CN116371407A - Yolk type core-shell catalyst Ni@HSS and preparation method thereof - Google Patents
Yolk type core-shell catalyst Ni@HSS and preparation method thereof Download PDFInfo
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- CN116371407A CN116371407A CN202211635080.9A CN202211635080A CN116371407A CN 116371407 A CN116371407 A CN 116371407A CN 202211635080 A CN202211635080 A CN 202211635080A CN 116371407 A CN116371407 A CN 116371407A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 239000011258 core-shell material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 210000002969 egg yolk Anatomy 0.000 title claims description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 151
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 48
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 31
- 239000002105 nanoparticle Substances 0.000 claims abstract description 28
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 23
- 239000003973 paint Substances 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000002920 hazardous waste Substances 0.000 claims abstract description 10
- 238000007233 catalytic pyrolysis Methods 0.000 claims abstract description 8
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- 239000004005 microsphere Substances 0.000 claims abstract description 3
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- 238000006243 chemical reaction Methods 0.000 claims description 24
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- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 17
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- 238000003756 stirring Methods 0.000 claims description 12
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- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 11
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- 238000001354 calcination Methods 0.000 claims description 11
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 11
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 11
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- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 239000002736 nonionic surfactant Substances 0.000 claims description 8
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims description 8
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- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
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- 238000001035 drying Methods 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 claims description 5
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical group [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 5
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- 102000002322 Egg Proteins Human genes 0.000 claims description 2
- 108010000912 Egg Proteins Proteins 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 235000013345 egg yolk Nutrition 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- 230000008021 deposition Effects 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 6
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 229910000531 Co alloy Inorganic materials 0.000 abstract description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 15
- 239000011257 shell material Substances 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005245 sintering Methods 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- FBWNMEQMRUMQSO-UHFFFAOYSA-N tergitol NP-9 Chemical compound CCCCCCCCCC1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 FBWNMEQMRUMQSO-UHFFFAOYSA-N 0.000 description 4
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- 239000008367 deionised water Substances 0.000 description 2
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- 238000011161 development Methods 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
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- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
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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
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/398—Egg yolk like
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a yolk-type core-shell catalyst Ni@HSS and a preparation method thereof, wherein a silicon dioxide hollow sphere is used as a shell layer, nickel nano particles are used as cores of yolk-type structures in the shell, and the nickel nano particles are highly dispersed in the silicon dioxide hollow microsphere; the silica hollow sphere is provided with rich mesoporous pore canals; wherein the mass fraction of nickel is 1-20wt%, the average size of nickel particles is 2-10 nm, the mass percentage of silicon dioxide is 80-99wt%, and the average size of the diameter of the silicon dioxide balls is 5-50 nm. The catalyst takes the non-noble metal nano nickel-cobalt alloy particles as an active center, reduces the cost of the catalyst, has better catalytic activity in the catalytic pyrolysis process of paint hazardous waste, and has excellent carbon deposition resistance and catalytic stability.
Description
Technical Field
The invention relates to the technical field of catalysts of core-shell structures, in particular to a yolk-type core-shell catalyst for thermal decomposition of hazardous wastes in paint production and chemical industry, which is suitable for treating toxic gases such as formaldehyde, benzene and the like in the catalytic pyrolysis industry of the hazardous wastes of paint.
Background
During the painting process, a portion of the paint is splashed outside the painted parts during the painting operation to form hazardous waste. At present, most enterprises absorb paint mist through circulating water of a paint spray booth to enable the paint mist to be condensed into paint waste residues, and then the waste residues are treated. Paint waste residues belong to dangerous wastes, and the improper treatment can cause great harm to the environment. The heat energy obtained by thermochemical treatment is an effective treatment mode for harmless and recycling of paint waste residues, but how to control sintering and carbon deposition of a catalyst under high temperature conditions in the thermochemical treatment process is a problem to be considered by adopting the method.
Researchers have performed thermodynamic simulations of different reaction temperatures, pressures, feed ratios, additional oxidants, and considered reactions for the formation of various carbons, leading to the general conclusion: high conversion can be achieved by operating at high temperature and low pressure; minimizing the formation of carbon deposits is particularly important for stable operation of the reaction process. The development of a catalyst with high activity, high stability, deactivation resistance and economic feasibility has important significance for successful industrialization of thermal decomposition of paint hazardous waste. Many researchers have been working on catalysts for thermal decomposition of paint hazard waste with high activity and stability. Among the various types of catalysts, noble metals, transition metals, supported catalysts, spinel, perovskite and mesoporous catalysts have been widely studied for use in this reaction.
The core-shell structure composite functional material is a multi-layer composite structural material formed by coating one nano material with another micro-nano material through physical or chemical acting force. The structure of the broad core-shell material is various, including hollow spheres, microcapsules, and the like.
The shell structure of the core-shell catalyst has better stability, and the threshold limiting effect can play a certain role in inhibiting the agglomeration of the core nano particles, so that the catalyst has better stability. The concrete steps are as follows: (1) The sintering of the active metal is prevented, so that the catalytic stability and the carbon deposition resistance are improved; (2) The interaction between the core-shell materials is enhanced due to the large contact interface area provided by the close contact of the materials; (3) If multiple active centers can be specifically designed, activity and selectivity can be improved; (4) The active site can be integrated or modified by regulating the component structure of the core-shell, so that the relevant performance of the catalyst can be further improved. The nano material with the core-shell structure can not only effectively prevent the deactivation phenomenon of nano particles caused by agglomeration, but also further realize the integration of active reaction positions by changing the components or the structure of the core particles or the components, the thickness and other factors of the shell layer so as to adapt to a complex catalytic reaction system.
The yolk-type core-shell structure is a novel core-shell structure with a cavity between the core and the shell. The nano particles with the yolk-shaped core-shell structure have the characteristics of a nano reactor, can provide a plurality of small independent micro reactors, realize the dispersion of substrate molecules, improve the reaction rate and improve the catalytic efficiency.
Patent document CN109225229a discloses a ni@siol 2 The preparation method of the catalyst with the core-shell structure comprises the steps of taking nickel nano particles as an inner core and taking silicon dioxide spheres as shell layers; wherein the mass fraction of nickel is 3-6wt%, the particle size of nickel is 1-4 nm, the mass percentage of silicon dioxide is 97-94 wt%, the diameter size of silicon dioxide sphere is 25-35 nm, and the catalyst is applied to methane carbon dioxide dry reforming reaction and has better activity. However, in the high-temperature catalysis process, the particle size of the metal particles is always difficult to control, and the nickel particles are sintered and agglomerated along with the temperature rise, so that the catalytic activity is greatly reduced, and the conversion rate of methane is reduced by more than 10% when the reaction is carried out at the temperature of more than 800 ℃. In addition, the stability of the catalyst is poorThis is because, as the reaction proceeds, ni sites are covered with a dense silica shell, which causes a loss in the number of active sites, and the catalytic activity thereof gradually decreases.
Disclosure of Invention
Aiming at the problems of easy carbon deposition, easy sintering, easy inactivation and the like of the catalyst in the existing catalytic pyrolysis process of paint hazardous wastes, the invention aims to provide an egg yolk type core-shell catalyst Ni@HSS and a preparation method thereof.
In order to achieve the above object, the technical scheme of the present invention is as follows:
the invention relates to a preparation method of a yolk-type core-shell catalyst Ni@HSS, which is characterized by comprising the following steps of:
s1, preparing metal nickel nano particles
(1) Mixing nickel source and 1, 2-hexadecane diol in the mixture of oleic acid, trioctylphosphine and oleylamine uniformly, and adding the mixture into N 2 Removing water and oxygen in the air in the atmosphere to obtain a mixed solution A;
(2) Heating the mixed solution A to 280-320 ℃, and keeping the constant temperature for reaction for 2-3 h; cooling to 80-100 ℃ to obtain mixed solution B;
(3) Dissolving the mixed solution B in a solution consisting of oleylamine and borane-tributylamine complex, and preserving heat for 2-3 hours at 90-100 ℃ to obtain a mixed solution C;
(4) Adding ethanol to precipitate the mixed solution C, separating to obtain a solid product, and washing with cyclohexane; drying to obtain metal nickel nano particles, and preserving under vacuum;
the nickel source is nickel (II) acetylacetonate, and the concentration of the nickel source in the mixed solution A is 0.05-0.17 mol/L; the concentration of the 1, 2-hexadecane diol in the mixed solution A is 0.05 to 0.2mol/L; the volume ratio of oleic acid to trioctylphosphine to oleylamine is (3-3.5): (4-5): 10, preferably a volume ratio of 3.2:4.6:10; wherein the mass concentration of the oleylamine is 60% -80%;
the molar ratio of the oleylamine to the borane-tributylamine complex is 1: (0.8-1);
s2, preparing yolk type core-shell catalyst Ni@HSS
(5) The cyclohexane, the Solvin nonionic surfactant and the ammonia water solution are stirred and mixed in a reaction bottle to obtain a mixed solution D; adding the metal nickel nano particles into a mixed solution of tetramethyl orthosilicate, octadecyl trimethoxy silane and cyclohexane, and uniformly mixing to obtain a mixture E;
(6) b, adding the mixture E into the mixed solution D, and continuously stirring for 60-90 min at the temperature of 30-40 ℃; centrifuging, precipitating, separating to obtain solid, washing with ethanol, and vacuum drying;
(8) Calcining the solid at 500-800 ℃ for 2-3 hours;
(9) Calcining the solid at 800-850 ℃ to obtain H 2 And N 2 In-situ reducing for 2-3 h to obtain the yolk type core-shell catalyst Ni@HSS;
the Sorpovine nonionic surfactant is a liquid nonionic surfactant, and has the chemical name of nonylphenol polyoxyethylene ether, such as igepal CO-630 of Sang Jing chemistry, ABEX AP470-Z of Rodiba.
Preferably, in the mixed solution D, the volume ratio of cyclohexane, the sorrow nonionic surfactant and the ammonia water is (25 to 30): (8-10): 1, preferably 25:8:1, a step of; stirring for at least 5min;
preferably, in the mixed solution E, the volume ratio (25-30) of cyclohexane, tetramethyl orthosilicate and octadecyl trimethoxy silane is as follows: (1-1.5): 1, preferably 25:1:1, a step of; the mass concentration of the metal nickel nano particles in the mixed solution E is 1.0-1.5 mol/L.
Preferably, the stirring temperature in the step (6) is 30 ℃, and the stirring time is 60min.
Preferably, the calcination temperature is 800 ℃, the calcination time is 2 hours, and the temperature rising rate is 2-5 ℃/min.
Preferably, in the step (9), the volume fraction of the hydrogen in the mixed gas is 5% -15%, the flow rate of the mixed gas is 90-120 mL/min (preferably 100 mL/min), and the reduction time is 1.5-3.5 h.
The yolk type core-shell catalyst Ni@HSS prepared by the method is characterized in that a silicon dioxide hollow sphere is taken as a shell layer, nickel nano particles are taken as cores of a yolk type structure in the shell, and the nickel nano particles are highly dispersed in the silicon dioxide hollow microsphere; the silica hollow sphere is provided with rich mesoporous pore canals; wherein the mass fraction of nickel is 1-20wt%, the average size of nickel particles is 2-10 nm, the mass percentage of silicon dioxide is 80-99wt%, and the average size of the diameter of the silicon dioxide balls is 5-50 nm; the pore canal on the silica hollow sphere is used for promoting the reaction of the internal active site and the external reactant, the nickel nano particle is completely limited in a zero-dimensional closed space by a shell layer, is protected by silica, has a complete geometric domain limiting effect, furthest limits migration and aggregation of the nickel particle, has no free space for carbon deposition growth in a closed space structure, has strong sintering resistance and carbon deposition resistance, and can not sinter at the temperature of more than 900 ℃ and is far higher than the sintering temperature of other types of catalysts.
The yolk type core-shell catalyst Ni@HSS is used for catalytic pyrolysis of paint hazardous waste, and particularly for catalytic pyrolysis treatment of toxic gases such as formaldehyde, benzene and the like.
Compared with the prior art, the invention has the beneficial effects that:
the yolk type core-shell catalyst Ni@HSS takes the non-noble metal nano nickel-cobalt alloy particles as active centers, greatly reduces the cost of the catalyst compared with noble metals, is simple to operate, and has good development prospect in industry. The catalyst prepared by the method has better activity and excellent catalytic stability in the catalytic pyrolysis process of paint hazardous waste; due to the existence of mesopores, the yolk shell structure has higher specific surface area, higher pore volume and higher mass transfer efficiency. Ni@SiO to comparative document 1 2 Compared with the core-shell catalyst, the Ni@HSS yolk type core-shell catalyst prepared by the invention has excellent catalytic activity even at a high temperature of more than 800 ℃, and the conversion rate of reactants is more than 90%; meanwhile, the catalyst has excellent stability, and the catalytic activity after 50 hours of reaction is reduced by less than 1%.
Drawings
Fig. 1 is a transmission electron microscope image of a yolk-type core-shell catalyst ni@hss of example 1.
FIG. 2 is the XRD patterns of the catalysts of example 1 and comparative examples 1-2.
FIG. 3 is a graph showing the conversion and catalytic stability test of the catalysts of example 1 and comparative examples 1-2 for formaldehyde gas in paint micro waste.
FIG. 4 is a thermal weight loss test of the catalysts of example 1 and comparative examples 1-2.
Detailed Description
It will be appreciated by persons skilled in the art that the present embodiment is provided for illustration only and not for limitation of the invention, and that modifications and variations may be made to the embodiment within the scope of the invention as defined in the appended claims.
Example 1
A preparation method of a yolk type core-shell catalyst Ni@HSS comprises the following steps:
s1, preparing metal nickel nano particles
(1) 1.54g of nickel (II) acetylacetonate and 1.56g of 1, 2-hexadecanediol are mixed homogeneously in 6.4mL oleic acid (OAc), 9.2mL trioctylphosphine (top, 90%) and 20mL oleylamine (OAm, mass concentration 70%) in N 2 Removing water and oxygen in the air in the atmosphere to obtain a mixed solution A;
(2) Heating the mixed solution A to 300 ℃, and keeping the constant temperature for reaction for 2 hours; cooling to 90 ℃ to obtain a mixed solution B;
(3) Rapidly dissolving the mixed solution B in a solution composed of 12.0mL of oleylamine and 1.58g of borane-tributylamine complex (BTB, 97%) and preserving heat at 90 ℃ for 1h to obtain a mixed solution C;
(4) Adding 50mL ethanol to precipitate the mixed solution C, separating to obtain a solid product, and washing with cyclohexane for 3 times; drying in a vacuum drying oven to obtain metal nickel nanoparticles with average size of about 5nm, and preserving under vacuum.
S2, preparing yolk type core-shell catalyst Ni@HSS
(5) 50mL of cyclohexane, 16mL of Sorptive surfactant (Igepal CO-630) and 2.0mL of ammonia water solution are mixed in a three-necked flask and stirred for 10min to obtain a mixed solution D; 3.0mmol of metallic nickel nano-particles are added into a mixed solution of 2.0mL of tetramethyl orthosilicate (TMOS, 98%), 2.0mL of octadecyl trimethoxysilane (C18 TMS, 90%) and 50mL of cyclohexane, and the mixture is uniformly mixed to obtain a mixture E;
(6) Adding the mixture E into the mixed solution D, and continuously stirring at 30 ℃ for 60min; centrifuging, precipitating, separating to obtain solid, washing with ethanol for 3 times, and vacuum drying at 100deg.C;
(8) Calcining the solid at 800 ℃ for 2 hours, wherein the temperature gradient is 3 ℃/min;
(9) H at 800 ℃ for the calcined solid 2 (volume fraction 10%) and N 2 The mixture is reduced for 2 hours in situ, the flow rate of the mixture is 100mL/min, and the yolk type core-shell catalyst Ni@HSS is obtained; wherein the mass fraction of nickel is 6wt%, the average size of nickel particles is 5nm, the mass fraction of silicon dioxide is 90wt%, and the average size of the diameter of the silicon dioxide spheres is 30nm.
Example 2
A preparation method of a yolk type core-shell catalyst Ni@HSS comprises the following steps:
s1, preparing metal nickel nano particles
(1) 3.54. 3.54 g Nickel (II) acetylacetonate was mixed with 1.56. 1.56g 1, 2-hexadecanediol in 6.4. 6.4mL oleic acid (OAc), 9.2. 9.2mL trioctylphosphine (top, 90%) and 20mL oleylamine (OAm, 70% by mass) uniformly in N 2 Removing water and oxygen in the air in the atmosphere to obtain a mixed solution A;
(2) Heating the mixed solution A to 300 ℃, and keeping the constant temperature for reaction for 2 hours; cooling to 90 ℃ to obtain a mixed solution B;
(3) Rapidly dissolving the mixed solution B in a solution composed of 12mL of oleylamine and 1.58g of borane-tributylamine complex (BTB, 97%) and preserving heat at 90 ℃ for 1h to obtain a mixed solution C;
(4) Adding 50mL ethanol to precipitate the mixed solution C, separating to obtain a solid product, and washing with cyclohexane for 4 times; drying in a vacuum drying oven to obtain metal nickel nanoparticles with average size of about 10nm, and preserving under vacuum.
S2, preparing yolk type core-shell catalyst Ni@HSS
(5) 50mL cyclohexane, 16mL of Sorptive vitamin nonionic surfactant (Igepal CO-630) and 2mL of ammonia water solution are mixed in a three-necked flask and stirred for 10min to obtain a mixed solution D; adding 6.0mmol of metallic nickel nano-particles into a mixed solution of 2mL of tetramethyl orthosilicate (TMOS, 98%), 2mL of octadecyl trimethoxysilane (C18 TMS, 90%) and 50mL of cyclohexane, and uniformly mixing to obtain a mixture E;
(6) Adding the mixture E into the mixed solution D, and continuously stirring at 30 ℃ for 60min; centrifuging, precipitating, separating to obtain solid, washing with ethanol for 3 times, and vacuum drying at 100deg.C;
(8) Calcining the solid at 800 ℃ for 2 hours, wherein the temperature gradient is 3 ℃/min;
(9) H at 800 ℃ for the calcined solid 2 (volume fraction 10%) and N 2 The mixture is reduced for 2 hours in situ, the flow rate of the mixture is 100mL/min, and the yolk type core-shell catalyst Ni@HSS is obtained; wherein the mass fraction of nickel is 15wt%, the average size of nickel particles is 10nm, the mass fraction of silicon dioxide is 82 and wt%, and the average size of the diameter of the silicon dioxide spheres is 30nm.
Example 3
A preparation method of a yolk type core-shell catalyst Ni@HSS comprises the following steps:
s1, preparing metal nickel nano particles
(1) 2.92 g Nickel (II) acetylacetonate was mixed with 1.56g 1, 2-hexadecanediol in 6.4mL oleic acid (OAc), 9.2mL trioctylphosphine (top, 90%) and 20mL oleylamine (OAm, 70% by mass) uniformly in N 2 Removing water and oxygen in the air in the atmosphere to obtain a mixed solution A;
(2) Heating the mixed solution A to 300 ℃, and keeping the constant temperature for reaction for 2 hours; cooling to 90 ℃ to obtain a mixed solution B;
(3) Rapidly dissolving the mixed solution B in a solution composed of 12mL of oleylamine and 1.58g of borane-tributylamine complex (BTB, 97%) and preserving heat at 90 ℃ for 1h to obtain a mixed solution C;
(4) Adding 50mL of ethanol to precipitate the mixed solution C, separating to obtain a solid product, and washing with cyclohexane for 4 times; drying in a vacuum drying oven to obtain metal nickel nanoparticles with average size of about 8nm, and preserving under vacuum.
S2, preparing yolk type core-shell catalyst Ni@HSS
(5) 50mL of cyclohexane, 16mL of Sorptive surfactant (Igepal CO-630) and mL of ammonia water solution are mixed in a three-necked flask and stirred for 10min to obtain a mixed solution D; adding 9mmol of metallic nickel nano particles into a mixed solution of 2mL of tetramethyl orthosilicate (TMOS, 98%), 2mL of octadecyl trimethoxysilane (C18 TMS, 90%) and 50mL of cyclohexane, and uniformly mixing to obtain a mixture E;
(6) Adding the mixture E into the mixed solution D, and continuously stirring at 30 ℃ for 60min; centrifuging, precipitating, separating to obtain solid, washing with ethanol for 3 times, and vacuum drying at 100deg.C;
(8) Calcining the solid at 800 ℃ for 2 hours, wherein the temperature gradient is 3 ℃/min;
(9) H at 800 ℃ for the calcined solid 2 (volume fraction 10%) and N 2 The mixture is reduced for 2 hours in situ, the flow rate of the mixture is 100mL/min, and the yolk type core-shell catalyst Ni@HSS is obtained; wherein the mass fraction of nickel is 10wt%, the average size of nickel particles is 8nm, the mass fraction of silicon dioxide is 86wt%, and the average size of silicon dioxide sphere diameter is 30nm.
Comparative example 1
This comparative example 1 is a comparative example of example 1, and catalyst Ni/HSS was prepared:
(1) 1.54g of Ni (NO 3 ) 2 •6H 2 O is dissolved in deionized water and stirred for 10min at 80 ℃ to obtain nickel nitrate solution;
(2) 5.0mL of tetramethyl orthosilicate (TMOS, 98%) and 5.0mL of octadecyl trimethoxysilane (C18 TMS, 90%) were thoroughly mixed and stirred at room temperature for 10min; then vacuum drying is carried out for 24 hours at the temperature of 10 ℃ to obtain solid HSS;
(3) Uniformly dripping nickel nitrate solution onto solid HSS, stirring for 10min, and vacuum drying at 100deg.C for 12 hr to obtain Ni/HSS; wherein the mass fraction of nickel is 6wt%, the average size of nickel particles is 8nm, the mass fraction of silicon dioxide is 90wt%, and the average size of silicon dioxide sphere diameter is 40nm.
Comparative example 2
Comparative example 2 is a comparative example of example 1, catalyst Ni/SiO was prepared 2 ：
(1) 1.54g of Ni (NO 3 ) 2 •6H 2 O is dissolved in deionized water and stirred for 10min at 80 ℃ to obtain nickel nitrate solution;
(2) Drop nickel nitrate solution into commercial SiO 2 Stirring for 10min, and vacuum drying at 100deg.C for 12 hr to obtain Ni/SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the mass fraction of nickel is 8wt%, the average size of nickel particles is 8nm, the mass fraction of silicon dioxide is 86wt%, and the average size of silicon dioxide sphere diameter is 50nm.
Application example 1
XRD characterization of the three different catalysts of example 1 and comparative examples 1-2, as shown in FIG. 2, was performed with catalyst Ni/HSS and catalyst Ni/SiO 2 In contrast, the catalyst ni@hss of the present invention has the smallest peak area. This means that catalyst Ni/HSS and catalyst Ni/SiO 2 The Ni particles in the catalyst Ni@HSS do not change obviously. The catalyst Ni@HSS of the invention has higher catalytic efficiency than the other two because Ni particles are smaller and have higher conversion efficiency.
The three different catalysts of example 1 and comparative examples 1-2 were subjected to thermogravimetric analysis, as can be seen from FIG. 4, catalyst Ni/SiO 2 Shows the most obvious weight loss phenomenon (21.9%), which indicates that the catalyst has the most serious carbon deposition, and is also the catalyst Ni/SiO 2 The main cause of the decrease in activity. The weight loss of the catalyst Ni/HSS is 9.1 percent, which is less than Ni/SiO 2 . However, no weight loss was found for catalyst ni@hss, indicating that catalyst ni@hss has excellent resistance to carbon deposition.
Three of example 1 and comparative examples 1 to 2 were usedThe conversion rate of harmful gas formaldehyde is studied by applying different catalysts to the catalytic pyrolysis process of paint hazardous waste, and as can be seen from figure 3, the conversion rate and stability of the catalyst Ni@HSS of the invention are obviously superior to those of the catalyst Ni/HSS of comparative example 1 and the catalyst Ni/SiO of comparative example 2 2 。
Claims (10)
1. The preparation method of the yolk type core-shell catalyst Ni@HSS is characterized by comprising the following steps of:
s1, preparing metal nickel nano particles
(1) Mixing nickel source and 1, 2-hexadecane diol in the mixture of oleic acid, trioctylphosphine and oleylamine uniformly, and adding the mixture into N 2 Removing water and oxygen in the air in the atmosphere to obtain a mixed solution A;
(2) Heating the mixed solution A to 280-320 ℃, and keeping the constant temperature for reaction for 2-3 h; cooling to 80-100 ℃ to obtain mixed solution B;
(3) Dissolving the mixed solution B in a solution consisting of oleylamine and borane-tributylamine complex, and preserving heat for 2-3 hours at 90-100 ℃ to obtain a mixed solution C;
(4) Adding ethanol to precipitate the mixed solution C, separating to obtain a solid product, and washing with cyclohexane; drying to obtain metal nickel nano particles, and preserving under vacuum;
s2, preparing yolk type core-shell catalyst Ni@HSS
(5) The cyclohexane, the Solvin nonionic surfactant and the ammonia water solution are stirred and mixed in a reaction bottle to obtain a mixed solution D; adding the metal nickel nano particles into a mixed solution of tetramethyl orthosilicate, octadecyl trimethoxy silane and cyclohexane, and uniformly mixing to obtain a mixture E;
(6) Adding the mixture E into the mixed solution D, and continuously stirring for 60-90 min at the temperature of 30-40 ℃; centrifuging, precipitating, separating to obtain solid, washing with ethanol, and vacuum drying;
(8) Calcining the solid at 500-800 ℃ for 2-3 hours;
(9) Calcining the solid at 800-850 ℃ to obtain H 2 And N 2 In situ in the gas mixture of (2)And (3) reducing for 2-3 h to obtain the yolk type core-shell catalyst Ni@HSS.
2. The preparation method of the yolk type core-shell catalyst Ni@HSS according to claim 1, wherein the nickel source is nickel (II) acetylacetonate, and the concentration of the nickel source in the mixed solution A is 0.05-0.17 mol/L; the concentration of the 1, 2-hexadecane diol in the mixed solution A is 0.05 to 0.2mol/L; the volume ratio of oleic acid to trioctylphosphine to oleylamine is (3-3.5): (4-5): 10.
3. the preparation method of the yolk-type core-shell catalyst Ni@HSS according to claim 2, wherein the volume ratio of oleic acid to trioctylphosphine to oleylamine is 3.2:4.6:10; wherein the mass concentration of the oleylamine is 60% -80%.
4. The method for preparing the yolk type core-shell catalyst Ni@HSS according to claim 1, wherein in the step (3), the molar ratio of oleylamine to borane-tributylamine complex is 1: (0.8-1).
5. The preparation method of the yolk type core-shell catalyst Ni@HSS according to claim 1, wherein the volume ratio of cyclohexane, a Sorption nonionic surfactant and ammonia water in the mixed solution D is (25-30): (8-10): 1, a step of; in the mixed solution E, the volume ratio of cyclohexane, tetramethyl orthosilicate and octadecyl trimethoxy silane is (25-30): (1-1.5): 1, wherein the mass concentration of the metal nickel nano particles in the mixed solution E is 1.0-1.5 mol/L.
6. The preparation method of the yolk type core-shell catalyst Ni@HSS according to claim 1, wherein the volume ratio of cyclohexane, a Sorvu nonionic surfactant and ammonia water in the mixed solution D is 25:8:1, a step of; in the mixed solution E, the volume ratio of cyclohexane, tetramethyl orthosilicate and octadecyl trimethoxy silane is 25:1:1.
7. the preparation method of the yolk type core-shell catalyst Ni@HSS according to claim 1, wherein the stirring temperature in the step (6) is 30 ℃ and the stirring time is 60min; the calcining temperature in the step (8) is 800 ℃, the calcining time is 2 hours, and the heating rate is 2-5 ℃/min.
8. The preparation method of the yolk-type core-shell catalyst Ni@HSS according to claim 1, wherein the volume fraction of hydrogen in the mixed gas in the step (9) is 5% -15%; the flow rate of the mixed gas is 90-120 mL/min, and the reduction time is 1.5-3.5 h.
9. The yolk-type core-shell catalyst Ni@HSS prepared according to any one of claims 1 to 8, wherein a silica hollow sphere is taken as a shell layer, nickel nanoparticles are taken as cores of yolk-type structures in the shell, and the nickel nanoparticles are highly dispersed in the silica hollow microsphere; the silica hollow sphere is provided with rich mesoporous pore canals; wherein the mass fraction of nickel is 1-20wt%, the average size of nickel particles is 2-10 nm, the mass percentage of silicon dioxide is 80-99wt%, and the average size of the diameter of the silicon dioxide balls is 5-50 nm.
10. The egg yolk type core-shell catalyst ni@hss according to claim 9, for catalytic pyrolysis of paint hazardous waste.
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