CN113546640B - NiO-CoMn 2 O 4 Preparation method of catalyst and application of catalyst in catalytic oxidative degradation of toluene - Google Patents
NiO-CoMn 2 O 4 Preparation method of catalyst and application of catalyst in catalytic oxidative degradation of toluene Download PDFInfo
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910002521 CoMn Inorganic materials 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 230000003197 catalytic effect Effects 0.000 title abstract description 21
- 238000010525 oxidative degradation reaction Methods 0.000 title abstract description 3
- 229910052596 spinel Inorganic materials 0.000 claims description 34
- 239000011029 spinel Substances 0.000 claims description 34
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000003980 solgel method Methods 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- 230000015556 catabolic process Effects 0.000 abstract description 10
- 238000006731 degradation reaction Methods 0.000 abstract description 10
- 230000003647 oxidation Effects 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 8
- 239000001301 oxygen Substances 0.000 abstract description 8
- 239000012855 volatile organic compound Substances 0.000 abstract description 6
- 238000011056 performance test Methods 0.000 abstract 1
- 229910044991 metal oxide Inorganic materials 0.000 description 11
- 150000004706 metal oxides Chemical class 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 239000002131 composite material Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000001354 calcination Methods 0.000 description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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Abstract
The invention belongs to the field of catalytic degradation of volatile organic compounds, and particularly provides a NiO-CoMn 2 O 4 A preparation method of a catalyst and application thereof in catalytic oxidative degradation of toluene. The invention synthesizes NiO-CoMn by adopting a two-step method 2 O 4 Catalyst, niO modified NiO-CoMn 2 O 4 Mn of it 4+ And Co 3+ The content and the lattice oxygen quantity are obviously improved, the content and the lattice oxygen quantity play a leading role in the catalytic oxidation process, the p-toluene shows the optimal catalytic activity, and the toluene catalytic oxidation performance test shows that the catalyst prepared by the method realizes the low-temperature effective degradation of the p-toluene, can realize the complete degradation of the toluene at 190 ℃ and realize the complete degradation of CO 2 The selectivity is more than 95%.
Description
Technical Field
The invention belongs to the field of catalytic degradation of volatile organic compounds, and researches a NiO-CoMn 2 O 4 A preparation method of a catalyst and application thereof in catalytic oxidative degradation of toluene.
Background
With the increasing environmental pollution, particularly the emission of Volatile Organic Compounds (VOCs) from various sources, emission abatement techniques are urgently needed in order to maintain a clean air environment. Catalytic oxidation has attracted considerable attention as one of the most efficient methods and strategies. Transition metal oxides are potential replacement catalysts due to their low cost and good activity. Furthermore, researchers have found that spinel-type catalysts have higher stability during catalytic oxidation than mixed metal oxides and perovskite. In spinel (AB) 2 O 4 ) In which the metals A and B are in tetrahedral and octahedral positions, the adjacent cations (A and B) can optimize the catalytic activity by electron exchange. To obtain excellent catalytic properties, it is desirable that the spinel have a larger surface area and a high abundance of defects.
Zou et al have constructed metal defects (manganese/cobalt vacancies) by defect engineering to increase the active sites of Oxygen Reduction Reactions (ORR), attempting to apply spinel-type catalysts to the oxidation of VOCs. Hosseini et al report spinel CoMn prepared by sol-gel method 2 O 4 80% toluene conversion was achieved at 320 ℃. In addition, CN108295866B discloses a nano flower spinel CoMn for catalytic oxidation of VOCs 2 O 4 The catalyst can reach 99% toluene removal rate at 220 ℃. However, this patent only shows a toluene conversion of up to 99%, but toluene is not necessarily all converted to the final product CO 2 I.e. without giving CO 2 Selectivity.
Disclosure of Invention
The invention synthesizes CoMn by oxalic acid sol-gel method 2 O 4 Spinel support and loaded by impregnation method to obtain NiO-CoMn 2 O 4 Catalyst modified by two-step processPost spinel NiO-CoMn 2 O 4 Catalyst, mn of 4+ And Co 3+ The content and the lattice oxygen quantity are obviously improved, and the improvement of the low-temperature oxidation activity of the toluene is realized by playing a leading role in the catalytic oxidation process.
The method comprises the following steps:
(1)CoMn 2 O 4 preparation of spinel
Weighing 0.5mol of cobalt acetate and 1mol of manganese acetate, dissolving in 50mL of distilled water, stirring at a constant temperature of 60-80 ℃ on a magnetic stirrer, adding 10mL of oxalic acid solution, finally drying in vacuum and placing in a muffle furnace for roasting for 2-6h at 400-600 ℃.
(2)NiO-CoMn 2 O 4 Preparation of the catalyst
Weighing 0.001-0.01 mol of nickel nitrate to prepare a solution with the concentration of 0.2mol/L, and mixing the solution with the solution according to the concentration of the nickel nitrate: coMn (CoMn) 2 O 4 Spinel=1:1 to 1:1.5 molar ratio, the above successfully prepared CoMn was added 2 O 4 Stirring spinel for 2-4h, soaking at room temperature for two days, vacuum drying, and calcining at 400-600deg.C for 2-6h to obtain NiO-CoMn 2 O 4 A catalyst.
NiO-CoMn prepared by the method 2 O 4 The catalyst is used for catalyzing and oxidizing to degrade toluene.
The beneficial effects of the invention are as follows:
NiO-CoMn 2 O 4 exhibits the most excellent catalytic oxidation activity for toluene and CO 2 The selectivity can realize complete degradation of toluene at 190 ℃ and CO 2 The selectivity is more than 95%.
Drawings
Figure 1 is an XRD pattern of the individual component catalysts.
FIG. 2 shows toluene conversion and CO for catalysts of different compositions 2 Yield plot.
FIG. 3 is CoMn 2 O 4 NiO and NiO-CoMn 2 O 4 Is a XPS full spectrum of (C).
Detailed Description
The following are combined and implementedExample, a two-step method for synthesizing NiO-CoMn 2 O 4 A preparation method for catalyzing and degrading toluene by a catalyst.
Example 1
(1)CoMn 2 O 4 Preparation of spinel
0.5mol of cobalt acetate and 1mol of manganese acetate were weighed, dissolved in 50mL of distilled water, stirred at constant temperature of 80℃on a magnetic stirrer, 10mL of oxalic acid solution was added, finally dried in vacuo and placed in a muffle furnace for calcination at 400℃for 3 hours.
(2)NiO-CoMn 2 O 4 Preparation of the catalyst
Weighing 0.001mol of nickel acid to prepare a solution with the concentration of 0.2mol/L, and mixing the solution with nickel nitrate: coMn (CoMn) 2 O 4 Spinel = 1:1 molar ratio, the above successfully prepared CoMn was added 2 O 4 Spinel, stirring for 4h, soaking at room temperature for two days, vacuum drying, and calcining at 400deg.C for 3h in muffle furnace to obtain composite metal oxide, which is called NiO-CoMn 2 O 4 。
Example 2
(1)CoMn 2 O 4 Spinel was prepared as in example 1.
(2)NiO-CoMn 2 O 4 Preparation of the catalyst-2
Weighing 0.001mol of nickel nitrate, preparing into 0.2mol/L solution, adding CoMn 2 O 4 The molar ratio of spinel to nickel nitrate is 1:1.2, stirring for 4 hours, soaking for two days at room temperature, vacuum drying, and roasting in a muffle furnace at 400 ℃ for 3 hours to obtain a composite metal oxide, which is named NiO-CoMn 2 O 4 -2。
Example 3
(1)CoMn 2 O 4 Preparation of spinel same as in example 1
(2)NiO-CoMn 2 O 4 Preparation of the catalyst-3
Weighing 0.001mol of nickel nitrate, preparing into 0.2mol/L solution, adding CoMn 2 O 4 The molar ratio of spinel to nickel nitrate was 1:1.5, stirred for 4h and immersed for two days at room temperature, most preferablyDrying in vacuum and roasting in a muffle furnace at 400 ℃ for 3 hours to obtain the composite metal oxide, which is named NiO-CoMn 2 O 4 -3。
Comparative example 1
Weighing 0.001mol of nickel nitrate in a crucible, and calcining for 3 hours in a muffle furnace at 400 ℃ to obtain pure metal oxide NiO 2 。
Comparative example 2
Weighing 0.5mol of cobalt acetate and 1mol of manganese acetate, dissolving in 50mL of distilled water, stirring at constant temperature of 80 ℃ on a magnetic stirrer, adding 10mL of oxalic acid solution, finally drying in vacuum and roasting in a muffle furnace at 400 ℃ for 3h to obtain CoMn 2 O 4 Spinel.
Comparative example 3
(1)CoMn 2 O 4 Spinel was prepared as in example 1.
(2)FeO-CoMn 2 O 4 Preparation of the catalyst
Weighing 0.001mol of ferric nitrate, preparing into a ferric nitrate solution with the concentration of 0.2mol/L, and adding CoMn 2 O 4 The molar ratio of spinel to ferric nitrate is 1:1, stirring is carried out for 4 hours, dipping is carried out for two days at room temperature, finally vacuum drying is carried out, and the mixture is placed in a muffle furnace for roasting for 3 hours at 400 ℃, thus obtaining the composite metal oxide FeO-CoMn 2 O 4 。
Comparative example 4
(1)CoMn 2 O 4 Spinel was prepared as in example 1.
(2)CeO-CoMn 2 O 4 Preparation of the catalyst
Weighing 0.001mol of cerium nitrate, preparing into a solution with the concentration of 0.2mol/L, and weighing the cerium nitrate: coMn (CoMn) 2 O 4 Spinel=1:1 molar ratio, add the prepared CoMn 2 O 4 Spinel, stirring for 4h, soaking for two days at room temperature, vacuum drying, and calcining at 400deg.C for 3h in muffle furnace to obtain composite metal oxide CeO-CoMn 2 O 4 。
Comparative example 5
(1)CoMn 2 O 4 Spinel was prepared as in example 1.
(2)CuO-CoMn 2 O 4 Preparation of the catalyst
Weighing 0.001mol of copper nitrate, preparing into a solution with the concentration of 0.2mol/L, and weighing the copper nitrate: coMn (CoMn) 2 O 4 Spinel = 1:1 molar ratio, add the prepared CoMn 2 O 4 Spinel, stirring for 4h, soaking at room temperature for two days, vacuum drying, and calcining at 400deg.C for 3h to obtain composite metal oxide CuO-CoMn 2 O 4 。
In FIG. 1, it can be seen from FIG. 1A that the main peaks of the pure metal oxide NiO correspond mainly to the (222), (400), (440) crystal planes, coMn 2 O 4 The peaks of (C) are mainly concentrated in the (101), (211), (321), (224) crystal planes, niO-CoMn 2 O 4 The successful synthesis of (C) is manifested by NiO and CoMn in its XRD pattern 2 O 4 Is a peak of (2); the main peaks of CuO are seen in FIG. 1B to correspond to the (110), (002), (111), (-202), (-113) crystal planes, cuO-CoMn 2 O 4 The successful synthesis of (2) is manifested by the appearance of peaks of (110), (111) of CuO; fe is seen in FIG. 1C 2 O 3 The main peaks of (C) correspond to the (012), (104), (110), (113), (024), (116), (214), (300) crystal planes, fe 2 O 3 -CoMn 2 O 4 Is characterized by the successful synthesis of Fe 2 O 3 Peaks of (012), (113), (116) crystal planes and CoMn 2 O 4 The simultaneous occurrence of peaks of (101), (204), (211) crystal planes; ceO is seen in FIG. 1D 2 The main peaks of (C) correspond to (111), (200), (220), (311), (222), (400), (331) crystal planes, ceO 2 -CoMn 2 O 4 The successful synthesis of (2) is mainly represented by CeO 2 (111), (200), (220), (331) and CoMn 2 O 4 (211), (224) crystal planes.
In FIG. 2, the individual pure component metal oxides and spinel CoMn are seen 2 O 4 Toluene conversion and carbon dioxide yield. CoMn is seen in FIG. 2A 2 O 4 Shows low-temperature catalytic activity compared with pure metal oxide, can realize complete degradation of the toluene at 275 ℃, and the pure metal oxide can realize complete degradation of the toluene at more than 300 DEG C. The carbon dioxide yield of each catalyst can be seen in fig. 2B, with the carbon dioxide yield sequence being consistent with the order of toluene conversions. FIG. 2C shows a graph of toluene conversion activity for each of the composite catalysts, and it can be seen that each composite catalyst has a toluene conversion activity sequence of NiO-CoMn 2 O 4 (T 100％ ＝190℃)>CeO 2 -CoMn 2 O 4 (T 100％ ＝220℃)>Fe 2 O 3 -CoMn 2 O 4 (T 100％ ＝245℃)>CuO-CoMn 2 O 4 (T 100％ =260℃). FIG. 2D shows the order of carbon dioxide yields of the individual components, which we can see is positive with respect to their catalytic activity. FIG. 2E, F explores CoMn 2 O 4 The effect of the relationship of the amounts of spinel and nickel nitrate on catalytic activity can be seen in FIG. 2, E, F, for CoMn 2 O 4 NiO-CoMn with a spinel to nickel nitrate ratio of 1:1 2 O 4 The catalyst has better catalytic activity than the other two catalysts with different proportions.
Table 1 toluene degradation rate, carbon dioxide yield and corresponding minimum activity temperature.
FIG. 3 is NiO, coMn 2 O 4 And NiO-CoMn 2 O 4 The XPS technique can be used to determine the valence states of cobalt, manganese and nickel elements and the adsorption of oxygen (O) a ) And lattice oxygen (O) β ) The specific content and ratio of (2) are shown in Table. NiO is introduced in NiO-CoMn 2 O 4 More Mn is exposed on the surface 4+ And Co 3+ And lattice oxygen (O) β ) And surface adsorption of oxygen (O) a ) As well as the proportion of (c), related studies have shown that these are all advantageous for the catalytic oxidation of toluene.
TABLE 2 NiO-CoMn 2 O 4 Surface relative atomic concentration of Co, mn, ni and O elements of (C)
Claims (6)
1. NiO-CoMn 2 O 4 The catalyst is characterized by comprising the following preparation method steps:
（1）CoMn 2 O 4 preparation of spinel
Synthesis of CoMn by sol gel method 2 O 4 Spinel;
（2）NiO-CoMn 2 O 4 preparation of the catalyst
Preparing nickel nitrate into solution, adding CoMn prepared in the step (1) 2 O 4 The spinel is stirred for 2 to 4 hours, immersed for two days at room temperature, then dried in vacuum and placed in a muffle furnace for roasting, thus obtaining NiO-CoMn 2 O 4 A catalyst.
2. The NiO-CoMn of claim 1 2 O 4 A catalyst characterized in that the CoMn of step (1) 2 O 4 The preparation method of the spinel comprises the following steps: weighing 0.5mol of cobalt acetate and 1mol of manganese acetate, dissolving in 50mL of distilled water, uniformly stirring at a constant temperature of 60-80 ℃ on a magnetic stirrer, adding 10mL of oxalic acid solution, vacuum drying and placing in a muffle furnace for 400-
Roasting at 600 ℃ for 2-6h to obtain CoMn 2 O 4 Spinel.
3. The NiO-CoMn of claim 1 2 O 4 The catalyst is characterized in that the concentration of the prepared nickel nitrate solution in the step (2) is 0.2 mol/L.
4. The NiO-CoMn of claim 1 2 O 4 The catalyst is characterized in that the nickel nitrate and CoMn in the step (2) 2 O 4 The molar ratio of spinel is 1:1.
5. the NiO-CoMn of claim 1 2 O 4 The catalyst is characterized in that the muffle furnace in the step (2) is roasted for 2-6h at 400-600 ℃.
6. The NiO-CoMn of claim 1 2 O 4 The catalyst is used for catalyzing and oxidizing to degrade toluene.
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| CN202110789748.4A CN113546640B (en) | 2021-07-13 | 2021-07-13 | NiO-CoMn 2 O 4 Preparation method of catalyst and application of catalyst in catalytic oxidative degradation of toluene |
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| CN202110789748.4A CN113546640B (en) | 2021-07-13 | 2021-07-13 | NiO-CoMn 2 O 4 Preparation method of catalyst and application of catalyst in catalytic oxidative degradation of toluene |
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