspension I into a 200mL polytetrafluoroethylene-lined hydrothermal kettle, performing hydrothermal treatment at 170 ℃ for 12h, cooling to room temperature, filtering with deionized water, washing to neutrality, drying in a 100 ℃ oven for 8h, and grinding with a mortar to obtain the attapulgite-based silicon source.
S2, weighing 10.2ml of ethylene glycol, putting into a beaker, weighing 2.1g of attapulgite-based silicon source, pouring into the beaker, putting into a stirring table, stirring until the mixture is uniformly mixed, adding 0.45ml of tetrabutyl titanate, uniformly mixing, and reacting for 4 hours at 140 ℃ to enable the silicon source and the titanium source to complete polymerization reaction, thus obtaining a reaction mixture containing Si-O-Ti polymer;
s3, adding 4.8g of tetrapropylammonium hydroxide into the reaction mixture, uniformly mixing, transferring into a polytetrafluoroethylene lining hydrothermal reaction kettle, performing hydrothermal crystallization at 170 ℃ for 24 hours, centrifuging, washing, drying at 100 ℃ for 8 hours, heating to 550 ℃ at a heating rate of 4 ℃/min in an air atmosphere, and calcining for 6 hours to obtain the attapulgite-derived lamellar mesoporous zeolite carrier.
S4, weighing 0.284g of nickel nitrate hexahydrate, dissolving in 60ml of deionized water and a solution with the volume ratio of ethanol being 2:1, adding 0.5g of the carrier, aging for 8 hours at normal temperature, placing on a stirring table, stirring for 4.5 hours at 70 ℃, placing in a 100 ℃ oven, drying for 8 hours, heating to 500 ℃ at the heating rate of 4 ℃/min under the air atmosphere, and calcining for 6 hours to obtain the attapulgite-derived nickel-titanium layer lamellar mesoporous catalyst with the number of 2#.
Example 3
The active ingredient nickel (Ni) content in the attapulgite-derived nickel-titanium layer flaky mesoporous catalyst prepared in the embodiment is 15wt%, and the titanium (Ti) content is 1.7wt%, and the preparation method is as follows:
s1, weighing 20g of mechanically ground attapulgite clay, dispersing in 150mL of 4mol/L hydrochloric acid solution to form suspension I, stirring on a stirring table for 4h, transferring the suspension I into a 200mL polytetrafluoroethylene-lined hydrothermal kettle, performing hydrothermal treatment at 180 ℃ for 10h, cooling to room temperature, filtering with deionized water, washing to neutrality, drying in a 110 ℃ oven for 12h, and grinding with a mortar to obtain the attapulgite-based silicon source.
S2, weighing 10ml of ethylene glycol, putting into a beaker, weighing 2g of attapulgite-based silicon source, pouring into the beaker, putting into a stirring table, stirring until the mixture is uniformly mixed, adding 0.48ml of tetrabutyl titanate, uniformly mixing, and reacting for 2 hours at 180 ℃ to enable the silicon source and the titanium source to complete polymerization reaction, thus obtaining a reaction mixture containing Si-O-Ti polymer;
s3, adding 4.8g of tetrapropylammonium hydroxide into the reaction mixture, uniformly mixing, transferring into a polytetrafluoroethylene lining hydrothermal reaction kettle, performing hydrothermal crystallization at 180 ℃ for 36 hours, centrifuging, washing, drying at 110 ℃ for 12 hours, heating to 550 ℃ at a heating rate of 4 ℃/min in an air atmosphere, and calcining for 8 hours to obtain the attapulgite-derived lamellar mesoporous zeolite carrier.
S4, weighing 0.46g of nickel nitrate hexahydrate, dissolving in 100ml of solution with the volume ratio of deionized water to ethanol being 2:1, adding 0.5g of the carrier, aging for 9 hours at normal temperature, placing on a stirring table, stirring for 4 hours at 80 ℃, placing into a baking oven at 110 ℃ for drying for 12 hours, and heating to 550 ℃ at the heating rate of 4 ℃/min under the air atmosphere for calcination for 5 hours to obtain the attapulgite-derived nickel-titanium lamellar mesoporous catalyst with the number of 3#.
Example 4
The active ingredient nickel (Ni) content in the attapulgite-derived nickel-titanium layer flaky mesoporous catalyst prepared in the embodiment is 20wt%, and the titanium (Ti) content is 1.3wt%, and the preparation method is as follows:
s1, weighing 20g of mechanically ground attapulgite clay, dispersing in 200mL of 3.5mol/L hydrochloric acid solution to form suspension I, stirring on a stirring table for 3h, transferring the suspension I into a 200mL polytetrafluoroethylene-lined hydrothermal kettle, performing hydrothermal treatment at 180 ℃ for 12h, cooling to room temperature, filtering with deionized water, washing to be neutral, drying in a 120 ℃ oven for 12h, and grinding with a mortar to obtain the attapulgite-based silicon source.
S2, weighing 10.2ml of ethylene glycol, putting into a beaker, weighing 2.2g of attapulgite-based silicon source, pouring into the beaker, putting into a stirring table, stirring until the mixture is uniformly mixed, adding 0.49ml of tetrabutyl titanate, uniformly mixing, and reacting for 1h at 200 ℃ to enable the silicon source and the titanium source to complete polymerization reaction, thus obtaining a reaction mixture containing Si-O-Ti polymer;
s3, adding 5g of tetrapropylammonium hydroxide into the reaction mixture, uniformly mixing, transferring into a polytetrafluoroethylene lining hydrothermal reaction kettle, performing hydrothermal crystallization at 180 ℃ for 36h, centrifuging, washing, drying at 120 ℃ for 12h, heating to 550 ℃ at a heating rate of 4 ℃/min in an air atmosphere, and calcining for 6h to obtain the attapulgite-derived lamellar mesoporous zeolite carrier.
S4, weighing 0.67g of nickel nitrate hexahydrate, dissolving in 80ml of solution with the volume ratio of deionized water to ethanol being 3:1, adding 0.5g of the carrier, aging for 12 hours at normal temperature, placing on a stirring table, stirring for 5 hours at 65 ℃, placing into a baking oven at 120 ℃ for drying for 12 hours, heating to 600 ℃ at the heating rate of 4 ℃/min under the air atmosphere, and calcining for 4.5 hours to obtain the attapulgite-derived nickel-titanium lamellar mesoporous catalyst with the number of No. 4.
Example 5
Structure determination of catalyst
Through N 2 The pore diameter of the catalyst prepared in example 1 was analyzed by adsorption-desorption test means, and the results are shown in fig. 5 and table 1.
TABLE 1
The above table shows pore size data of the catalyst, which shows that the pore size of the catalyst is about two and three nanometers, which belongs to the mesoporous scale, and in addition, as can be seen from fig. 5A, the nitrogen adsorption-desorption isotherm of the catalyst is classified as type IV with an H1 type hysteresis loop, which shows that it has a regular pore structure, and the catalyst is proved to be a regular lamellar mesoporous material, the pore size distribution is narrower, and the pore size distribution of N/TS of fig. 5B clearly illustrates this.
Referring to fig. 6, the xrd pattern showed a very complete characteristic peak at 2θ=24.4°, without fragmentation, indicating successful incorporation of the titanium species into the zeolite framework. Referring to FIG. 7, the signal generated at 210nm in the US-Vis pattern is attributed to the 2p electron-to-Ti bond oxygen 4+ The 3d empty orbital transition of the ion, which is subjected to charge transfer, can be confirmed to contain framework titanium. The shoulder peak at 310nm is attributed to extra-framework anatase TiO 2 The peak intensity at 210nm is very high, which indicates that most of the titanium is incorporated into the lamellar support derived from attapulgite.
Example 6
Performance test for preparing hydrogen-rich gas by catalytic biomass tar and model steam reforming of biomass tar
0.1 to 0.5g of the No. 1 to No. 4 catalyst is taken in a fixed bed reactor and subjected to 100mL/min and 10vol percent of H 2 /N 2 Performance test is carried out after reduction treatment for 2h at 600-800 ℃ in the flow, the feeding flow rate of raw materials is 0.0001mol/min, steam supply is obtained by injecting water into an evaporator through a peristaltic pump, the water injection speed of the pump can be adjusted to change the water-carbon ratio (S/C), the water-carbon ratio in the feeding is 1:1.5-3, and the weight hourly space time is 0.0047-0.008 min -1 Table 2 laboratory biomass tar and model steam reforming to hydrogen-rich gas performance test
From the results, the catalyst can realize that the raw material conversion rate can reach more than 95%, the hydrogen yield can reach more than 65%, the hydrogen selectivity can reach more than 70%, and the catalyst can maintain good stability within 30 hours.
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 preparation method of the attapulgite-derived nickel-titanium layer lamellar mesoporous catalyst is characterized by comprising the following steps of:
s1, dispersing attapulgite in a hydrochloric acid solution, performing hydrothermal treatment at 150-200 ℃ for 10-15 hours, and filtering, washing and drying to obtain an attapulgite-based silicon source;
s2, adding an attapulgite-based silicon source into ethylene glycol, uniformly mixing, adding a titanium source, and then reacting for 1-4 hours at the temperature of 100-200 ℃ to obtain a reaction mixture containing Si-O-Ti polymer;
s3, adding a template agent into the reaction mixture, uniformly mixing, performing hydrothermal crystallization treatment at 150-200 ℃ for 24-36 hours, and centrifuging, washing, drying and calcining the obtained product to obtain the attapulgite-derived lamellar mesoporous zeolite carrier;
s4, loading nickel on the attapulgite-derived lamellar mesoporous zeolite carrier by an impregnation method, and drying and calcining to obtain the attapulgite-derived nickel-titanium lamellar mesoporous catalyst.
2. The method for preparing the attapulgite-derived nickel-titanium lamellar mesoporous catalyst according to claim 1, wherein the nickel content in the catalyst is 5-20wt% and the titanium content is 1.0-3.5wt%.
3. The method for preparing the attapulgite-derived nickel-titanium lamellar mesoporous catalyst according to claim 1 or 2, wherein in step S1, the concentration of the hydrochloric acid solution is 4mol/L, and the dosage ratio of the attapulgite to the hydrochloric acid solution is 1g: 5-10 mL.
4. The method for preparing the attapulgite-derived nickel-titanium lamellar mesoporous catalyst according to claim 1 or 2, wherein in the step S2, tetrabutyl titanate is selected as the titanium source, and the dosage ratio of the attapulgite-based silicon source, the tetrabutyl titanate titanium source and ethylene glycol is 2-2.2 g: 0.45-0.5 mL: 10-10.2 mL.
5. The method for preparing the attapulgite-derived nickel-titanium lamellar mesoporous catalyst according to claim 1 or 2, wherein in the step S3, the template agent is tetrapropylammonium hydroxide, and the mass ratio of the template agent to the attapulgite-based silicon source is 2.5-7.5 g: 1-3 g, wherein the calcination treatment conditions are as follows: air atmosphere, temperature 550 ℃ and time 6-8 h.
6. The method for preparing the attapulgite-derived nickel-titanium lamellar mesoporous catalyst according to claim 1 or 2, wherein in step S4, the impregnation method comprises the following steps: dissolving nickel precursor salt in water and ethanol according to the volume ratio of 2-3: 1, then aging for 8-12 h at normal temperature, and stirring for 5-8 h at 60-80 ℃.
7. The method for preparing the attapulgite-derived nickel-titanium lamellar mesoporous catalyst according to claim 1 or 2, wherein in step S4, the drying treatment conditions are as follows: the temperature is 100-120 ℃ and the time is 8-12 h; the calcination treatment conditions are as follows: air atmosphere, temperature 500-600 deg.c and time 4-6 hr.
8. An attapulgite-derived nickel-titanium layered platelet-shaped mesoporous catalyst, characterized by being prepared according to the preparation method of any one of claims 1 to 7.
9. The use of an attapulgite-derived nickel-titanium layered platelet-shaped mesoporous catalyst according to claim 8 for the steam reforming of biomass tar and its modeling material to produce hydrogen-rich gas.
10. Biological materialThe method for preparing the hydrogen-rich gas by steam reforming of the tar and the model thereof is characterized by comprising the following steps: the biomass tar or the model thereof is used as a reaction raw material, and the catalyst as defined in claim 8 is added for reaction under the following reaction conditions: the dosage of the catalyst is 0.1-0.5 g, and the water-carbon ratio in the feed is 1:1.5 to 3, and the weight hourly space velocity is 0.0047 to 0.008min -1 The reaction temperature is 600-800 ℃; the catalyst reduction conditions were: at 100-150 mL/min, 10-15 vol% H 2 /N 2 Treating in the flow at 600-800 deg.c for 1-3 hr.
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