CN112973730B - Ni-Ir/SiO 2 Bimetallic catalyst and preparation method and application thereof - Google Patents

Ni-Ir/SiO 2 Bimetallic catalyst and preparation method and application thereof Download PDF

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CN112973730B
CN112973730B CN202110196976.0A CN202110196976A CN112973730B CN 112973730 B CN112973730 B CN 112973730B CN 202110196976 A CN202110196976 A CN 202110196976A CN 112973730 B CN112973730 B CN 112973730B
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陈海军
孙嘉明
张金强
朱跃钊
孙红旗
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Nanjing Tech University
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Abstract

The invention relates to Ni-Ir/SiO 2 The bimetallic catalyst and its preparation method and application are characterized by that the catalyst is made up by using SiO 2 The carrier is Ni, ni accounts for 2.0-4.0% of the carrier, ir accounts for 0.2-0.6% of the carrier, and the mass ratio of Ni to Ir is 5-9; the preparation method comprises the following steps: adsorption of metal cations, adsorption of complex metal anions to form SiO 2 Loading double salt, washing the product, drying, introducing into reducing atmosphere, heating and reducing to obtain Ni-Ir/SiO 2 A bimetallic catalyst. The invention obtains Ni-Ir/SiO with small particle size and designable particles 2 The bimetallic catalyst can generate a photo-thermal synergistic effect in a dry reforming reaction and has higher efficiency under a relatively low temperature condition.

Description

Ni-Ir/SiO 2 Bimetallic catalyst and preparation method and application thereof
Technical Field
The invention relates to a preparation method of a bimetallic catalyst and a methane dry reforming application thereof, in particular to Ni-Ir/SiO 2 A bimetallic catalyst and a preparation method and application thereof belong to the field of interdisciplinary subjects of energy, materials and chemical industry.
Background
Methane dry reforming reaction (DRM) can simultaneously and effectively utilize CO 2 And CH 4 The two greenhouse gases are used for preparing synthesis gas, and can be directly used as raw materials for carbonylation reaction, dimethyl ether synthesis and Fischer-Tropsch synthesis. DRM can be carried out only at a high temperature (800-1000 ℃), and the requirements on reaction and heat exchanger materials are high; meanwhile, the catalyst is easy to deposit carbon and deactivate at high temperature. Therefore, designing a new process and a suitable catalyst to lower the DRM reaction temperature and improve the stability thereof is still a hot issue of research.
Bimetallic catalysts refer to catalysts comprising two metals, having a unique geometric and electronic structure, and a synergistic effect that exists between the two metals, which typically perform better than their parent metals. Bimetallic catalysts have found wide application in reactions including reforming, selective hydrogenation and dehydrogenation, and acetoxylation. For a DRM system, ni-dominated cheap bimetal can play a synergistic role between two metals by combining microstructure regulation, and the cost is reduced on the basis of obtaining better catalytic performance.
Kunlun Ding et al invented a synthetic method of supported bimetallic nanoparticles based on surface inorganic metal coordination chemistry, which obtains supported double salts (DCSs) with precise anion-cation ratio by electrostatic interaction, and then the supported double salts (DCSs) are subjected to H 2 Reducing to obtain the supported bimetallic catalyst. The method avoids the problem of competitive adsorption of different metal cations in the traditional impregnation method and coprecipitation method, and solves the problem of dissolution of DCSs in the synthesis of the bimetallic catalyst, and the obtained bimetallic nanoparticles have particle sizes less than 3nm and narrow particle size distribution. The catalytic performance of the prepared bimetallic catalyst in the selective hydrogenation reaction of acetylene is obviously better than that of the parent metal (Science 02 Nov 2018, vol.362, issue 6414, pp.560-564). However, in the stage of complex anion adsorption, the preparation method directly mixes the anion solution with dichloromethane in one pot, and the extraction and liquid separation effects are poor, so that the target product is difficult to obtain, or the product efficiency is low.
Solar energy can be used as a heat source for dry reforming, but the problem of high reaction temperature still exists, and the catalyst is easy to deactivate; at the same time, there is "hot spot" damage to the high temperature reactor. Through the synergistic action of light and heat, the effective combination of the light and the heat can surpass the effect which can be achieved by independent thermal catalysis and photocatalysis, the efficiency of catalytic reaction can be improved, and the reaction temperature can be reduced.
Disclosure of Invention
The invention aims to overcome the existing working limitation and provides a Ni-Ir/SiO 2 The invention also provides a preparation method of the bimetallic catalyst and application of the bimetallic catalyst.
The invention improves the preparation method of the bimetallic catalyst in the literature, combines the requirements of photo-thermal synergy, and obtains the Ni-Ir/SiO with small particle size and designable particles 2 Bimetallic catalyst capable of producing a photothermal synergistic effect in a dry reforming reaction in phaseHas higher efficiency under low temperature.
The technical scheme of the invention is as follows: ni-Ir/SiO 2 Bimetallic catalyst, characterized by the fact that it is made of SiO 2 The carrier is Ni accounting for 2.0-4.0% of the carrier, ir accounting for 0.2-0.6% of the carrier, and the mass ratio of Ni and Ir is 5-9. The expression is as follows: xNi-yIr/SiO 2 Wherein x and y are loading amounts, x% is the mass fraction of Ni, and y% is the mass fraction of Ir.
Preferably Ni-Ir/SiO 2 The particle size of the bimetallic catalyst particles is 2-4 nm.
The invention also provides a method for preparing the Ni-Ir/SiO 2 The method for preparing the bimetallic catalyst comprises the following specific steps:
adsorption of metal cations
a) Mixing SiO 2 Adding into strong alkali solution, and performing ultrasonic dispersion; repeatedly washing with deionized water until the pH of the obtained clear liquid is 9.1-9.4; the obtained SiO 2 Redispersing in deionized water;
b) Using peristaltic pump to SiO 2 Dropwise adding a nickel salt solution into deionized water at the speed of 0.1-0.5 mL/min, uniformly mixing after dropwise adding, and centrifugally drying; obtaining SiO loaded with nickel 2 ；
Adsorption of B complex metal anions
c) Mixing Na 2 IrCl 6 Mixing the aqueous solution and tetrabutylammonium bromide aqueous solution, adding CH 2 Cl 2 Shaking for 5-30 min and centrifuging to obtain the upper oil phase;
d) Anion adsorption: siO loaded with nickel 2 The product is dissolved in CH 2 Cl 2 Dripping the mixture into the oil phase solution by using a peristaltic pump at the dripping speed of 0.1-0.5 mL/min, and uniformly mixing to form SiO 2 A supported double salt (DCS);
c product is CH 2 Cl 2 Washing and drying the solution; placing the dried product in a tubular furnace, introducing a reducing atmosphere, heating to 390-420 ℃, and reducing for 30-60 min; obtaining Ni-Ir/SiO 2 A bimetallic catalyst.
Preferred procedurea) The ultrasonic dispersion time is 20-50 min, and the ultrasonic dispersion frequency is 25-80 KHz; the strong alkali solution is NaOH and KOH solution, the concentration of the strong alkali solution is 0.005-0.015 mol/L, the volume amount of the strong alkali solution and SiO 2 The mass ratio of (A) to (B) is 20-50 mL/g; the obtained SiO 2 Volume amount of deionized water and SiO redispersed in deionized water 2 The mass ratio of (A) to (B) is 20 to 50mL/g.
Preferably, the nickel salt in step b) is Ni (NH) 3 ) 6 Cl 2 Or Ni (NH) 3 ) 6 Br 2 (ii) a The concentration of the nickel salt solution is 0.02-0.1 mol/L.
Preference is given to Na as described in step c) 2 IrCl 6 The concentration of the water solution is 0.001-0.006 mol/L, and the concentration of the water solution of tetrabutylammonium bromide is 0.002-0.01 mol/L; na (Na) 2 IrCl 6 And tetrabutylammonium bromide in a molar ratio of 1 (1.8-3). CH in step c) 2 Cl 2 The amount of (A) is generally 20 to 40mL/g SiO 2 。
Preference is given to CH as described in step d) 2 Cl 2 Volume amount of (3) and SiO loaded with Ni 2 The mass ratio of (A) to (B) is 20 to 40mL/g.
Preferably, the reducing atmosphere in the step C is hydrogen; the rate of temperature rise is 2-20 ℃/min.
The invention also provides the Ni-Ir/SiO prepared by the method 2 The bimetallic catalyst is applied to photo-thermal synergistic methane dry reforming reaction.
Has the advantages that:
(1) The step of dripping the mixed solution is controlled by a peristaltic pump to slowly drip, so that the complexing effect is enhanced, and the generation rate of the target bimetallic catalyst is improved;
(2)Ni-Ir/SiO 2 the bimetallic nano-particles can regulate and control the proportion, the intermetallic action is controllable, the particle size of the nano-particles is smaller, the distribution is more uniform, and the particle size is about 2-4 nm.
(3) Mixing Ni-Ir/SiO 2 The method is used for the photothermal catalysis methane dry reforming reaction, the DRM reaction temperature is obviously reduced, and the original thermocatalysis effect at a higher temperature can be achieved at a relatively lower reaction temperature.
Detailed Description
Example 1
Methane dry reforming catalyst Ni-Ir/SiO 2 Preparation and testing of photo-thermal catalytic performance
(1)3.6Ni-0.54Ir/SiO 2 Preparation of the catalyst
Adsorption of metal cations
1g of SiO 2 Adding into 25mL of 0.013mol/L NaOH solution, and performing ultrasonic treatment for 40min at the ultrasonic frequency of 70KHz; repeatedly washing with deionized water until the pH of the obtained clear liquid is 9.31; the obtained SiO 2 Redissolved in 25mL deionized water;
using peristaltic pump to SiO 2 Adding 20mL of Ni (NH) with the concentration of 0.03mol/L into deionized water dropwise 3 ) 6 Cl 2 The dropping speed of the solution is 0.5mL/min, the solution is evenly mixed and centrifugally dried after the dropping is finished, and SiO with 3.6 percent of Ni load capacity is obtained 2 ；
Adsorption of B Complex Metal anions
Respectively measuring 14mL of 0.002mol/L Na 2 IrCl 6 Mixing the solution with 6mL of 0.01mol/L tetrabutylammonium bromide solution, and adding 40mL of CH 2 Cl 2 Mixing, shaking for 30min, centrifuging, and collecting upper oil phase;
anion adsorption: 1g of SiO loaded with Ni 2 Product 40mL CH was added 2 Cl 2 Dripping into the oil phase solution by using a peristaltic pump at the dripping speed of 0.1mL/min, and uniformly mixing to form SiO 2 A supported double salt (DCS);
product is CH 2 Cl 2 Washing and drying the solution;
the product is placed in a tube furnace and H is introduced 2 Heating to 400 ℃ at a speed of 10 ℃/min, and reducing for 40min.
(2) Testing of photo-thermal catalytic Properties
Weighing 30mg of catalyst, placing the catalyst in a reactor, and purging the reactor with Ar to remove internal air after confirming that the sealing is correct; will H 2 Introducing into a reactor, heating to 400 ℃ at a heating rate of 10 ℃/min, maintaining for 60min, and pre-activating before reaction as a catalyst; cooling the activated catalyst to normal temperatureWarm, again introduce Ar to remove H 2 (ii) a Reacting gas (CH) 4 /CO 2 /Ar =48, 4, 20 mL/min) was fed into the reactor. The light intensity is adjusted to 5W/cm 2 The reaction temperature was 500 ℃ and the catalytic performance was evaluated.
The prepared 3.6Ni-0.54Ir/SiO 2 The catalyst nanoparticles have a particle size of about 2.5nm 2 Conversion 46.1%, CH 4 The conversion was 33.6%. Conventional thermal catalysts are not active at this temperature.
Example 2
Methane dry reforming catalyst Ni-Ir/SiO 2 Preparation and testing of photo-thermal catalytic performance
(1)3Ni-0.51Ir/SiO 2 Preparation of the catalyst
Adsorption of metal cations
1g of SiO 2 Adding into 35mL of 0.08mol/L NaOH solution, and performing ultrasonic treatment for 50min at the ultrasonic frequency of 80KHz; repeatedly washing with deionized water until the pH of the obtained clear liquid is 9.2; the obtained SiO 2 Redissolved in 40mL deionized water;
using peristaltic pump to SiO 2 5mL of Ni (NH) with the concentration of 0.1mol/L is dripped into deionized water 3 ) 6 Cl 2 The dropping speed of the solution is 0.1mL/min, the solution is evenly mixed and centrifugally dried after the dropping is finished, and SiO with 3 percent of Ni load is obtained 2 ；
Adsorption of B complex metal anions
Respectively measuring 7mL of 0.004mol/L Na 2 IrCl 6 The solution and 14mL of 0.005mol/L tetrabutylammonium bromide solution are mixed, and 30mL of CH is added 2 Cl 2 Mixing, shaking for 20min, centrifuging to obtain upper oil phase;
anion adsorption: 1g of SiO loaded with Ni 2 Product 30mL CH was added 2 Cl 2 Dripping into the oil phase solution by using a peristaltic pump at the dripping speed of 0.4mL/min, and uniformly mixing to form SiO 2 A supported double salt (DCS);
product is with CH 2 Cl 2 Washing and drying the solution;
the product is placed in a tubeIn the furnace, H is introduced 2 Heating to 390 ℃ at the speed of 5 ℃/min and reducing for 60min.
(2) Testing of photo-thermal catalytic Properties
The catalyst performance was evaluated with reference to the conditions of example 1.
The prepared 3Ni-0.51Ir/SiO 2 The catalyst nanoparticles had a particle size of about 2nm, CO 2 Conversion 43.3%, CH 4 The conversion was 31.2%.
Example 3
Methane dry reforming catalyst Ni-Ir/SiO 2 Preparation and testing of photo-thermal catalytic performance
(1)2.5Ni-0.45Ir/SiO 2 Preparation of the catalyst
Adsorption of metal cations
1g of SiO 2 Adding into 22mL of 0.015mol/L NaOH solution, and performing ultrasonic treatment for 45min at an ultrasonic frequency of 60KHz; repeatedly washing with deionized water until the pH of the obtained clear liquid is 9.35; the obtained SiO 2 Redissolved in 30mL deionized water;
SiO using peristaltic pump 2 Adding 17mL of Ni (NH) with the concentration of 0.025mol/L into deionized water in a dropwise manner 3 ) 6 Cl 2 The dropping speed of the solution is 0.4mL/min, the solution is evenly mixed and centrifugally dried after the dropping is finished, and SiO with the Ni load of 2.5 percent is obtained 2 ；
Adsorption of B complex metal anions
Respectively measuring 5mL of 0.0052mol/L Na 2 IrCl 6 Mixing the solution and 10mL of 0.007mol/L tetrabutylammonium bromide solution, and adding 35mL of CH 2 Cl 2 Mixing, shaking for 25min, centrifuging to obtain upper oil phase;
anion adsorption: 1g of SiO loaded with Ni 2 Product 35mL CH was added 2 Cl 2 Dripping into the oil phase solution by using a peristaltic pump at the dripping speed of 0.3mL/min, and uniformly mixing to form SiO 2 A supported double salt (DCS);
product is CH 2 Cl 2 Washing and drying the solution;
the product is placed in a tube furnace and H is introduced 2 At a rate of 2 deg.C/minHeating to 410 ℃ and reducing for 50min.
(2) Testing of photo-thermal catalytic Properties
The catalyst performance was evaluated with reference to the conditions of example 1.
The prepared 2.5Ni-0.45Ir/SiO 2 The catalyst nanoparticles have a particle size of about 2.2nm and CO is present in the catalyst 2 Conversion was 42.5%, CH 4 The conversion was 30.8%.
Example 4
Methane dry reforming catalyst Ni-Ir/SiO 2 Preparation and testing of photo-thermal catalytic performance
(1)2.2Ni-0.26Ir/SiO 2 Preparation of the catalyst
Adsorption of metal cations
1g of SiO 2 Adding the mixture into 50mL of 0.005mol/L KOH solution, and carrying out ultrasonic treatment for 20min at the ultrasonic frequency of 25KHz; repeatedly washing with deionized water until the pH of the obtained clear liquid is 9.19; the obtained SiO 2 Redissolved in 50mL deionized water;
using peristaltic pump to SiO 2 6mL of Ni (NH) with the concentration of 0.06mol/L is dripped into deionized water 3 ) 6 Br 2 The dropping speed of the solution is 0.2mL/min, the solution is uniformly mixed and centrifugally dried after the dropping is finished, and SiO with the Ni load of 2.2 percent is obtained 2 ；
Adsorption of B complex metal anions
Measuring 10mL of 0.0023mol/L Na 2 IrCl 6 Mixing the solution with 7mL of 0.006mol/L tetrabutylammonium bromide solution, adding 25mL of CH 2 Cl 2 Mixing, shaking for 10min, centrifuging to obtain upper oil phase;
anion adsorption: 1g of SiO loaded with Ni 2 Product 25mL CH was added 2 Cl 2 Dripping into the oil phase solution by using a peristaltic pump at the dripping speed of 0.2mL/min, and uniformly mixing to form SiO 2 A supported double salt (DCS);
product is with CH 2 Cl 2 Washing and drying the solution;
the product is placed in a tube furnace and H is introduced 2 Heating to 415 ℃ at a speed of 20 ℃/min, and reducing for 35min.
(2) Testing of photo-thermal catalytic Properties
The catalyst performance was evaluated with reference to the conditions of example 1.
The prepared 2.2Ni-0.26Ir/SiO 2 The catalyst nanoparticles have a particle size of about 3.5nm 2 Conversion 39.6%, CH 4 The conversion was 27.3%.
Example 5
Methane dry reforming catalyst Ni-Ir/SiO 2 Preparation and testing of photo-thermal catalytic performance
(1)3.4Ni-0.54Ir/SiO 2 Preparation of the catalyst
Adsorption of metal cations
1g of SiO 2 Adding into 30mL 0.01mol/L KOH solution, and performing ultrasonic treatment for 30min at the ultrasonic frequency of 40KHz; repeatedly washing with deionized water until the pH of the obtained clear liquid is 9.25; the obtained SiO 2 Redissolved in 30mL deionized water;
using peristaltic pump to SiO 2 10mL of Ni (NH) with the concentration of 0.058mol/L is dripped into deionized water 3 ) 6 Br 2 The dropping speed of the solution is 0.3mL/min, the solution is evenly mixed and centrifugally dried after the dropping is finished, and SiO with 3.4 percent of Ni load capacity is obtained 2 ；
Adsorption of B complex metal anions
9mL of 0.0015mol/L of Na is weighed respectively 2 IrCl 6 Mixing the solution with 15mL of 0.0027mol/L tetrabutylammonium bromide solution, adding 20mL of CH 2 Cl 2 Mixing, shaking for 5min, centrifuging, and collecting upper oil phase;
anion adsorption: 1g of SiO loaded with Ni 2 Product 20mL CH was added 2 Cl 2 Dripping into the oil phase solution by using a peristaltic pump at the dripping speed of 0.5mL/min, and uniformly mixing to form SiO 2 A supported double salt (DCS);
product is with CH 2 Cl 2 Washing and drying the solution;
the product is placed in a tube furnace and H is introduced 2 Heating to 405 deg.C at 15 deg.C/min, and reducing for 30min.
(2) Testing of photo-thermal catalytic Properties
The catalyst performance was evaluated with reference to the conditions of example 1.
The prepared 3.4Ni-0.54Ir/SiO 2 The catalyst nanoparticles had a particle size of about 2.9nm and CO 2 Conversion 41.5%, CH 4 The conversion was 29.2%.

Claims (8)

1. Ni-Ir/SiO 2 Bimetallic catalyst, characterized by the fact that it is made of SiO 2 The carrier is Ni, ni accounts for 2.0-4.0% of the carrier, ir accounts for 0.2-0.6% of the carrier, and the mass ratio of Ni to Ir is 5-9; the preparation method comprises the following steps:
adsorption of metal cations
a) Mixing SiO 2 Adding into strong alkali solution, and performing ultrasonic dispersion; washing with deionized water until the pH of the obtained clear liquid is 9.1-9.4; the obtained SiO 2 Redispersing in deionized water;
b) To SiO 2 Dropwise adding a nickel salt solution into deionized water at the dropping speed of 0.1-0.5 mL/min, uniformly mixing after the dropwise adding is finished, and centrifugally drying; obtaining SiO loaded with nickel 2 ；
Adsorption of B complex metal anions
c) Mixing Na 2 IrCl 6 Mixing the aqueous solution and tetrabutylammonium bromide aqueous solution, adding CH 2 Cl 2 Shaking for 5-30 min and centrifuging to obtain the upper oil phase;
d) Anion adsorption: siO loaded with nickel 2 The product is dissolved in CH 2 Cl 2 Then the mixture is dripped into the oil phase solution with the dripping speed of 0.1-0.5 mL/min, and SiO is formed after uniform mixing 2 A supported double salt (DCS); product is with CH 2 Cl 2 Washing and drying the solution; placing the dried product in a tubular furnace, introducing a reducing atmosphere, heating to 390-420 ℃, and reducing for 30-60 min; obtaining Ni-Ir/SiO 2 A bimetallic catalyst.
2. The Ni-Ir/SiO of claim 1 2 Bimetallic catalyst, characterised by particles of catalyst particlesThe diameter is 2-4 nm.
3. The Ni-Ir/SiO of claim 1 2 The bimetallic catalyst is characterized in that the ultrasonic dispersion time in the step a) is 20-50 min, and the ultrasonic dispersion frequency is 25-80 KHz; the strong alkali solution is NaOH and KOH solution, the concentration of the strong alkali solution is 0.005-0.015 mol/L, the volume amount of the strong alkali solution and SiO 2 The mass ratio of (A) to (B) is 20-50 mL/g; the obtained SiO 2 Volume amount of deionized water and SiO redispersed in deionized water 2 The mass ratio of (A) to (B) is 20 to 50mL/g.
4. The Ni-Ir/SiO of claim 1 2 A bimetallic catalyst, characterized in that the nickel salt in step b) is Ni (NH) 3 ) 6 Cl 2 Or Ni (NH) 3 ) 6 Br 2 (ii) a The concentration of the nickel salt solution is 0.02-0.1 mol/L.
5. The Ni-Ir/SiO of claim 1 2 Bimetallic catalyst, characterized in that Na as described in step c) 2 IrCl 6 The concentration of the water solution is 0.001-0.006 mol/L, and the concentration of the water solution of tetrabutylammonium bromide is 0.002-0.01 mol/L; na (Na) 2 IrCl 6 And tetrabutylammonium bromide in a molar ratio of 1 (1.8-3).
6. The Ni-Ir/SiO of claim 1 2 Bimetallic catalyst, characterized in that CH as described in step d) 2 Cl 2 Volume amount of (3) and SiO loaded with Ni 2 The mass ratio of (A) to (B) is 20 to 40mL/g.
7. The Ni-Ir/SiO of claim 1 2 The bimetallic catalyst is characterized in that the reducing atmosphere in the step C is hydrogen; the rate of temperature rise is 2-20 ℃/min.
8. The Ni-Ir/SiO as claimed in claim 1 2 The application of bimetallic catalyst in photo-thermal synergistic dry reforming reaction.
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