CN114160147A - Composite oxide catalyst for synchronously removing VOCs and NOx in sulfur-containing flue gas and preparation method and application thereof - Google Patents
Composite oxide catalyst for synchronously removing VOCs and NOx in sulfur-containing flue gas and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a composite oxide catalyst for synchronously removing VOCs and NOx in sulfur-containing flue gas and a preparation method and application thereof. The catalyst is prepared by adopting a coprecipitation method, and the specific steps comprise: (1) adding an active metal source into deionized water, and uniformly stirring to obtain a precursor solution, wherein the active metal source contains at least one element of Cu, Ce and Ti; (2) slowly adding ammonia water into the precursor solution to adjust the pH until precipitation occurs; (3) and washing the obtained precipitate with deionized water, drying and calcining to finally obtain the composite oxide catalyst for synchronously removing VOCs and NOx in the sulfur-containing flue gas. The catalyst prepared by the method of the invention shows excellent synchronous removal performance and stability of VOCs and NOx under complex flue gas conditions.
Description
Technical Field
The invention belongs to the technical field of air pollution control, and particularly relates to a composite metal oxide catalyst for synchronously removing VOCs and NOx in sulfur-containing flue gas and application thereof.
Background
Near ground surface O3The main source is the reaction of nitrogen oxides (NOx) and volatile organic pollutants (VOCs) in the presence of a catalyst for the irradiation of light in order to reduce O3Pollution, and controlling the emission of precursors thereof is particularly important.
The industrial fixed source is one of the main sources of atmospheric pollutants, and the discharged flue gas components of the industrial fixed source are complex and contain NOx, VOCs and SO2And the like. At present, mature denitration technology and treatment standard exist for controlling NOx emission in flue gas, but no effective treatment and targeted control technology and technology exist for VOCs. Because the concentration of VOCs in flue gases is much less than the concentration of NOx, it is technically and economically sound to control both NOx and VOCs simultaneously in one treatment unit, rather than to build redundant facilities to remove VOCs, for investment cost and site space constraints. Furthermore, from theoretical studies, the temperature window for NOx removal overlaps with the temperature window for VOCs degradation, and the SCR catalyst also has the ability to oxidatively remove VOCs. Therefore, the simultaneous removal of NOx and VOCs using existing denitrifiers is the most economical and effective means.
At present V2O5-WO3/TiO2The catalytic material which is most widely applied in the industrial flue gas denitration process has an excellent denitration effect within the temperature window range of 300-400 ℃, but has a poor removal effect on VOCs in flue gas, and contains SO2The catalyst is easy to have a poisoning phenomenon under the complex smoke condition, so that the activity is reduced. Therefore, the development of a dual-function catalyst suitable for synchronously removing VOCs and NOx in the sulfur-containing complex flue gas is needed.
Disclosure of Invention
The invention provides a composite oxide catalyst for synchronously removing VOCs and NOx in sulfur-containing flue gas, which is prepared by adopting a coprecipitation method, shows excellent synchronous removal activity of NOx and VOCs within the range of 240-380 ℃, can still keep stable activity in the sulfur-containing complex flue gas, and has good application prospect in the direction of removing multiple pollutants in the sulfur-containing flue gas. The method comprises the following specific steps:
(1) adding an active metal source into deionized water, transferring to a magnetic stirrer after ultrasonic treatment, continuously stirring until the active metal source is completely dissolved, continuously stirring for 3 hours at room temperature to form a stable precursor solution,
(2) and dropwise adding ammonia water with a certain concentration into the precursor solution at room temperature, and continuously stirring until the pH value of the solution reaches 10-11 and precipitation occurs. Washing the obtained precipitate with deionized water, drying, rolling, screening, and finally calcining to obtain the composite oxide catalyst for synchronously removing VOCs and NOx in sulfur-containing flue gas.
In the step (1), the active metal source is Cu (NO)3)2、Ce(NO3)3、Ti(SO4)2And the dosage of Cu/Ce/Ti is 0-5 mmol, 0-5 mmol and 15mmol respectively, and the preferable Cu/Ce/Ti molar ratio is 3: 2: 15, under the condition, the synchronous removal activity of VOCs and NOx of the catalyst reaches the highest.
In the step (2), the mass percentage concentration of the ammonia water solution is 10-15%.
In the step (2), the drying temperature of the precipitate is 70-80 ℃, the drying time is 10-12 hours, the final calcining temperature of the catalyst is 400-600 ℃, and the calcining time is 3-5 hours.
The invention also provides application of the catalyst in synchronous removal of VOCs and NOx in flue gas within a wide temperature window range, and the catalyst shows synchronous removal performance of VOCs and NOx under the condition that the temperature window is 240-390 ℃.
The invention further provides application of the catalyst in synchronous removal of VOCs and NOx in sulfur-containing complex flue gas, and the catalyst can keep stable synchronous removal activity of VOCs and NOx in flue gas under the environment of 300-500 ppm of sulfur-containing flue gas.
Compared with the prior art, the invention has the main advantages that:
the catalyst prepared by adopting a coprecipitation method has excellent synchronous removal efficiency of VOCs and NOx at 240-380 (in)>90%) and when applied to a sulfur-containing flue gas environment, contains 300-500 ppm SO2The activity of synchronously removing VOCs and NOx still can be kept stable in a complex smoke environment, so that the method has an application prospect in the field of synchronously removing multiple pollutants in smoke.
Drawings
FIG. 1 is an XRD analysis of a composite oxide catalyst for the simultaneous removal of VOCs and NOx from sulfur-containing flue gas, as prepared in example 1;
FIG. 2 is a test chart of toluene degradation activity under flue gas conditions of composite oxide catalysts for synchronous removal of VOCs and NOx in sulfur-containing flue gas, respectively prepared in examples 1 to 7;
FIG. 3 is a test chart of the activity of the composite oxide catalyst for simultaneous removal of VOCs and NOx from a sulfur-containing flue gas, prepared in example 8;
FIG. 4 is a sulfur resistance activity test chart of the composite oxide catalyst for the simultaneous removal of VOCs and NOx from sulfur-containing flue gas prepared in example 8;
FIG. 5 is a sulfur resistance activity test chart of the composite oxide catalyst for the simultaneous removal of VOCs and NOx from sulfur-containing flue gas prepared in example 8.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Example 1
(1) Precursor gel preparation
According to the ratio of n (Cu) to n (Ce) in the final sample: n (ti) ═ 0: 5: 15, cerium nitrate (Ce (NO) was weighed3)3) And sulfurTitanium acid (Ti (SO)4)2) Adding into deionized water, dispersing by using ultrasonic, and stirring for 1h at room temperature until the precursor solution is fully dissolved. Slowly adding ammonia water with the mass percentage concentration of 15% into the precursor solution at room temperature, and continuously stirring until the pH value of the solution reaches 10 and precipitates appear.
(2) Material purification
And repeatedly washing the obtained precipitate for 3-5 times by using deionized water through centrifugation, drying at 80 ℃ for 12h, and finally calcining at 400 ℃ for 5h to obtain the composite oxide catalyst for synchronously removing VOCs and NOx in sulfur-containing flue gas, wherein the composite oxide catalyst is marked as Ce 5/Ti.
(3) Toluene degradation Activity test
Grinding and screening the obtained catalyst to 40-60 meshes, placing the catalyst in a fixed bed quartz tube reactor in a simulated atmosphere (toluene: 50ppm, NO: 500ppm, NH)3：500ppm，O2: 10 vol%, the remainder N2) The degradation performance of the sample at 150-390 ℃ in toluene is tested, and the total gas flow is 200mL/min (space velocity SV is 120000mL g-1h-1)。
Fig. 1 is an SEM photograph of the catalyst for low-temperature plasma co-denitrification prepared in example 1, and it can be seen that the catalyst prepared by the present invention has a very stable cubic structure.
Example 2
(1) Precursor gel preparation
According to the ratio of n (Cu) to n (Ce) in the final sample: n (ti) ═ 1: 4: 15 molar ratio of copper nitrate (Cu (NO)3)2) Cerium nitrate (Ce (NO)3)3) And titanium sulfate (Ti (SO)4)2) Adding into deionized water, dispersing by using ultrasonic, and stirring for 1h at room temperature until the precursor solution is fully dissolved. Slowly adding 10% ammonia water into the precursor solution at room temperature, and continuously stirring until the pH value of the solution reaches 11 and precipitates appear.
(2) Material purification
And repeatedly washing the obtained precipitate for 3-5 times by using deionized water through centrifugation, drying at 80 ℃ for 11h, and finally calcining at 500 ℃ for 5h to obtain the composite oxide catalyst for synchronously removing VOCs and NOx in sulfur-containing flue gas, wherein the composite oxide catalyst is recorded as Cu1Ce 4/Ti.
(3) Toluene degradation Activity test
Grinding and screening the obtained catalyst to 40-60 meshes, placing the catalyst in a fixed bed quartz tube reactor in a simulated atmosphere (toluene: 50ppm, NO: 500ppm, NH)3：500ppm，O2: 10 vol%, the remainder N2) The degradation performance of the sample at 150-390 ℃ in toluene is tested, and the total gas flow is 200mL/min (space velocity SV is 120000mL g-1h-1)。
Example 3
(1) Precursor gel preparation
According to the ratio of n (Cu) to n (Ce) in the final sample: n (ti) ═ 2: 3: 15 molar ratio of copper nitrate (Cu (NO)3)2) Cerium nitrate (Ce (NO)3)3) And titanium sulfate (Ti (SO)4)2) Adding into deionized water, dispersing by using ultrasonic, and stirring for 1h at room temperature until the precursor solution is fully dissolved. Slowly adding ammonia water with the mass percent concentration of 12% into the precursor solution at room temperature, and continuously stirring until the pH value of the solution reaches 10 and precipitates appear.
(2) Material purification
And repeatedly washing the obtained precipitate for 3-5 times by using deionized water through centrifugation, drying at 80 ℃ for 12h, and finally calcining at 480 ℃ for 5h to obtain the composite oxide catalyst for synchronously removing VOCs and NOx in sulfur-containing flue gas, wherein the composite oxide catalyst is recorded as Cu2Ce 3/Ti.
(3) Toluene degradation Activity test
Grinding and screening the obtained catalyst to 40-60 meshes, placing the catalyst in a fixed bed quartz tube reactor in a simulated atmosphere (toluene: 50ppm, NO: 500ppm, NH)3：500ppm，O2: 10 vol%, the remainder N2) The degradation performance of the sample at 150-390 ℃ in toluene is tested, and the total gas flow is 200mL/min (space velocity SV is 120000mL g-1h-1)。
Example 4
(1) Precursor gel preparation
According to the ratio of n (Cu) to n (Ce) in the final sample: n (ti) ═ 2.5: 2.5: 15 molar ratio of copper nitrate (Cu (NO)3)2) Cerium nitrate (Ce (NO)3)3) And titanium sulfate (Ti (SO)4)2) Adding into deionized water, dispersing by using ultrasonic, and stirring for 1h at room temperature until the precursor solution is fully dissolved. Slowly adding ammonia water with the mass percent concentration of 14% into the precursor solution at room temperature, and continuously stirring until the pH value of the solution reaches 10 and precipitates appear.
(2) Material purification
And repeatedly washing the obtained precipitate for 3-5 times by using deionized water through centrifugation, drying at 70 ℃ for 11h, and finally calcining at 500 ℃ for 3h to obtain the composite oxide catalyst for synchronously removing VOCs and NOx in sulfur-containing flue gas, wherein the composite oxide catalyst is recorded as Cu2.5Ce2.5/Ti.
(3) Toluene degradation Activity test
Grinding and screening the obtained catalyst to 40-60 meshes, placing the catalyst in a fixed bed quartz tube reactor in a simulated atmosphere (toluene: 50ppm, NO: 500ppm, NH)3：500ppm，O2: 10 vol%, the remainder N2) The degradation performance of the sample at 150-390 ℃ in toluene is tested, and the total gas flow is 200mL/min (space velocity SV is 120000mL g-1h-1)。
Example 5
(1) Precursor gel preparation
According to the ratio of n (Cu) to n (Ce) in the final sample: n (ti) ═ 3: 2: 15 molar ratio of copper nitrate (Cu (NO)3)2) Cerium nitrate (Ce (NO)3)3) And titanium sulfate (Ti (SO)4)2) Adding into deionized water, dispersing by using ultrasonic, and stirring for 1h at room temperature until the precursor solution is fully dissolved. Slowly adding ammonia water with the mass percent concentration of 15% into the precursor solution at room temperature, and continuously stirring until the pH value of the solution reaches 10 and precipitates appear.
(2) Material purification
And repeatedly washing the obtained precipitate for 3-5 times by using deionized water through centrifugation, drying at 75 ℃ for 12h, and finally calcining at 500 ℃ for 5h to obtain the composite oxide catalyst for synchronously removing VOCs and NOx in sulfur-containing flue gas, wherein the composite oxide catalyst is recorded as Cu3Ce 2/Ti.
(3) Toluene degradation Activity test
Grinding and screening the obtained catalyst to 40-60 meshes, placing the catalyst in a fixed bed quartz tube reactor in a simulated atmosphere (toluene: 50ppm, NO: 500ppm, NH)3：500ppm，O2: 10 vol%, the remainder N2) The degradation performance of the sample at 150-390 ℃ in toluene is tested, and the total gas flow is 200mL/min (space velocity SV is 120000mL g-1h-1)。
The X-ray diffraction pattern of the catalyst (fig. 1) indicates that we successfully prepared the CuCeTi catalyst and had a higher degree of crystallinity.
Example 6
(1) Precursor gel preparation
According to the ratio of n (Cu) to n (Ce) in the final sample: n (ti) ═ 4: 1: 15 molar ratio of copper nitrate (Cu (NO)3)2) Cerium nitrate (Ce (NO)3)3) And titanium sulfate (Ti (SO)4)2) Adding into deionized water, dispersing by using ultrasonic, and stirring for 1h at room temperature until the precursor solution is fully dissolved. Slowly adding ammonia water with the mass percent concentration of 15% into the precursor solution at room temperature, and continuously stirring until the pH value of the solution reaches 11 and precipitates appear.
(2) Material purification
And repeatedly washing the obtained precipitate for 3-5 times by using deionized water through centrifugation, drying at 80 ℃ for 12h, and finally calcining at 420 ℃ for 4h to obtain the composite oxide catalyst for synchronously removing VOCs and NOx in sulfur-containing flue gas, wherein the composite oxide catalyst is marked as Cu4Ce 1/Ti.
(3) Toluene degradation Activity test
Grinding and screening the obtained catalyst to 40-60 meshes, placing the catalyst in a fixed bed quartz tube reactor in a simulated atmosphere (toluene: 50ppm, NO: 500ppm, NH)3：500ppm，O2: 10 vol%, the remainder N2) The degradation performance of the sample at 150-390 ℃ in toluene and the total gas content are testedThe flow rate is 200mL/min (space velocity SV 120000mL g-1h-1)。
Example 7
(1) Precursor gel preparation
According to the ratio of n (Cu) to n (Ce) in the final sample: n (ti) ═ 5: 0: 15 molar ratio of copper nitrate (Cu (NO)3)2) And titanium sulfate (Ti (SO)4)2) Adding into deionized water, dispersing by using ultrasonic, and stirring for 1h at room temperature until the precursor solution is fully dissolved. Slowly adding ammonia water with the mass percentage concentration of 15% into the precursor solution at room temperature, and continuously stirring until the pH value of the solution reaches 10 and precipitates appear.
(2) Material purification
And repeatedly washing the obtained precipitate for 3-5 times by using deionized water through centrifugation, drying at 75 ℃ for 12h, and finally calcining at 500 ℃ for 4h to obtain the composite oxide catalyst for synchronously removing VOCs and NOx in sulfur-containing flue gas, wherein the composite oxide catalyst is recorded as Cu 5/Ti.
(3) Toluene degradation Activity test
Grinding and screening the obtained catalyst to 40-60 meshes, placing the catalyst in a fixed bed quartz tube reactor in a simulated atmosphere (toluene: 50ppm, NO: 500ppm, NH)3：500ppm，O2: 10 vol%, the remainder N2) The degradation performance of the sample at 150-390 ℃ in toluene is tested, and the total gas flow is 200mL/min (space velocity SV is 120000mL g-1h-1)。
The samples obtained above were subjected to a toluene degradation test under flue gas conditions according to the toluene degradation activity test method of examples 1 to 7, and the results are shown in fig. 2, from which it is understood that the catalyst prepared by the method of the present invention exhibits excellent toluene degradation effect even under flue gas conditions, with Cu3Ce2Ti being a preferred formulation.
Example 8
(1) Precursor gel preparation
According to the ratio of n (Cu) to n (Ce) in the final sample: n (ti) ═ 3: 2: 15 molar ratio of copper nitrate (Cu (NO)3)2) Cerium nitrate (Ce (NO)3)3) And titanium sulfate(Ti(SO4)2) Adding into deionized water, dispersing by using ultrasonic, and stirring for 1h at room temperature until the precursor solution is fully dissolved. Slowly adding ammonia water with the mass percent concentration of 15% into the precursor solution at room temperature, and continuously stirring until the pH value of the solution reaches 10 and precipitates appear.
(2) Material purification
And repeatedly washing the obtained precipitate for 3-5 times by using deionized water through centrifugation, drying at 75 ℃ for 12h, and finally calcining at 400 ℃ for 4.5h to obtain the composite oxide catalyst for synchronously removing VOCs and NOx in sulfur-containing flue gas, wherein the composite oxide catalyst is recorded as Cu3Ce 2/Ti.
(4) Toluene and NO synchronous removal activity test
Grinding and screening the obtained catalyst to 40-60 meshes, placing the catalyst in a fixed bed quartz tube reactor in a simulated atmosphere (toluene: 50ppm, NO: 500ppm, NH)3：500ppm，O2: 10 vol%, the remainder N2) The degradation performance of the sample at 150-390 ℃ in toluene is tested, and the total gas flow is 200mL/min (space velocity SV is 120000mL g-1h-1)。
(4) Test for Sulfur resistance
Grinding and screening the obtained catalyst to 40-60 meshes, placing the catalyst in a fixed bed quartz tube reactor in a simulated atmosphere (toluene: 50ppm, SO)2：200/500ppm，O2: 10 vol%, the remainder N2) The degradation performance of the sample at 150-390 ℃ in toluene is tested, and the total gas flow is 200mL/min (space velocity SV is 120000mL g-1h-1)。
Fig. 3 is a result of activity test for synchronously removing toluene and NO in the catalyst prepared in example 8, and it can be seen from the figure that the catalyst prepared in the present invention can effectively achieve the synchronous removal of toluene and NO, and the effective degradation temperature range is 243-380 ℃.
FIGS. 4 and 5 show the catalyst prepared in example 8 at 200ppm SO and 500ppm SO, respectively2As shown in a test result of toluene degradation activity in an air atmosphere, the catalyst prepared by the method can still keep long-time stability in sulfur-containing flue gas, and has an industrial application prospect.
The above examples of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A composite oxide catalyst for synchronously removing VOCs and NOx in sulfur-containing flue gas is characterized by being prepared by a coprecipitation method, and comprising the following specific steps:
(1) adding an active metal source into deionized water, carrying out ultrasonic treatment, transferring to a magnetic stirrer, and continuously stirring until the active metal source is completely dissolved to form a stable precursor solution, wherein the active metal source contains more than one element of Cu, Ce or Ti;
(2) dropwise adding an ammonia water solution into the precursor solution at room temperature and continuously stirring until the solution reaches a certain pH value and precipitates; washing the obtained precipitate with deionized water, drying, rolling, screening, and finally calcining to obtain the composite oxide catalyst for synchronously removing VOCs and NOx in sulfur-containing flue gas.
2. The composite oxide catalyst for synchronously removing VOCs and NOx in sulfur-containing flue gas according to claim 1, wherein in the step (1), the active metal source is more than one of copper nitrate, cerium nitrate or titanium sulfate.
3. The composite oxide catalyst for synchronously removing VOCs and NOx in sulfur-containing flue gas according to claim 1, wherein the use amounts of Cu/Ce/Ti are 0-5 mmol, 0-5 mmol and 15mmol, respectively.
4. The composite oxide catalyst for synchronously removing VOCs and NOx in sulfur-containing flue gas according to claim 1, wherein in the step (2), the mass percentage concentration of the ammonia water solution is 10-15%;
in the step (2), the pH value of the solution is 10-11.
5. The composite oxide catalyst for synchronously removing VOCs and NOx in sulfur-containing flue gas according to claim 1, wherein in the step (2), the drying temperature of the precipitate is 70-80 ℃, and the drying time is 10-12 h.
6. The composite oxide catalyst for synchronously removing VOCs and NOx in sulfur-containing flue gas according to claim 1, wherein in the step (2), the calcination temperature of the precipitate is 400-500 ℃.
7. The composite oxide catalyst for synchronously removing VOCs and NOx in sulfur-containing flue gas according to claim 1, wherein in the step (2), the calcination time is 3-5 h.
8. A composite oxide catalyst prepared by the method of any one of claims 1 to 7.
9. The use of the composite oxide catalyst of claim 8 for the simultaneous removal of VOCs and NOx, wherein the de-NOx temperature and test temperature for the removal of VOCs range from 150 to 390 ℃.
10. Use of the composite oxide catalyst of claim 8 for the simultaneous removal of VOCs and NOx, characterized in that SO in flue gas2The content of (B) is 200 to 500 ppm.
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| CN115155565A (en) * | 2022-05-13 | 2022-10-11 | 浙江大学 | Preparation method and application of Mn-based composite metal oxide catalyst for removing VOCs at low temperature |
| CN115608351A (en) * | 2022-10-24 | 2023-01-17 | 五邑大学 | Composite material and preparation method and application thereof |
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