CN116272986B - 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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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 39
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 23
- 239000007789 gas Substances 0.000 claims abstract description 23
- 239000013110 organic ligand Substances 0.000 claims abstract description 22
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003546 flue gas Substances 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 20
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 16
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 238000011010 flushing procedure Methods 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 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
- 239000012621 metal-organic framework Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 4
- 125000005842 heteroatom Chemical group 0.000 abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 238000007306 functionalization reaction Methods 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 description 15
- 239000013148 Cu-BTC MOF Substances 0.000 description 14
- NOSIKKRVQUQXEJ-UHFFFAOYSA-H tricopper;benzene-1,3,5-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1.[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 NOSIKKRVQUQXEJ-UHFFFAOYSA-H 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 13
- 230000003647 oxidation Effects 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 12
- 238000005119 centrifugation Methods 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 6
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- 239000000843 powder Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000013084 copper-based metal-organic framework Substances 0.000 description 5
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000000643 oven drying Methods 0.000 description 5
- 229910021642 ultra pure water Inorganic materials 0.000 description 5
- 239000012498 ultrapure water Substances 0.000 description 5
- 239000006004 Quartz sand Substances 0.000 description 3
- 239000012494 Quartz wool Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003916 acid precipitation Methods 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
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- 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
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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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
- B01J23/72—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/202—Hydrogen
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
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- B01D2251/204—Carbon monoxide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
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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 airtight 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 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 the synthesis gas is used as a reducing agent for catalyzing and removing NO in flue gas, so that H 2 -SCR is combined with CO-SCR, the problem of poor oxygen resistance in CO-SCR is solved, and the problem of poor denitration activity of non-noble metals in H 2 -SCR is solved.
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 x is one of the important reasons for the formation of acid rain and acid mist, and is also an important component for the formation of 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、H2、CHx compounds, wherein CO is widely present in the flue gas, so that the cost of production, transportation and storage can be saved, and the CO can be removed together with NO x and converted into N 2 and CO 2, thereby realizing win-win. However, when oxygen is present, O 2 can produce competitive adsorption with NO, which leads to preferential reaction of CO with O 2 and reduced catalytic activity. H 2 can react with NO under the oxygen-enriched condition to generate harmless N 2 and H 2O,H2 -SCR with high catalytic activity, but the problems of narrow temperature window and poor selectivity exist all the time, and the high-activity catalysts used in the field of H 2 -SCR are all noble metal supported catalysts, so that the price is high, the resources are rare, and the application and development of the catalysts are limited.
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, 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 used as a reducing agent to combine CO and H 2 for NO removal, so that the denitration efficiency and the oxidation resistance of the catalyst are both obviously improved, and the catalyst has a relatively high industrial application value.
Disclosure of Invention
The invention aims to provide a preparation method of a Cu-based SCR denitration catalyst, which uses synthesis gas with CO and H 2 as main components as a reducing agent, combines H 2 -SCR with CO-SCR, uses the synthesis gas reducing agent for catalyzing and removing NO in flue gas, realizes complementation, and improves low-temperature denitration activity and 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 microchannel reactor 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.
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.
Furthermore, the synthesis gas with the main components of CO and H 2 is used as a reducing agent to catalyze and remove NO in the flue gas, 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) According to the invention, the synthesis gas is used as a reducing agent for catalytic removal of NO in flue gas, and H 2 -SCR is combined with CO-SCR to realize complementation, so that the problem of poor oxidation resistance in CO-SCR is solved, the problem of poor denitration activity of non-noble metals in H 2 -SCR is solved, and the low-temperature denitration activity and oxidation resistance are remarkably improved.
(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 a raw material gas which uses CO and H 2 as main components and is used as chemical raw materials. According to the invention, H 2 -SCR and CO-SCR are combined, and the synthetic gas reducing agent is used for catalyzing and removing NO in the flue gas, so that complementation is realized, and the low-temperature denitration activity and the oxidation resistance are improved. 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 synthesis gas with the main components of CO and H 2 is used as a reducing agent to catalyze and remove NO in the flue gas;
Wherein, co=1000 ppm, h 2 =1000 ppm, and the catalytic temperature is 25-500 ℃.
According to the invention, H 2 -SCR and CO-SCR are combined, and synthesis gas is used as a reducing agent for catalytic removal of NO in flue gas, so that complementation is realized, and low-temperature denitration activity and 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 carbonization 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: the performance evaluation of the catalyst for catalyzing and removing NO in the flue gas by taking synthesis gas (the main components are H 2 and 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 atmospheres used for the test were 500ppm NO (denoted NO in), 1000ppm CO (denoted CO in), and 1000ppm H 2 (denoted H 2in), with N 2 as the balance gas. The total volume flow was 110mL/min and GHSV was 50,000h -1. The catalytic activity of the powder catalyst was evaluated using fourier transform infrared spectroscopy FTIR to determine the NO (denoted NO out) exit concentration over a temperature range of 25 ℃ to 500 ℃;
The concentration of O 2 used in the catalyst antioxidant test was 1vol% O 2;
the denitration conversion rate is calculated by adopting the following formula:
The proportion of H 2 used in the experiment was 5000ppm, the proportion of CO was 2000ppm and the proportion of NO 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 (denoted NO in), 1000ppm CO (denoted CO in) and N 2 as balance gas. The total volume flow was 100mL/min and GHSV was 50,000h -1. The catalytic activity of the powder catalyst was evaluated using fourier transform infrared spectroscopy FTIR to determine the NO (denoted NO out) exit concentration over a temperature range of 25 ℃ to 500 ℃;
The concentration of O 2 used in the catalyst antioxidant test was 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: and (3) taking H 2 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 was tested for 500ppm NO (denoted as NO in),1000ppm H2 (denoted as H 2in) and 5vol% o 2 with N 2 as balance gas total volume flow rate 100mL/min GHSV 50,000H -1 the outlet concentration of NO (denoted as NO out) was determined using fourier transform infrared spectroscopy FTIR and the catalytic activity of the powder catalyst was evaluated in the temperature range 25 ℃ to 500 ℃;
the denitration conversion rate is calculated by adopting the following formula:
the proportion of H 2 used in the experiment was 5000ppm and the proportion of NO was 1250ppm.
The test results are shown in FIGS. 5-7.
In FIG. 5 the CO-SCR is comparative example 1, the H 2 -SCR is comparative example 2, and the 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. The method has the advantages that the synthetic gas is used as a reducing agent for catalytic removal of NO in the flue gas, and the H 2 -SCR is combined with the CO-SCR, so that the low-temperature denitration activity is remarkably improved.
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 fig. 6-7, the synthesis gas is used as a reducing agent for catalytic removal of NO in the flue gas, and the combination of H 2 -SCR and CO-SCR significantly improves 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 (7)
1. An application of a Cu-based SCR denitration catalyst in catalyzing and removing NO in flue gas is characterized in that,
The application is as follows: taking synthesis gas with main components of CO and H 2 as a reducing agent, and catalyzing and removing NO in the flue gas, wherein the catalysis temperature is 25-500 ℃;
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; the organic ligand in the organic ligand solution is 1,3, 5-trimesic acid;
(2) And roasting the catalyst precursor under the protection of inert gas to obtain the Cu-based SCR denitration catalyst.
2. The use 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 use 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 2 g:30-38ml.
4. The use according to claim 1, wherein,
In the step (1), the solvent in the organic ligand solution is absolute ethyl alcohol;
The mass volume ratio of the organic ligand to the solvent in the organic ligand solution is 1g:30-38ml.
5. The use 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 use 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 use 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.
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