CN113042053A - Co applied to propane catalytic oxidation in rice hull powder mediated preparation3O4-SiO2Method for preparing catalyst - Google Patents
Co applied to propane catalytic oxidation in rice hull powder mediated preparation3O4-SiO2Method for preparing catalyst Download PDFInfo
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 17
- 239000001294 propane Substances 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 title claims abstract description 15
- 230000003647 oxidation Effects 0.000 title claims abstract description 11
- 230000001404 mediated effect Effects 0.000 title claims description 8
- 240000007594 Oryza sativa Species 0.000 title 1
- 241000209094 Oryza Species 0.000 claims abstract description 87
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 43
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 43
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- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 43
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 43
- 229910018540 Si C Inorganic materials 0.000 claims abstract description 36
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 36
- 238000001354 calcination Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000002360 preparation method Methods 0.000 claims abstract description 16
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- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 33
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 16
- 239000002028 Biomass Substances 0.000 abstract description 15
- 235000013339 cereals Nutrition 0.000 abstract description 13
- 239000002245 particle Substances 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 238000005470 impregnation Methods 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000005764 inhibitory process Effects 0.000 abstract 1
- 238000003917 TEM image Methods 0.000 description 5
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 2
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- 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
- B01J23/75—Cobalt
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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Abstract
The invention discloses a method for preparing Co applied to propane catalytic oxidation by rice hull powder mediation3O4‑SiO2A method of preparing the catalyst. The method is characterized in that: firstly, pretreating rice hull powder through acid washing and calcination to prepare a rice hull powder Si-C template with large specific surface area, and then, carrying out an impregnation method on Co3O4Embedded in the pore structure of the rice hull powder Si-C template; finally, removing the biomass carbon component in the rice hull powder Si-C template through low-temperature calcination, and controlling and synthesizing Co with fine grain size3O4. The results show that the rice hull powder Si-C template is paired with Co3O4The particles play a role in limiting the range; co inhibition by the presence of biomass carbon3O4The reduction of the calcination temperature can inhibit Co agglomeration3O4And (4) growing the particles. The preparation method has the advantages of simple process, strong operability, wide raw material source and low cost, and meets the environmental requirements.
Description
Technical Field
The invention relates to Co3O4-SiO2Especially a method for preparing Co with fine grain size by using rice hull powder as Si-C template3O4The method of (1).
Background
In recent years, Co3O4Materials are of great interest and have found applications in a variety of fields such as gas sensing, energy storage and conversion, and catalytic oxidation reactions. Co3O4As a special transition metal oxide, the compound has the advantages of mixed cation valence, strong oxidation-reduction capability, good toxicity resistance, rich oxygen species and the like, so that Co is used as a catalyst for preparing the compound3O4Can be used as the best alternative of the noble metal catalyst. But during the preparation process, the temperature is high (mostly 500 deg.C)oC or above) causes easy growth of particles and serious limitation of Co due to sintering agglomeration3O4The application in the field of catalysis. In response to the problem, the synthesis of Co by using molecular sieve as a carrier has been reported in related documents3O4The results show that the molecular sieve template can effectively inhibit Co3O4Grain growth to greatly reduce Co3O4The grain size of (a). However, the method has high requirements on the molecular sieve, and if a special pore channel structure is required, the cost is high. New preparation strategy is adopted to inhibit the growth and agglomeration of particles, for Co3O4The theoretical research and application of the method have important significance.
The rice hulls have limited use due to their corrosion resistance, low nutritional content and high ash content. In some regions of the world it is desirable to have,disposal of the hulls also entails additional costs and may even lead to contamination problems. The rice hull powder after pretreatment has the characteristics of more pore structures, large specific surface area and the like, so that the rice hull powder is applied to preparing Co with fine grain size3O4The biomass value of the rice hull can be fully utilized.
The invention prepares Co with fine grain size by using rice hull powder Si-C template as a carrier through an impregnation method3O4The results show that the Co prepared by the method3O4-SiO2Has better propane catalytic oxidation performance.
Disclosure of Invention
The invention aims to provide fine grain size Co3O4The preparation method has the advantages of simple process, strong operability, wide raw material source and low cost, and meets the environmental requirements.
In order to achieve the purpose, the invention adopts the following technical scheme:
co prepared by rice hull powder mediation and applied to propane catalytic oxidation3O4-SiO2A method of catalyzing, comprising the steps of:
1) weighing rice hull powder, adding the rice hull powder into 10wt% of dilute hydrochloric acid, and magnetically stirring for 15 hours at room temperature; then washing the rice hull powder by deionized water until the pH value is 7, and centrifugally drying to obtain pretreated rice hull powder;
2) placing the pretreated rice hull powder obtained in the step 1) in a crucible, calcining at constant temperature in a muffle furnace, and collecting a black powder sample, namely a rice hull powder Si-C template;
3) 2.91 g of Co (NO) are weighed out3)2Adding the mixture into 100 mL of deionized water, and magnetically stirring the mixture at room temperature until the mixture is completely dissolved;
4) weighing the rice hull powder Si-C template obtained in the step 2) and transferring the rice hull powder Si-C template to 20 mL Co (NO) obtained in the step 3)3)2Soaking in the solution for 15 hr, and placing at 80 deg.CoC, drying in an oven, and collecting a black powder sample;
5) putting the black powder obtained in the step 4) into a muffle furnace, and calcining for 4 h in air atmosphere to obtain Co3O4-SiO2。
The rice hull powder mediated preparation is applied to the Co for propane catalytic oxidation3O4-SiO2A process for the preparation of a catalyst, characterized by: the calcination constant temperature of the rice hull powder in the step 1) is 400-600-oAnd C, calcining for constant temperature of 0.5-4 h.
The rice hull powder mediated preparation is applied to the Co for propane catalytic oxidation3O4-SiO2A process for the preparation of a catalyst, characterized by: the mass of the rice hull powder Si-C template in the step 4) is 1-2 g.
The rice hull powder mediated preparation is applied to the Co for propane catalytic oxidation3O4-SiO2A process for the preparation of a catalyst, characterized by: the constant temperature for calcining the black powder in the step 5) is 400-600-oC。
Specifically, the invention adopts an impregnation method to prepare Co with fine grain size by taking rice hull powder as a Si-C template3O4-SiO2. The method comprises the following specific steps:
1) weighing rice hull powder, adding the rice hull powder into 10wt% of dilute hydrochloric acid, and magnetically stirring for 15 hours at room temperature; then washing the rice hull powder by deionized water until the pH value is 7, and centrifugally drying to obtain pretreated rice hull powder;
2) placing the rice hull powder obtained in the step 1) in a crucible, calcining at constant temperature in a muffle furnace, and collecting a black powder sample to obtain a rice hull powder Si-C template;
3) 2.91 g Co (NO) are weighed out3)2Adding the mixture into 100 mL of deionized water, and magnetically stirring the mixture at room temperature until the mixture is completely dissolved;
4) weighing rice hull powder Si-C template and transferring to 20 mL Co (NO) obtained in step 3)3)2Soaking in the solution for 15 hr, and placing at 80 deg.CoC, drying in an oven, and collecting a black powder sample;
5) putting the black powder obtained in the step 4) into a muffle furnace, and calcining in an air atmosphere to obtain Co3O4-SiO2。
In the step 2), the calcining constant temperature of the rice husk powder is 400-600 oAnd C, calcining for constant temperature of 0.5-4 h.
In the step 4), the mass of the rice hull powder Si-C template is 1-2 g.
In the step 5), the constant temperature for calcining the black powder is 400-oC。
The invention has the following remarkable advantages:
1) the Si-C template used by the invention is from rice hull powder, and has wide source range and low price.
2) The invention effectively inhibits Co by utilizing the pore channel structure (confinement effect) of the rice hull powder Si-C template and the residual biomass carbon3O4To produce Co of fine grain size3O4。
3) The invention prepares Co by taking rice hull powder Si-C template as a carrier3O4Reduction of Co by lowering the calcination temperature3O4The grain size of (a).
Drawings
FIG. 1 shows Co prepared by using rice hull powder Si-C templates with different biomass carbon contents obtained in example 1 as carriers3O4-SiO2XRD pattern of (a).
FIG. 2 shows Co prepared using rice hull powder as a template, obtained in examples 1 to 43O4-SiO2XRD pattern of (a).
FIG. 3 is an SEM image obtained from examples 1-4, wherein: (a) SEM images of rice husk powder after acid washing, (c) and (d) calcination of pretreated rice husk powder SiO2SEM picture of-16.3% C template, (e), (f) 450 ℃ -10.5% Co3O4/(SiO2SEM picture of-16.3% C), (g), (h) 450 ℃ -10.5% Co3O4/SiO2SEM image of (d).
FIG. 4 is a TEM image obtained in examples 1-4, in which: (a-1), (a-2) and (a-3)550 ℃ -10.5% Co3O4/(SiO2TEM images of 16.3% C), (b-1), (b-2) and (b-3)450 ℃ -10.5% Co3O4/(SiO2TEM images of 16.3% C), (C-1), (C-2) and (C-3)450 ℃ -10.5% Co3O4/SiO2A TEM image of (a).
FIG. 5 shows 10.5% Co obtained in examples 1 to 43O4-SiO2The catalyst is 8000 ppm C3H8/N2Space velocity of 12000 mL h-1 g-1And (3) a propane catalytic oxidation performance graph under the test condition.
FIG. 6 is 450 ℃ -10.5% Co obtained in example 33O4/(SiO2-16.3% C) catalyst at 8000 ppm C3H8/N2Space velocity of 12000 mL h-1 g-1Cycle test performance plots under test conditions.
Detailed Description
Example 1
1) 20 g of rice hull powder (Jiangsu Liong hong Kong) was weighed into 300 mL of dilute hydrochloric acid with a mass fraction of 10wt%, and stirred magnetically at room temperature for about 15 hours.
2) Washing the rice hull powder obtained in the step 1) with deionized water for at least 8 times until the pH value is 7, and centrifugally drying to obtain pretreated rice hull powder;
3) placing the rice hull powder obtained in the step 2) into a crucible, and placing the crucible into a muffle furnace to obtain 5 partsoThe temperature rising rate of C/min is increased from room temperature to 450oAnd C, keeping the temperature for 2 hours to obtain a rice hull powder Si-C template with the biomass carbon content of 16.3 wt%.
4) 2.91 g of Co (NO) are weighed out3)2·6H2O was added to 100 mL of deionized water and then magnetically stirred at room temperature until completely dissolved.
5) 1.25 g of a rice hull powder Si-C template with a carbon content of 16.3 wt.% was transferred to 20 mL of Co (NO) obtained in step 4)3)2Soaking in the solution for 15 hr, and placing at 80 deg.CoC, drying in an oven, and collecting a black powder sample;
6) placing the black powder obtained in the step 5) in a crucible with the weight of 5oC/min heating rate in muffle 550oCalcining the mixture C at constant temperature for 4 hours, and collecting a black powder sample to obtain Co3O4Co loading of 10.5wt%3O4-SiO2(550-10.5% Co3O4/(SiO2-16.3 % C))。
Example 2 (varying amounts of residual Biomass carbon)
550-10.5% Co was prepared using the rice husk powder Si-C template of example 13O4/(SiO216.3% C), respectively synthesizing 10.5wt% Co with the rice hull powder with the biomass carbon content of 10.6wt%, 20.5wt% and 30.0wt% as the Si-C template3O4-SiO2The different synthesis processes are that the constant temperature duration of the step 3) in the step (1) is different, namely 3 h, 1.5 h and 1 h. (2) The rice hull powder Si-C templates in the step 5) have different usage amounts: when the carbon content of the biomass is 10.6wt%, 1.17 g of rice hull powder is weighed as a Si-C template to obtain 550-10.5% of Co3O4/(SiO2-10.6% C) sample; when the carbon content of the biomass is 20.5wt%, 1.57 g of rice hull powder is weighed as a Si-C template to obtain 550-10.5% of Co3O4/(SiO2-20.5% C) sample; when the carbon content of the biomass is 30.0wt%, 1.79 g of rice hull powder is weighed as a Si-C template to obtain 550-10.5% of Co3O4/(SiO230.0% C) samples, the remaining steps are completely identical.
XRD test shows that Co prepared with rice hull powder with different carbon contents and Si-C template as carrier3O4The XRD data (FIG. 1) of (A) shows that Co can be obtained by the method3O4Position of diffraction peak thereof and Co3O4Matched with the standard map (JCPDS, 078-1969). Calculated by the Sheer formula (Table 1), Co is obtained when the rice hull powder with the carbon content of 16.3 percent is used as the Si-C template3O4Has a minimum grain size of 17.1 nm.
TABLE 1 Co of the samples prepared in examples 1-43O4Particle size (calculated by the scherrer equation) and specific surface area data.
Example 3 (different calcination temperatures)
Prepared by the same method as example 1Rice hull powder with biomass carbon content of 16.3wt% is used as a Si-C template to synthesize 450-10.5% Co3O4/(SiO216.3% C), the synthesis process being different in that the calcination temperature in step 6) is 450oAnd C, the rest steps are completely consistent.
Example 4 (different Rice husk powder templates)
1) 20 g of rice hull powder (Jiangsu Liong hong Kong) was weighed into 300 mL of dilute hydrochloric acid with a mass fraction of 10wt%, and stirred magnetically at room temperature for about 15 hours.
2) Washing the rice hull powder obtained in the step 1) with deionized water for at least 8 times until the pH value is 7, and centrifugally drying to obtain pretreated rice hull powder;
3) placing the pretreated rice hull powder obtained in the step 2) in a crucible with the weight of 5oC/min heating rate in muffle 550oCalcining for 4 h, and collecting a white powder sample, namely the rice hull powder SiO2A template;
4) 2.91 g of Co (NO) are weighed out3)2·6H2O was added to 100 mL of deionized water and then magnetically stirred at room temperature until completely dissolved.
5) 1.09 g of rice hull powder SiO2Template transfer to 20 mL Co (NO) from step 4)3)2Soaking in the solution for 15 hr, and placing at 80 deg.CoC, drying in an oven, and collecting a powder sample;
6) placing the powder obtained in the step 5) in a crucible with the weight of 5oC/min heating rate in muffle furnace 450oCalcining the mixture C at constant temperature for 4 hours, and collecting black powder samples to obtain the Co with the concentration of 450-10.5 percent3O4/SiO2。
Co prepared by taking rice hull powder as template3O4-SiO2The XRD pattern (FIG. 2) and the particle size of the sample calculated according to the Sheerer equation (Table 1) show that when the Si-C template of rice hull powder with 16.3% of carbon content is used as the carrier and the calcination temperature is 450 DEGoC, Co produced3O4The smallest grain size (11.2 nm) indicates that Co favors fine grain size in the presence of a suitable amount of biomass carbon and at lower calcination temperatures3O4And (4) synthesizing.
Pretreated rice hull powder and 10.5% Co obtained by scanning electron microscope experiment3O4-SiO2SEM image of (fig. 3). As can be seen from the graphs a-d in FIG. 3, the rice hull powder after the acid washing-calcining pretreatment showed SiO2The morphology of nanoparticle stacking; it can be seen from the e-f diagram of FIG. 3 that Co is loaded3O4The rice hull powder still maintains SiO2Morphology of nanoparticle stacking, indicating Co3O4Present in SiO2The nano particles are stacked to generate a pore channel structure.
10.5% Co obtained by transmission electron microscope experiment3O4-SiO2TEM image of (fig. 4). As can be seen from FIG. 4, SiO is compared with rice hull powder2Template, Co3O4The dispersity on the rice hull powder Si-C template is higher, which shows that the existence of biomass carbon is favorable for Co3O4Is more easily formed into fine grain size Co3O4. Co can be seen from the graphs a-3, b-3 and c-3 in FIG. 43O4The lattice fringes are clearly visible, and the interplanar spacing corresponding to the lattice fringes is 0.244 nm, which is equivalent to that of Co3O4X-ray diffraction pattern of (2)311The spacing is identical.
The 10.5 percent Co shown in figure 5 is obtained by the propane catalytic oxidation performance test3O4-SiO2Performance test graphs. From FIG. 5, it can be seen that 450 ℃ -10.5% Co3O4/(SiO216.3% C) is better than 550 ℃ -10.5% Co3O4/(SiO2-16.3% C) and 450 ℃ -10.5% Co3O4/SiO2Co of fine particle size was confirmed3O4And the biomass carbon in the rice hull powder Si-C template is beneficial to improving the catalytic oxidation performance of the propane.
FIG. 6 is 450 ℃ -10.5% Co3O4/(SiO2-16.3% C) cycle performance test chart for catalytic propane oxidation. As can be seen from FIG. 6, after 5 cycles of performance testing, 450-10.5% Co3O4/(SiO2Almost no change in the performance of the-16.3% C) catalyst, indicating 450 ℃ to 10.5% Co3O4/(SiO216.3% C) catalyst has good thermal stability.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (4)
1. Co prepared by rice hull powder mediation and applied to propane catalytic oxidation3O4-SiO2A method of catalyzing, comprising the steps of:
1) weighing rice hull powder, adding the rice hull powder into 10wt% of dilute hydrochloric acid, and magnetically stirring for 15 hours at room temperature; then washing the rice hull powder by deionized water until the pH value is 7, and centrifugally drying to obtain pretreated rice hull powder;
2) placing the pretreated rice hull powder obtained in the step 1) in a crucible, calcining at constant temperature in a muffle furnace, and collecting a black powder sample, namely a rice hull powder Si-C template;
3) 2.91 g of Co (NO) are weighed out3)2Adding the mixture into 100 mL of deionized water, and magnetically stirring the mixture at room temperature until the mixture is completely dissolved;
4) weighing the rice hull powder Si-C template obtained in the step 2) and transferring the rice hull powder Si-C template to 20 mL Co (NO) obtained in the step 3)3)2Soaking in the solution for 15 hr, and placing at 80 deg.CoC, drying in an oven, and collecting a black powder sample;
5) putting the black powder obtained in the step 4) into a muffle furnace, and calcining for 4 h in air atmosphere to obtain Co3O4-SiO2。
2. The rice hull powder-mediated preparation of Co for propane catalytic oxidation according to claim 13O4-SiO2A process for the preparation of a catalyst, characterized by: the calcination constant temperature of the rice hull powder in the step 1) is 400-600-oAnd C, calcining for constant temperature of 0.5-4 h.
3. The rice hull powder-mediated preparation of Co for propane catalytic oxidation according to claim 1 or 23O4-SiO2A process for the preparation of a catalyst, characterized by: the mass of the rice hull powder Si-C template in the step 4) is 1-2 g.
4. The rice hull powder-mediated preparation of Co for propane catalytic oxidation according to claim 1 or 2 or 33O4-SiO2A process for the preparation of a catalyst, characterized by: the constant temperature for calcining the black powder in the step 5) is 400-600-oC。
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