CN116272986A - Cu-based SCR denitration catalyst and preparation method and application thereof - Google Patents
Cu-based SCR denitration catalyst and preparation method and application thereof Download PDFInfo
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- 238000006555 catalytic reaction Methods 0.000 claims description 6
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- 229910052786 argon Inorganic materials 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
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- 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
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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Abstract
The invention discloses a Cu-based SCR denitration catalyst and a preparation method and application thereof. A preparation method of a Cu-based SCR denitration catalyst comprises the following steps: (1) The nitrate aqueous solution and the organic ligand alcohol solution are subjected to opposite flushing by utilizing a double-channel closed jet impact continuous micro-channel reactor (CJI-CMR), and after the reaction is finished, the catalyst precursor is obtained through centrifugal washing and drying; (2) And roasting the catalyst precursor under the protection of inert gas to obtain the Cu-based SCR denitration catalyst. According to the Cu-based SCR denitration catalyst, the preparation method and the application thereof, the carbon-based composite material is obtained through thermal decomposition of a Metal Organic Framework (MOF), and the Cu-based SCR denitration catalyst has the characteristics of layered pores, controllable morphology and easiness in functionalization with other hetero atoms, and is used for catalyzing and removing NO in flue gas by taking synthesis gas as a reducing agent, and H is taken as a catalyst 2 ‑SCR combines with CO-SCR, which solves the problem of poor oxidation resistance in CO-SCR and H 2 The problem of poor denitration activity of non-noble metals in SCR.
Description
Technical Field
The invention belongs to the technical field of denitration catalysts, and particularly relates to a Cu-based SCR denitration catalyst, and a preparation method and application thereof.
Background
With the rapid development of industrialization, the regional composite air pollution problem characterized by ozone, acid rain and the like is remarkable, and the regional composite air pollution problem is harmful to human bodies and the environment, so that the sustainable development of society and economy is severely restricted. NO (NO) x Is one of the important reasons for forming acid rain and acid mist, and is also an important component for forming photochemical smog.
The selective catalytic reduction technology is the flue gas denitration technology which is most widely applied at present, and the common reducing agent mainly comprises NH 3 、CO、H 2 、CH x The compound, in which CO is widely present in flue gas, can save production, transportation and storage costs, and can also be used with NO x Together take off and convert into N 2 And CO 2 Win-win is realized. But when oxygen is present, O 2 Will produce competitive adsorption with NO, leading to CO preferentially with O 2 And (3) reacting to reduce the catalytic activity. H 2 Can react with NO under the oxygen-enriched condition to generate harmless N 2 And H 2 O，H 2 SCR has high catalytic activity, but has the problems of narrow temperature window and poor selectivity, and is characterized by H 2 The catalysts with high activity used in the SCR field are all noble metal supported catalysts, which are expensive and scarce in resources, limiting their application and development.
The Cu-based material has high catalytic activity in SCR reaction and can be compared with noble metal catalyst. The derivative catalyst obtained by pyrolysis of the Metal Organic Framework (MOF) serving as a self-sacrifice template has high catalytic activity, and the problem of poor thermal stability of the MOF material in the field of thermal catalysis is avoided. At present, the common preparation methods of MOF materials mainly comprise a solvothermal method, a microwave method and a direct mixing method, and most of the methods have the defects of long reaction time, discontinuous reaction and the like in the process of preparing the MOF materials.
In view of the above, the invention provides a new SCR denitration catalyst, a preparation method and application thereof, wherein a transient nano sedimentation method (FNP) is adopted to prepare a precursor Cu-BTC, and then the precursor Cu-BTC is carbonized under the protection of inert gas to prepare a composite carbon material Cu/C, and synthesis gas is taken as a reducing agent to carry out CO and H 2 The combination is used for NO removal together, the denitration efficiency and the oxidation resistance of the catalyst are obviously improved, and the catalyst has stronger industrial application value.
Disclosure of Invention
The invention aims to provide a preparation method of a Cu-based SCR denitration catalyst, which uses CO and H 2 Synthesis gas as main component is used as reducing agent, H is used as catalyst 2 The combination of the SCR and the CO-SCR realizes complementation by using a synthetic gas reducing agent for catalyzing and removing NO in the flue gas, and improves the low-temperature denitration activity and the oxidation resistance.
In order to achieve the above purpose, the technical scheme adopted is as follows:
the preparation method of the Cu-based SCR denitration catalyst comprises the following steps:
(1) The method comprises the steps of (1) carrying out opposite flushing on nitrate aqueous solution and organic ligand alcohol solution by utilizing a microchannel reactor, and after the reaction is finished, centrifugally washing and drying to obtain a catalyst precursor;
(2) And roasting the catalyst precursor under the protection of inert gas to obtain the Cu-based SCR denitration catalyst.
Further, in the step (1), the micro-channel reactor is a double-channel closed jet impact continuous micro-channel reactor (CJI-CMR);
the injection flow rate of the injector is 70mL/min;
the mass ratio of the organic ligand to the nitrate is 1:1.8-2.2.
Further, in the step (1), the nitrate is copper nitrate;
the mass volume ratio of nitrate to water in the nitrate aqueous solution is 2g:30-38ml.
Further, in the step (1), the solvent in the organic ligand solution is absolute ethanol;
the organic ligand in the organic ligand solution is 1,3, 5-trimesic acid;
the mass volume ratio of the organic ligand to the solvent in the organic ligand solution is 1g:30-38ml.
In the step (1), water is adopted for centrifugal washing for 3 times, and then alcohol is adopted for centrifugal washing for 1 time.
Further, in the step (1), the centrifugal speed is 5000-7000rpm, and the time is 6-10min;
drying at 55-65deg.C under vacuum for 11-13h;
in the step (2), the inert gas is argon;
the roasting temperature is 550-650 ℃ and the roasting time is 2.5-3.5h.
Still further, in the step (1), the centrifugal speed is 6000rpm, and the time is 8min;
drying at 60deg.C under vacuum for 12 hr;
in the step (2), the roasting temperature is 600 ℃ and the time is 3.0h.
The invention also aims to provide a Cu-based SCR denitration catalyst which is prepared by the preparation method and has the characteristics of layered pores, controllable morphology and easiness in functionalization with other hetero atoms.
The invention also aims to provide the application of the Cu-based SCR denitration catalyst in catalyzing and removing NO in flue gas, and the Cu-based SCR denitration catalyst can be used for low-temperature denitration.
Further, the main components are CO and H 2 The synthesis gas is used as a reducing agent, NO in the flue gas is removed by catalysis, and the catalysis temperature is 25-500 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) Compared with the traditional intermittent synthesis method, the method can effectively solve the problem of uneven macro mixing, can enable materials to rapidly enter a microchannel, has the advantages of continuity, rapidness, high loading rate, industrialization and the like, and is a very promising material preparation method.
(2) The invention takes the synthesis gas as the reducing agent for catalyzing and removing NO in the flue gas, and H is taken as the reducing agent 2 The combination of the-SCR and the CO-SCR realizes complementation, solves the problem of poor oxygen resistance in the CO-SCR and solves the problem of H 2 The problem of poor denitration activity of non-noble metals in SCR (selective catalytic reduction) obviously improves the low-temperature denitration activity and the oxidation resistance.
(3) The invention uses the synthetic gas as the reducing agent for catalyzing and removing NO in the flue gas, the production method is different, the composition of the synthetic gas has great difference, and after the synthetic gas is prepared, the carbon monoxide can be reduced and the hydrogen content can be improved through the water gas reaction (shift reaction). Simplified manufacture, reduced equipment, lower cost and investment, and stronger industrial application value.
Drawings
FIG. 1 is a flow chart of a preparation of a dual-channel closed jet impingement continuous microchannel reactor (CJI-CMR) for Cu-MOF synthesis;
FIG. 2 is an XRD spectrum of the synthesized Cu-MOF;
FIG. 3 is an SEM image of the synthesized Cu-MOF;
FIG. 4 is a simplified schematic of a catalyst performance testing apparatus;
FIG. 5 is a graph of denitration performance of a catalyst in different reducing agent atmospheres;
FIG. 6 is a graph of the oxidation resistance of a catalyst in a syngas reductant atmosphere;
FIG. 7 is a graph of the oxidation resistance of a catalyst in a CO reductant atmosphere.
Detailed Description
In order to further illustrate the Cu-based SCR denitration catalyst and the preparation method and application thereof, the purpose of the invention is expected, and the specific implementation, structure, characteristics and efficacy of the Cu-based SCR denitration catalyst according to the present invention are described in detail below with reference to the preferred embodiments. In the following description, different "an embodiment" or "an embodiment" do not necessarily refer to the same embodiment. Furthermore, the particular features, structures, or characteristics of one or more embodiments may be combined in any suitable manner.
The Cu-based SCR denitration catalyst, the preparation method and the application thereof are further described in detail by combining specific examples:
aiming at the problems existing in the existing flue gas SCR denitration technology, the preparation method of the Cu-based SCR denitration catalyst is provided, wherein the synthesis gas is CO and H 2 Is a main component and is used as a raw material gas of chemical raw materials. The invention uses H 2 The combination of the SCR and the CO-SCR realizes complementation by using a synthetic gas reducing agent for catalyzing and removing NO in the flue gas, and improves the low-temperature denitration activity and the oxidation resistance. The catalyst comprises precursor Cu-BTC and Cu/C catalyst prepared after carbonization, and the simple and easy-to-industrialize double-channel closed jet impact continuous micro-channel reactor (CJI-CMR) is used for synthesizing Cu-MOF, so that the catalyst has important industrial significance. The Cu/C catalyst of the carbon-based nanocomposite is obtained by thermal decomposition of a Metal Organic Framework (MOF), and has the characteristics of layered pores, controllable morphology and easiness in functionalization with other hetero atoms. These properties make it a catalyst with high activity.
The technical scheme adopted by the invention is as follows:
the preparation method of the Cu-based SCR denitration catalyst comprises the following steps:
(1) The method comprises the steps of (1) carrying out opposite flushing on nitrate aqueous solution and organic ligand alcohol solution by utilizing a microchannel reactor, and after the reaction is finished, centrifugally washing and drying to obtain a catalyst precursor;
(2) And roasting the catalyst precursor under the protection of inert gas to obtain the Cu-based SCR denitration catalyst.
Preferably, the microchannel reactor in the step (1) is a two-channel closed jet impact continuous microchannel reactor (CJI-CMR);
the injection flow rate of the injector is 70mL/min;
the mass ratio of the organic ligand to the nitrate is 1:1.8-2.2.
Preferably, in the step (1), the nitrate is copper nitrate;
the mass volume ratio of nitrate to water in the nitrate aqueous solution is 2g:30-38ml.
Preferably, in the step (1), the solvent in the organic ligand solution is absolute ethanol;
the organic ligand in the organic ligand solution is 1,3, 5-trimesic acid;
the mass volume ratio of the organic ligand to the solvent in the organic ligand solution is 1g:30-38ml.
Preferably, in the step (1), water is firstly adopted for centrifugal washing for 3 times, and then alcohol is adopted for centrifugal washing for 1 time.
Preferably, in the step (1), the centrifugal speed is 5000-7000rpm, and the time is 6-10min;
drying at 55-65deg.C under vacuum for 11-13h;
in the step (2), the inert gas is argon;
the roasting temperature is 550-650 ℃ and the roasting time is 2.5-3.5h.
Further preferably, in the step (1), the centrifugal speed is 6000rpm, and the time is 8min;
drying at 60deg.C under vacuum for 12 hr;
in the step (2), the roasting temperature is 600 ℃ and the time is 3.0h.
The Cu-based SCR denitration catalyst is prepared by the preparation method. The preparation method comprises a precursor (MOF) and a carbonized catalyst, wherein the precursor is a metal organic framework material Cu-BTC, and the carbonized and pyrolyzed carbon-based nanocomposite Cu/C is obtained.
The Cu-based SCR denitration catalyst can be used for removing NO in flue gas by catalysis, and can be used for low-temperature denitration.
Preferably, the main components are CO and H 2 The synthesis gas is used as a reducing agent to catalyze and remove NO in the flue gas;
wherein co=1000 ppm, h 2 =1000 ppm, catalytic temperature 25-500 ℃.
The invention uses H 2 The combination of the SCR and the CO-SCR takes the synthetic gas as a reducing agent for catalytic removal of NO in the flue gas, so that complementation is realized, and the low-temperature denitration activity and the oxidation resistance are improved.
Example 1: with the device of FIG. 1, cu-BTC is prepared by utilizing a double-channel closed jet impact continuous micro-channel reactor (CJI-CMR), and a Cu/C catalyst is prepared by carbonizing in a tube furnace under the protection of inert gas;
the preparation method of the Cu/C catalyst comprises the following specific steps:
(1) 2g of copper nitrate trihydrate is weighed and dissolved in 34mL of ultrapure water under stirring to obtain solution A; 1g of 1,3, 5-trimesic acid is taken in 34mL of absolute ethyl alcohol, and is stirred and dissolved to obtain solution B.
(2) And (3) injecting the A, B solution obtained in the step (1) into a double-channel closed jet impact continuous micro-channel reactor (CJI-CMR), wherein the injection rate of an injector is set to be 70mL/min, and obtaining a blue solution.
(3) And (3) centrifuging the solution obtained after the hydrothermal treatment in the step (2) in a centrifuge, washing 3 times with water and washing 1 time with alcohol. The centrifuge speed was 6000rpm each time and the centrifugation time was 8min.
(4) And (3) placing the product after centrifugation in the step (3) in a vacuum drying oven, and vacuum drying at 60 ℃ for 12 hours to obtain a Cu-BTC precursor, namely a catalyst precursor.
(5) And (3) placing the Cu-BTC precursor obtained in the step (4) in a tube furnace, heating to 600 ℃ at a constant speed of 5 ℃/min, and roasting for 3 hours at constant temperature to obtain the Cu/C catalyst.
XRD and SEM measurements were carried out on the catalyst prepared in example 1, and the results are shown in FIGS. 2-3. As can be seen from FIGS. 2-3, cu/C catalysts were prepared.
Example 2: by synthesis gas (main component H 2 And CO) is used as a reducing agent for evaluating the performance of the catalyst for catalyzing and removing NO in the flue gas;
the Cu/C catalyst prepared in example 1 was used for denitration performance test, which was performed in a fixed bed reactor, which was a stainless steel tube having an inner diameter of 10.0mm, and quartz sand and quartz wool were placed in the reaction tube to ensure contact between the powder catalyst and the thermocouple before the experiment was performed, as shown in fig. 1. The atmosphere used for the test was 500ppm NO (expressed as NO in ) 1000ppm CO (expressed as CO in ) And 1000ppm H 2 (denoted as H 2in ) In N 2 Is an equilibrium gas. The total volume flow is 110mL/min, and GHSV is 50,000h -1 . Using a FourierFTIR of the Fourier transform infrared spectrum to determine NO (expressed as NO out ) An outlet concentration, evaluating the catalytic activity of the powder catalyst in a temperature range of 25 ℃ to 500 ℃;
o used in catalyst antioxidant test 2 At a concentration of 1vol% O 2 ；
The denitration conversion rate is calculated by adopting the following formula:
h used in the experiments 2 The content ratio was 5000ppm, the CO content ratio was 2000ppm, and the NO content ratio was 1250ppm.
Comparative example 1: the performance evaluation of the catalyst for catalyzing and removing NO in the flue gas by taking CO as a reducing agent;
the Cu/C catalyst prepared in example 1 was used for denitration performance test, which was performed in a fixed bed reactor, which was a stainless steel tube having an inner diameter of 10.0mm, and quartz sand and quartz wool were placed in the reaction tube to ensure contact between the powder catalyst and the thermocouple before the experiment was performed, as shown in fig. 1. The atmosphere used for the test was 500ppm NO (expressed as NO in ) 1000ppm CO (expressed as CO in ) In N 2 Is an equilibrium gas. The total volume flow is 100mL/min, and GHSV is 50,000h -1 . Determination of NO (expressed as NO) using fourier transform infrared spectroscopy FTIR out ) An outlet concentration, evaluating the catalytic activity of the powder catalyst in a temperature range of 25 ℃ to 500 ℃;
o used in catalyst antioxidant test 2 At a concentration of 1vol% O 2 ；
The denitration conversion rate is calculated by adopting the following formula:
the CO content ratio used in the experiment was 2000ppm and the NO content ratio was 1250ppm.
Comparative example 2: by H 2 For catalytic removal of smoke as reducing agentAnd (5) evaluating the performance of the catalyst of NO in the gas.
The Cu/C catalyst prepared in example 1 was used for denitration performance test, which was performed in a fixed bed reactor, which was a stainless steel tube having an inner diameter of 10.0mm, and quartz sand and quartz wool were placed in the reaction tube to ensure contact between the powder catalyst and the thermocouple before the experiment was performed, as shown in fig. 1. The atmosphere used for the test was 500ppm NO (expressed as NO in )，1000ppm H 2 (denoted as H 2in ) And 5vol% O 2 In N 2 Is an equilibrium gas. The total volume flow is 100mL/min, and GHSV is 50,000h -1 . Determination of NO (expressed as NO) using fourier transform infrared spectroscopy FTIR out ) An outlet concentration, evaluating the catalytic activity of the powder catalyst in a temperature range of 25 ℃ to 500 ℃;
the denitration conversion rate is calculated by adopting the following formula:
h used in the experiments 2 The content ratio was 5000ppm and the NO content ratio was 1250ppm.
The test results are shown in FIGS. 5-7.
In FIG. 5, the CO-SCR is comparative example 1, H 2 SCR is comparative example 2 and Synagas-SCR is example 2. As can be seen from FIG. 5, example 2 was catalyzed at 25-150℃and comparative examples 1-2 were not; and the catalytic effect is also better than that of comparative examples 1-2. Description of the use of Synthesis gas as reducing agent for catalytic removal of NO from flue gas, H 2 The combination of SCR and CO-SCR significantly improves the low-temperature denitration activity.
FIG. 6 is a graph of the oxidation resistance of a catalyst in a syngas reductant atmosphere; FIG. 7 is a graph of the oxidation resistance of a catalyst in a CO reductant atmosphere. As can be seen from FIGS. 6-7, the synthesis gas is used as a reducing agent for catalytic removal of NO in flue gas, and H is used as a catalyst 2 -SCR in combination with CO-SCR, significantly improving the oxidation resistance.
Example 3.
The specific operation steps are as follows:
(1) 2g of copper nitrate trihydrate is weighed and dissolved in 30mL of ultrapure water under stirring to obtain solution A; 1g of 1,3, 5-trimesic acid is taken in 38mL of absolute ethyl alcohol, and is stirred and dissolved to obtain solution B.
(2) And (3) injecting the A, B solution obtained in the step (1) into a double-channel closed jet impact continuous micro-channel reactor (CJI-CMR), wherein the injection rate of an injector is set to be 70mL/min, and obtaining a blue solution.
(3) And (3) centrifuging the solution obtained in the step (2) in a centrifuge, washing 3 times with water and washing 1 time with alcohol. The centrifuge speed was 5000rpm each time and the centrifugation time was 10min.
(4) And (3) placing the product after centrifugation in the step (3) in a vacuum drying oven, and vacuum drying at 55 ℃ for 13 hours to obtain a Cu-BTC precursor, namely a catalyst precursor.
(5) And (3) placing the Cu-BTC precursor obtained in the step (4) in a tube furnace, heating to 550 ℃ at a constant speed of 5 ℃/min, and roasting at constant temperature for 3.5 hours to obtain the Cu/C catalyst.
Example 4.
The specific operation steps are as follows:
(1) 2g of copper nitrate trihydrate is weighed and dissolved in 38mL of ultrapure water under stirring to obtain solution A; 1g of 1,3, 5-trimesic acid is taken in 30mL of absolute ethyl alcohol, and is stirred and dissolved to obtain solution B.
(2) And (3) injecting the A, B solution obtained in the step (1) into a double-channel closed jet impact continuous micro-channel reactor (CJI-CMR), wherein the injection rate of an injector is set to be 70mL/min, and obtaining a blue solution.
(3) And (3) centrifuging the solution obtained in the step (2) in a centrifuge, washing 3 times with water and washing 1 time with alcohol. The centrifuge speed was 7000rpm each time and the centrifugation time was 6min.
(4) And (3) placing the product after centrifugation in the step (3) in a vacuum drying oven, and vacuum drying for 11h at 65 ℃ to obtain a Cu-BTC precursor, namely a catalyst precursor.
(5) And (3) placing the Cu-BTC precursor obtained in the step (4) in a tube furnace, heating to 650 ℃ at a constant speed of 5 ℃/min, and roasting for 2.5 hours at constant temperature to obtain the Cu/C catalyst.
Example 5.
The method comprises the following specific steps:
(1) 2.2g of copper nitrate trihydrate is weighed into 34mL of ultrapure water and stirred for dissolution, so as to obtain solution A; 1g of 1,3, 5-trimesic acid is taken in 36mL of absolute ethyl alcohol, and is stirred and dissolved to obtain solution B.
(2) And (3) injecting the A, B solution obtained in the step (1) into a double-channel closed jet impact continuous micro-channel reactor (CJI-CMR), wherein the injection rate of an injector is set to be 70mL/min, and obtaining a blue solution.
(3) And (3) centrifuging the solution obtained in the step (2) in a centrifuge, washing 3 times with water and washing 1 time with alcohol. The centrifuge speed was 6000rpm each time and the centrifugation time was 10min.
(4) And (3) placing the product after centrifugation in the step (3) in a vacuum drying oven, and vacuum drying at 60 ℃ for 13 hours to obtain a Cu-BTC precursor, namely a catalyst precursor.
(5) And (3) placing the Cu-BTC precursor obtained in the step (4) in a tube furnace, heating to 600 ℃ at a constant speed of 5 ℃/min, and roasting for 3 hours at constant temperature to obtain the Cu/C catalyst.
Example 6.
The method comprises the following specific steps:
(1) 1.8g of copper nitrate trihydrate is weighed into 30mL of ultrapure water, stirred and dissolved to obtain solution A; 1g of 1,3, 5-trimesic acid is taken in 36mL of absolute ethyl alcohol, and is stirred and dissolved to obtain solution B.
(2) And (3) injecting the A, B solution obtained in the step (1) into a double-channel closed jet impact continuous micro-channel reactor (CJI-CMR), wherein the injection rate of an injector is set to be 70mL/min, and obtaining a blue solution.
(3) And (3) centrifuging the solution obtained in the step (2) in a centrifuge, washing 3 times with water and washing 1 time with alcohol. The centrifuge speed was 6000rpm each time and the centrifugation time was 10min.
(4) And (3) placing the product after centrifugation in the step (3) in a vacuum drying oven, and vacuum drying for 11h at 65 ℃ to obtain a Cu-BTC precursor, namely a catalyst precursor.
(5) And (3) placing the Cu-BTC precursor obtained in the step (4) in a tube furnace, heating to 650 ℃ at a constant speed of 5 ℃/min, and roasting for 2.5 hours at constant temperature to obtain the Cu/C catalyst.
The Cu-based SCR denitration catalyst and the preparation method and application thereof provided by the invention are used for synthesizing Cu-MOF through the double-channel closed jet impact continuous micro-channel reactor (CJI-CMR), have the advantages of continuity, rapidness, high loading rate, industrialization and the like, and are a very promising material preparation method. Thermal decomposition of Metal Organic Framework (MOF) materials yields carbon-based nanocomposites with layered porosity, morphology is controllable and easy to functionalize with other heteroatoms. These properties make it a catalyst with high activity. Meanwhile, the synthetic gas is used as a reducing agent, and the denitration efficiency and the oxidation resistance of the catalyst are both obviously improved. Has stronger industrial application value.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the embodiment of the present invention in any way, but any simple modification, equivalent variation and modification of the above embodiment according to the technical substance of the embodiment of the present invention still fall within the scope of the technical solution of the embodiment of the present invention.
Claims (10)
1. The preparation method of the Cu-based SCR denitration catalyst is characterized by comprising the following steps of:
(1) The method comprises the steps of (1) carrying out opposite flushing on nitrate aqueous solution and organic ligand alcohol solution by utilizing a microchannel reactor, and after the reaction is finished, centrifugally washing and drying to obtain a catalyst precursor;
(2) And roasting the catalyst precursor under the protection of inert gas to obtain the Cu-based SCR denitration catalyst.
2. The method according to claim 1, wherein,
in the step (1), the microchannel reactor is a double-channel closed jet impact continuous microchannel reactor;
the injection flow rate of the injector is 70mL/min;
the mass ratio of the organic ligand to the nitrate is 1:1.8-2.2.
3. The method according to claim 1, wherein,
in the step (1), the nitrate is copper nitrate;
the mass volume ratio of nitrate to water in the nitrate aqueous solution is 2g:30-38ml.
4. The method according to claim 1, wherein,
in the step (1), the solvent in the organic ligand solution is absolute ethyl alcohol;
the organic ligand in the organic ligand solution is 1,3, 5-trimesic acid;
the mass volume ratio of the organic ligand to the solvent in the organic ligand solution is 1g:30-38ml.
5. The method according to claim 1, wherein,
in the step (1), water is adopted for centrifugal washing for 3 times, and then alcohol is adopted for centrifugal washing for 1 time.
6. The method according to claim 1, wherein,
in the step (1), the centrifugal speed is 5000-7000rpm, and the time is 6-10min;
drying at 55-65deg.C under vacuum for 11-13h;
in the step (2), the inert gas is argon;
the roasting temperature is 550-650 ℃ and the roasting time is 2.5-3.5h.
7. The method according to claim 6, wherein,
in the step (1), the centrifugal speed is 6000rpm, and the time is 8min;
drying at 60deg.C under vacuum for 12 hr;
in the step (2), the roasting temperature is 600 ℃ and the time is 3.0h.
8. A Cu-based SCR denitration catalyst prepared by the preparation method of any one of claims 1 to 7.
9. The use of the Cu-based SCR denitration catalyst of claim 8 for catalytic removal of NO from flue gas.
10. The use according to claim 9, wherein,
with CO and H as main components 2 The synthesis gas is used as a reducing agent, NO in the flue gas is removed by catalysis, and the catalysis temperature is 25-500 ℃.
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