CN108144614B - Catalyst for catalytic oxidation - Google Patents
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- CN108144614B CN108144614B CN201711489568.4A CN201711489568A CN108144614B CN 108144614 B CN108144614 B CN 108144614B CN 201711489568 A CN201711489568 A CN 201711489568A CN 108144614 B CN108144614 B CN 108144614B
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 29
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- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 58
- 239000010941 cobalt Substances 0.000 claims abstract description 58
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000919 ceramic Substances 0.000 claims abstract description 28
- -1 cobalt metal oxide Chemical class 0.000 claims abstract description 15
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 14
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- 238000000034 method Methods 0.000 claims description 14
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- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 23
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 20
- 239000005977 Ethylene Substances 0.000 abstract description 20
- 239000010815 organic waste Substances 0.000 abstract description 10
- 239000002912 waste gas Substances 0.000 abstract description 5
- 230000007774 longterm Effects 0.000 abstract description 3
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- 238000012512 characterization method Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
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- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000007084 catalytic combustion reaction Methods 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910021281 Co3O4In Inorganic materials 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- JAWGVVJVYSANRY-UHFFFAOYSA-N cobalt(3+) Chemical compound [Co+3] JAWGVVJVYSANRY-UHFFFAOYSA-N 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
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J35/56—
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- B01J35/612—
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- B01J35/613—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The present invention relates to a catalyst for catalytic oxidation. The catalyst for catalytic oxidation comprises cobalt metal oxide as an active ingredient and honeycomb ceramics as a carrier, wherein the active ingredient is loaded on the honeycomb ceramics, and the content ratio of divalent cobalt element to trivalent cobalt element in the cobalt metal oxide is more than 3. The catalyst provided by the invention has higher catalytic oxidation activity on organic waste gas by controlling the proportion of divalent cobalt element and trivalent cobalt element in the catalyst components, can realize high-efficiency long-term stable removal of the organic waste gas at lower temperature (220-280 ℃), wherein the removal rate of the ethylene waste gas exceeds 99% at 230 ℃, and the ethylene concentration reaches 5000mg/m3This removal efficiency is maintained.
Description
Technical Field
The invention relates to the technical field of waste gas treatment and catalysts, in particular to a catalyst for catalytic oxidation.
Background
Volatile Organic Compounds (VOCs) not only directly harm human health, but also can perform photochemical reaction with nitrogen oxides under certain meteorological conditions to cause the concentration of ozone in the atmosphere to be increased or the ozone reacts with free radicals in the atmosphere to form secondary aerosol pollutants, and play a very important role in forming pollutants such as ozone, dust haze and the like in the atmosphere. In recent years, with the continuous enhancement of the control of the VOCs, the concentration of ozone does not decrease or increase reversely, which indicates that the control of the VOCs needs to control the discharge concentration and discharge amount, and further needs to consider the elimination of components with high reaction activity such as alkenes, alkynes, aldehydes, ketones and the like.
At present, in the aspect of treating the high-activity VOCs components, direct combustion and catalytic combustion oxidation methods are the mainstream treatment methods. The direct combustion oxidation method has high combustion reaction temperature and large energy consumption in the process, and the application safety of the direct combustion oxidation method is also tested; the catalytic combustion oxidation method reduces the activation energy in the combustion oxidation reaction process by means of a catalyst, so that the oxidation temperature is obviously reduced, and the advantages in the aspects of safety and energy consumption are obvious. In the catalytic oxidation treatment process, the preparation and use of a good catalyst with high catalytic activity and high targeting (aiming at the catalytic combustion of high-activity VOCs components such as olefin and the like) are of great importance to the whole process. At present, common commercial catalysts in the field of catalytic combustion treatment of high-activity VOCs components have good catalytic combustion effects on most of low-concentration volatile organic pollutants; the active ingredients of the catalyst comprise precious metals such as Pt/Pd/Au/Ru and the like, so that the cost is high, the cost is high when the catalyst is applied to the treatment of high-concentration organic waste gas, and the economic benefit is poor; and the heat resistance stability is poor in the using process, the catalyst is easy to be poisoned and lose activity, and the defects limit the application and popularization of the catalyst in the treatment of high-concentration organic waste gas. In recent years, non-noble metal catalysts such as Fe/Ni/Cu/Mn and the like are continuously emerged, the performance is good, the price is relatively low, but the catalytic oxidation process still needs to be carried out under a higher temperature condition (for example, patent CN 106076351A and patent CN 103301853A). Therefore, the novel non-noble metal catalyst is developed, the low-temperature efficient and stable removal of the active VOCs components such as olefin is realized, and the economic benefit and the social benefit for environmental pollution treatment, energy conservation and consumption reduction are very obvious.
Disclosure of Invention
Based on the catalyst, the invention provides the catalyst for catalytic oxidation, the catalyst can obviously reduce the reaction temperature of catalytic oxidation, and the organic waste gas can be efficiently and stably removed for a long time under the condition of lower temperature (220-280 ℃).
The specific technical scheme is as follows:
a catalyst for catalytic oxidation, comprising a cobalt metal oxide as an active ingredient and a honeycomb ceramic as a carrier, the active ingredient being supported on the honeycomb ceramic, the content ratio of a divalent cobalt element to a trivalent cobalt element in the cobalt metal oxide being greater than 3.
In some of these embodiments, the cobalt metal oxide comprises CoO, Co2O3And Co3O4。
In some of these embodiments, the content ratio of the divalent cobalt element to the trivalent cobalt element in the cobalt metal oxide is greater than 3 and less than 4.
In some of these embodiments, the material of the honeycomb ceramic is selected from at least one of cordierite, alumina, silica, and silicon carbide.
In some of these embodiments, the honeycomb ceramic is cordierite.
In some embodiments, the total mass of the cobalt element in the cobalt metal oxide accounts for 0.1-15 wt% of the total weight of the catalyst.
In some embodiments, the total mass of cobalt element in the cobalt metal oxide accounts for 2-10 wt% of the total weight of the catalyst.
In some of the embodiments, the specific surface area of the catalyst is 1-100 m2/g。
In some of the embodiments, the specific surface area of the catalyst is 2-4 m2/g。
The catalyst for catalytic oxidation provided by the invention has the following advantages:
(1) the invention provides the catalyst by loading the active component on the honeycomb ceramic and controlling the ratio of divalent cobalt element to trivalent cobalt element in the active componentHas higher catalytic oxidation activity on organic waste gas (especially ethylene and hydrocarbon compounds below C4), can realize high-efficiency long-term stable removal of the organic waste gas under the condition of lower temperature (220-280 ℃), for example, the removal rate on the ethylene waste gas exceeds 99 percent at 230 ℃, and the ethylene concentration reaches 5000mg/m3This removal efficiency is maintained. The catalytic performance can be further improved by controlling the specific surface area of the catalyst and the content of the cobalt element.
(2) The reaction temperature for removing the organic waste gas by the catalyst oxidation provided by the invention is far lower than that of the traditional incineration technology, and the energy self-sustaining of the whole treatment system can be realized under a certain condition by recovering the energy released by oxidizing part of the organic waste gas, no external energy is needed, and the energy consumption and carbon dioxide emission required in the process of treating the organic waste gas are effectively reduced.
(3) The active components of the catalyst provided by the invention are transition metal and transition metal oxide, no noble metal is needed, the raw materials are cheap and easy to obtain, and the manufacturing cost and the use cost of the catalyst are obviously reduced.
(4) The active components of the catalyst provided by the invention are loaded on the honeycomb catalyst carrier, the air flow is smooth, the operation pressure is reduced, the long-term stable catalytic effect can be kept, and the catalyst has good industrial application prospect.
Drawings
FIG. 1 is an X-ray diffraction (XRD) characterization pattern of a catalyst sample from example 1;
FIG. 2 is an X-ray photoelectron spectroscopy (XPS) characterization of a sample of the catalyst of example 1;
FIG. 3 is a graph comparing the performance curves of sample one and sample two of example 1;
FIG. 4 is a graph of the effect of cobalt content on catalyst performance;
figure 5 is a graph of durability data for catalysts under pilot study conditions.
Detailed Description
In order to facilitate understanding of the present invention, the present invention will be further specifically described with reference to specific examples, while the following embodiments are set forth merely to illustrate the invention and not to limit the scope of the invention, and non-essential modifications and adjustments made by those skilled in the art according to the idea provided by the invention belong to the scope of the invention.
Example 1
And respectively obtaining a catalyst sample I and a catalyst sample II by adopting different preparation methods, and controlling the content of the metal cobalt element of the sample I to be consistent with that of the sample II.
The preparation method of the first sample comprises the following steps: preparing a cobalt nitrate aqueous solution (with the concentration of 67 mg/mL) at room temperature, soaking the honeycomb ceramic in the aqueous solution for 4 hours, taking out the honeycomb ceramic, draining off water on the surface of the honeycomb ceramic, placing the honeycomb ceramic in an oven, drying the honeycomb ceramic for 4 hours at the temperature of 80 ℃, taking out the honeycomb ceramic, placing the honeycomb ceramic in the oven, roasting the honeycomb ceramic for 4 hours at the temperature of 250 ℃, simultaneously introducing air from one end of the oven and discharging the air from the other end of the oven, and obtaining a first catalyst sample without circulating hot air of the oven.
The preparation method of the second sample comprises the following steps: preparing a cobalt nitrate aqueous solution (with the concentration of 67 mg/mL) at room temperature, placing the honeycomb ceramic in the aqueous solution, soaking for 4 hours, taking out, draining off water on the surface of the honeycomb ceramic, placing the honeycomb ceramic in a baking oven, drying for 4 hours at the temperature of 80 ℃, taking out, placing in the baking oven, baking for 4 hours at the temperature of 250 ℃, and circulating in the baking oven all the time without discharging hot air to prepare a catalyst sample II.
Specific surface area (BET), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) characterizations were performed on two catalyst samples prepared in this example, the XRD spectra are shown in fig. 1, and the XPS spectra are shown in fig. 2.
The BET characterization result shows that the specific surface area of the sample I reaches 2.2497, which is obviously higher than that of the sample II, namely 0.9001.
XRD characterization results show that the active component in the catalyst sample is cobalt metal oxide including CoO and Co2O3And Co3O4In particular, divalent cobalt oxide is used as the main component.
The XPS characterization result shows that the transition metal cobalt element is 794.8 +/-0 in a narrow spectrum.The peaks of 3eV and 779.7 + -0.3 eV correspond to trivalent cobalt (Co)3+) And divalent cobalt (Co)2+) The content of cobalt elements with different valence states is calculated by the aid of peak areas, wherein the content of the divalent cobalt element of the sample I is more than 75 percent, and the content ratio of the divalent cobalt element to the trivalent cobalt element is more than 3; the content ratio of the bivalent cobalt element and the bivalent cobalt element of the second sample is lower than the corresponding numerical value of the first sample.
According to the content of metallic cobalt element, the relative content of bivalent cobalt in the sample I is estimated to be 0.019 g/g of carrier, and the relative content of bivalent cobalt in the sample II is estimated to be 0.018 g/g of carrier.
The catalytic performance of the two catalyst samples prepared in this example was tested. The removal efficiency of the two catalyst samples on ethylene was tested by means of a fixed bed catalytic reaction tower, wherein the ethylene gas concentration was 3000mg/m3The space velocity of the fixed bed catalytic reaction tower is 2000-30000 h-1The concentration of ethylene gas at the inlet and outlet is measured by FID detector, and the temperature at the inlet and outlet of the fixed bed catalytic reaction tower is measured by thermocouple thermometer.
And (3) testing results: the temperature difference of the two samples reaching the same removal rate when ethylene is removed by oxidation is found, wherein the temperature of the first sample reaching 98 percent of removal rate is 260 ℃, the temperature of the second sample reaching 98 percent of removal rate is 300 ℃, and the low-temperature catalytic performance of the first sample is obviously better than that of the second sample. The catalytic performance curves for the two samples are shown in figure 3.
The effect of the specific surface area and the valence state of the two samples on their catalytic oxidation effect is shown in table 1.
TABLE 1 influence of specific surface area and valence on catalytic oxidation effect
| Catalyst and process for preparing same | The content wt% of cobalt element | Divalent cobalt/trivalent cobalt | Specific surface area m2/g | T98/℃ |
| Sample No | 2.5 | 3.15 | 2.2497 | 260 |
| Sample No. 2 | 2.5 | 2.71 | 0.9001 | 300 |
Example 2
Catalyst samples were prepared according to the preparation method of sample one of example 1, and catalyst small particle samples of different cobalt loadings were obtained by accumulating (increasing) the number of soaks. The catalyst soaked once had a cobalt loading of 0.0321 g/g support (i.e., 3.21 wt%), the catalyst soaked twice had a cobalt loading of 0.0617 g/g support (i.e., 6.17 wt%), and the catalyst soaked three times had a cobalt loading of 0.09 g/g support (i.e., 9 wt%). The loading of cobalt element increases with the accumulation of soaking times. The values of the cobalt (II)/cobalt (III) and the specific surface areas of the three catalyst samples prepared in this example are all comparable to those of the sample of example 1.
Three catalyst samples prepared in this example were tested for catalytic performance. The test method is as follows: the ethylene gas in the steel cylinder is taken as a processing object, and the concentration of the ethylene gas at the inlet of the catalytic reaction tower is controlled at 5000mg/m3Left and right, the airspeed is controlled at 10000 h-1Three catalyst samples were tested for catalytic performance.
The results show that: the removal rate of ethylene at about 230 ℃ was more than 99% in the sample with 6.17wt% of cobalt (sample four), and the removal rate of 99% in the sample with 3.21wt% of cobalt (sample three) was about 250 ℃; meanwhile, the sample with a cobalt content of 9wt% (sample five) has significantly lower performance than the sample with a cobalt content of 6.17wt% under the same temperature conditions. Comparing these three samples, the sample with a cobalt content of 6.17wt% outperformed the two others. The performance curves for the three samples of this example are shown in FIG. 4.
Example 3
Referring to the preparation method of the first sample in example 1, a pilot study is carried out on a catalyst with an active component equivalent to that of the first sample in example 1, exhaust gas of a PE (polyethylene) storage bin in a certain petrochemical area is used as an exhaust gas source, the exhaust gas flow is 400cmh, the main pollutant component is ethylene, and the concentration is 200-3000 mg/m3The temperature in the fixed bed catalytic reaction tower is 270 ℃, the ethylene gas concentration is detected by FID, and the ethylene gas concentration at the outlet of the fixed bed catalytic reaction tower is detected to be less than 10 mg/m3The pilot test results are shown in Table 2.
TABLE 2 catalyst (sample one) removal efficiency in units of mg/m for ethylene in a pilot study3
| Gas source | Total hydrocarbons | Methane | Non-methane total hydrocarbons | Time of sampling |
| Before treatment | 2022.1 | 2.28 | 2019.8 | 2016-12-07 |
| After treatment | 6.57 | 2.27 | 4.30 | 2016-12-07 |
As can be seen from Table 2, the catalyst of the present invention has high removal efficiency for ethylene waste gas in the exhaust gas of the actual petrochemical region at a lower temperature, the removal efficiency at 270 ℃ reaches 99%, and the reduction effect for ethylene waste gas is obvious.
Example 4
The catalyst of example 3 was tested for durability, and the exhaust gas was the PE bin vent gas from a petrochemical region, the major component was ethylene, and the concentration was 200-3The flow rate was 400cmh, the catalytic reaction temperature was 270 ℃, the durability test was carried out by continuously testing the catalyst for 800h by the method of example 3, and the removal efficiency of ethylene remained above 99% after 800h, and the test results are shown in fig. 5. As can be seen from FIG. 5, the catalyst of the present invention has high removal rate of ethylene oxide, high durability, complete appearance and good performance.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (7)
1. A catalyst for catalytic oxidation, characterized by comprising a cobalt metal oxide as an active ingredient and a honeycomb ceramic as a carrier, the active ingredient being supported on the honeycomb ceramic, the cobalt metal oxide having a content ratio of a divalent cobalt element to a trivalent cobalt element of more than 3 and less than 4, the cobalt metal oxide comprising CoO, Co, and a catalyst for catalytic oxidation2O3And Co3O4；
The catalyst is prepared by the following method: preparing a cobalt nitrate aqueous solution at room temperature, placing the honeycomb ceramic in the aqueous solution for soaking for 4 hours, taking out the honeycomb ceramic, draining the water on the surface of the honeycomb ceramic, placing the honeycomb ceramic in a baking oven, drying for 4 hours at the temperature of 80 ℃, taking out the honeycomb ceramic and placing the honeycomb ceramic in an oven, baking for 4 hours at the temperature of 250 ℃, simultaneously introducing air from one end of the oven, discharging the air from the other end of the oven, and keeping hot air of the oven from circulating.
2. The catalyst for catalytic oxidation according to claim 1, wherein the material of the honeycomb ceramic is at least one selected from the group consisting of cordierite, alumina, silica and silicon carbide.
3. The catalyst for catalytic oxidation according to claim 2, wherein the material of the honeycomb ceramic is cordierite.
4. The catalyst for catalytic oxidation according to claim 1, wherein the total mass of cobalt element in the cobalt metal oxide is 0.1 to 15wt% based on the total weight of the catalyst.
5. The catalyst for catalytic oxidation according to claim 4, wherein the total mass of cobalt element in the cobalt metal oxide accounts for 2-10 wt% of the total weight of the catalyst.
6. The catalyst for catalytic oxidation according to claim 1, having a specific surface area of 1 to 100 m2/g。
7. The catalyst for catalytic oxidation according to claim 6, having a specific surface area of 2 to 4m2/g。
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| CN101138728A (en) * | 2007-10-19 | 2008-03-12 | 华南理工大学 | Metallic oxide mixture catalyzer for purifying organic waste gas and method of preparing the same |
| CN106732576A (en) * | 2015-11-19 | 2017-05-31 | 中国石油化工股份有限公司 | A kind of catalyst for catalytic oxidation and its preparation method and application |
| CN107096526A (en) * | 2016-02-22 | 2017-08-29 | 江苏中科睿赛污染控制工程有限公司 | A kind of catalysis oxidation VOCs composite catalyst, preparation method and purposes |
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| CN101138728A (en) * | 2007-10-19 | 2008-03-12 | 华南理工大学 | Metallic oxide mixture catalyzer for purifying organic waste gas and method of preparing the same |
| CN106732576A (en) * | 2015-11-19 | 2017-05-31 | 中国石油化工股份有限公司 | A kind of catalyst for catalytic oxidation and its preparation method and application |
| CN107096526A (en) * | 2016-02-22 | 2017-08-29 | 江苏中科睿赛污染控制工程有限公司 | A kind of catalysis oxidation VOCs composite catalyst, preparation method and purposes |
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