CN118105995A - Porous ceramic SCR denitration catalyst and preparation method thereof - Google Patents
Porous ceramic SCR denitration catalyst and preparation method thereof Download PDFInfo
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- CN118105995A CN118105995A CN202211512307.0A CN202211512307A CN118105995A CN 118105995 A CN118105995 A CN 118105995A CN 202211512307 A CN202211512307 A CN 202211512307A CN 118105995 A CN118105995 A CN 118105995A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 239000000919 ceramic Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 239000002699 waste material Substances 0.000 claims abstract description 19
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 17
- 229960000892 attapulgite Drugs 0.000 claims abstract description 17
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 17
- 239000002893 slag Substances 0.000 claims abstract description 17
- 239000010959 steel Substances 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910003454 ytterbium oxide Inorganic materials 0.000 claims abstract description 10
- 229940075624 ytterbium oxide Drugs 0.000 claims abstract description 10
- JEROREPODAPBAY-UHFFFAOYSA-N [La].ClOCl Chemical compound [La].ClOCl JEROREPODAPBAY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims description 35
- 239000002243 precursor Substances 0.000 claims description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 14
- 238000010304 firing Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- LEYFXTUKPKKWMP-UHFFFAOYSA-K trichloroytterbium;hexahydrate Chemical group O.O.O.O.O.O.Cl[Yb](Cl)Cl LEYFXTUKPKKWMP-UHFFFAOYSA-K 0.000 claims description 9
- UJBPGOAZQSYXNT-UHFFFAOYSA-K trichloroerbium;hexahydrate Chemical group O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Er+3] UJBPGOAZQSYXNT-UHFFFAOYSA-K 0.000 claims description 8
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical group O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 claims description 7
- 150000000917 Erbium Chemical class 0.000 claims description 6
- 150000001225 Ytterbium Chemical class 0.000 claims description 6
- 150000002603 lanthanum Chemical class 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims 1
- 238000003915 air pollution Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
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- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003546 flue gas Substances 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000012495 reaction gas Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
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- 239000011593 sulfur Substances 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- KWMNWMQPPKKDII-UHFFFAOYSA-N erbium ytterbium Chemical compound [Er].[Yb] KWMNWMQPPKKDII-UHFFFAOYSA-N 0.000 description 1
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- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
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- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- 230000004083 survival effect Effects 0.000 description 1
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical class [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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Abstract
The invention relates to the fields of waste resource utilization, environmental protection catalytic materials and air pollution treatment, and discloses a porous ceramic SCR denitration catalyst, which comprises a porous ceramic carrier, and an active component and a cocatalyst which are loaded on the surface of the porous ceramic carrier; wherein the active component contains lanthanum oxychloride; the promoter contains ytterbium oxide and erbium oxide; the raw materials for preparing the porous ceramic carrier comprise waste steel slag, attapulgite, active carbon, nano iron powder and a forming agent. The porous ceramic SCR denitration catalyst has higher NO x removal efficiency, is low in cost and has a wide market prospect.
Description
Technical Field
The invention relates to the fields of waste resource utilization, environment-friendly catalytic materials and air pollution treatment, in particular to a porous ceramic SCR denitration catalyst and a preparation method thereof.
Background
Nitrogen oxides (NO x) are one of the main pollutants in the atmosphere and have great harm to human health and animal and plant survival. The excessive NO x is far more than the self-purification capability of the atmosphere, seriously harms the ecological environment, can cause acid rain and nitrogen deposition, and can cause pollution and harm to the environment. NO x reacts with oxygen and other components in the air in the atmosphere to form nitrates which recombine into fine particles (such as PM 2.5) causing photochemical air pollution. Therefore, the development of NO x is of great importance.
The method for removing NO x by NH 3 Selective Catalytic Reduction (SCR) has the characteristics of mature technology, high removal efficiency and the like, and is widely applied at home and abroad. At present, the commercial catalyst is generally vanadium-tungsten-titanium series denitration catalyst, but the catalyst has higher requirements on the operation temperature, the optimal operation temperature is generally 350-400 ℃, and in industrial production, sulfide and dust in flue gas can have toxic action on the denitration catalyst due to the fact that the desulfurization and dust removal device is arranged behind the denitration device, so that the service life of the catalyst is greatly reduced. If the denitration device is arranged at the tail end of the desulfurization and dust removal device, the problem of reduced service life of the catalyst can be avoided. However, after desulfurization and dust removal, the temperature of the flue gas is about 150 ℃, and the existing commercial catalyst is not suitable for removing nitrogen oxides under the low-temperature condition. Therefore, the development of the denitration catalyst meeting the actual industrial smoke condition under the low-temperature condition has profound significance.
The existing patent at home and abroad discloses a low-temperature SCR denitration catalyst and a preparation method thereof. Patent application CN201811441127.1 discloses a method for improving water-resistant and sulfur-resistant properties of manganese-based low-temperature SCR denitration catalyst, which adopts hydrophobic polytetrafluoroethylene as a package or dopant, and adopts simple dispersion in a reactor filled with absolute ethyl alcohol, and the manganese-based low-temperature SCR denitration catalyst with excellent water-resistant and sulfur-resistant properties can be prepared through mixing, stirring, filtering, drying and calcining the manganese-based catalyst. The catalyst effectively improves the sulfur and water resistance of the catalyst, but the NO x removal efficiency is only 80% at 150 ℃, and the NOx removal efficiency still needs to be improved. Patent CN112742413B discloses a low-temperature SCR denitration catalyst, and a preparation method and application thereof, the low-temperature SCR denitration catalyst comprises a carrier, an active component and rare earth oxide, the carrier is a doped titanium dioxide nanotube doped with metal oxide; the active component is a mixture of MnO x and FeO y, and the catalyst has excellent water resistance, sulfur resistance and stability, and can be suitable for low-temperature denitration of high-water-content flue gas such as natural gas, but the titanium dioxide nanotube is used, so that the economic cost is high, and large-scale industrial application is difficult to realize.
Disclosure of Invention
The invention aims to solve the problems of low removal efficiency and the like of an SCR denitration catalyst in the prior art, and provides a porous ceramic SCR denitration catalyst and a preparation method thereof, wherein the porous ceramic SCR denitration catalyst has higher NO x removal efficiency.
In order to achieve the above object, a first aspect of the present invention provides a porous ceramic SCR denitration catalyst, which includes a porous ceramic support, and an active component and a promoter supported on the surface of the porous ceramic support;
wherein the active component contains lanthanum oxychloride;
The promoter contains ytterbium oxide and erbium oxide;
the raw materials for preparing the porous ceramic carrier comprise waste steel slag, attapulgite, active carbon, nano iron powder and a forming agent.
Preferably, the weight ratio of the porous ceramic carrier, the active component and the cocatalyst is 100:5-15:2-8.
Preferably, the weight ratio of ytterbium oxide to erbium oxide is 1:0.2-0.5.
Preferably, the molding agent is polyvinyl alcohol.
The second aspect of the invention provides a preparation method of the porous ceramic SCR denitration catalyst, which comprises the following steps:
(1) Mixing waste steel slag, attapulgite, active carbon and nano iron powder with a forming agent solution, granulating, and calcining to obtain a porous ceramic carrier;
(2) Mixing lanthanum salt with water to obtain an active component precursor solution;
(3) Mixing ytterbium salt and erbium salt with water to obtain a promoter precursor solution;
(4) Mixing the porous ceramic carrier with the active component precursor solution, stirring at 60-80 ℃ to be dried, then conducting first roasting, cooling a product obtained by the first roasting, mixing with a hydrochloric acid solution, adsorbing for 1-2h, conducting second roasting, then mixing a product obtained by the second roasting with the cocatalyst precursor solution, stirring at 60-80 ℃ to be dried, and finally conducting third roasting.
Preferably, in the step (1), the weight ratio of the waste steel slag, the attapulgite, the activated carbon, the nano iron powder and the forming agent solution is 60-80:10-20:5-10:5-10:5-10.
Preferably, the molding agent solution is a polyvinyl alcohol solution.
Preferably, the concentration of the polyvinyl alcohol solution is 5 to 10 wt%.
Preferably, the conditions of the calcination include: the temperature is 1100-1300 ℃ and the time is 2-4h.
Preferably, in step (2), the lanthanum salt is lanthanum nitrate hexahydrate.
Preferably, in step (3), the ytterbium salt is ytterbium chloride hexahydrate.
Preferably, the erbium salt is erbium chloride hexahydrate.
Preferably, in step (4), the conditions of the first firing include: the temperature is 400-500 ℃ and the time is 2-4h.
Preferably, the concentration of the hydrochloric acid solution is 20-30 wt%.
Preferably, in step (4), the conditions of the second firing include: the temperature is 500-600 ℃ and the time is 2-3h.
Preferably, in step (4), the conditions of the third firing include: the temperature is 400-600 ℃ and the time is 2-4h.
The invention takes porous ceramic which is prepared by firing waste steel slag, attapulgite, active carbon, nano iron powder and a forming agent as a carrier, wherein the active carbon is taken as a pore-forming agent, and the porous ceramic carrier is prepared by calcining and pore-forming, and the porous ceramic SCR denitration catalyst has the advantages that: (1) The nano iron powder is added into the catalyst carrier, and the excellent heat conduction property of the nano iron powder is beneficial to rapidly leading out the heat released in the selective catalytic reduction process of NH 3, so that the chemical reaction efficiency is quickened, and the NO x removal efficiency is improved; (2) The porous structure of the catalyst has rich pore canal structure and high internal porosity, is favorable for loading active components on the surface of the catalyst, and prolongs the contact time of reaction gas and the active components, thereby improving the NO x removal efficiency.
Drawings
FIG. 1 is an activity diagram of the catalysts prepared in examples 1 to 3;
FIG. 2 is an activity chart of the catalysts prepared in comparative examples 1 to 3.
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a porous ceramic SCR denitration catalyst, which comprises a porous ceramic carrier, and an active component and a cocatalyst which are loaded on the surface of the porous ceramic carrier;
wherein the active component contains lanthanum oxychloride;
The promoter contains ytterbium oxide and erbium oxide;
the raw materials for preparing the porous ceramic carrier comprise waste steel slag, attapulgite, active carbon, nano iron powder and a forming agent.
In the porous ceramic SCR denitration catalyst according to the present invention, preferably, the molding agent is polyvinyl alcohol.
In the porous ceramic SCR denitration catalyst of the present invention, preferably, the weight ratio of the porous ceramic carrier, the active component and the cocatalyst is 100:5-15:2-8, specifically can be 100:5: 2. 100:5: 4. 100:5: 6. 100:5: 8. 100:10: 2. 100:10: 4. 100:10: 6. 100:10: 8. 100:15: 2. 100:15: 4. 100:15:6 or 100:15:8.
In the porous ceramic SCR denitration catalyst of the present invention, preferably, the weight ratio of ytterbium oxide to erbium oxide is 1:0.2 to 0.5, and can be specifically 1:0.2, 1:0.3, 1:0.4 or 1:0.5.
In the porous ceramic SCR denitration catalyst disclosed by the invention, the forming agent is polyvinyl alcohol.
The second aspect of the invention provides a preparation method of the porous ceramic SCR denitration catalyst, which comprises the following steps:
(1) Mixing waste steel slag, attapulgite, active carbon and nano iron powder with a forming agent solution, granulating, and calcining to obtain a porous ceramic carrier;
(2) Mixing lanthanum salt with water to obtain an active component precursor solution;
(3) Mixing ytterbium salt and erbium salt with water to obtain a promoter precursor solution;
(4) Mixing the porous ceramic carrier with the active component precursor solution, stirring at 60-80 ℃ to be dried, then conducting first roasting, cooling a product obtained by the first roasting, mixing with a hydrochloric acid solution, adsorbing for 1-2h, conducting second roasting, then mixing a product obtained by the second roasting with the cocatalyst precursor solution, stirring at 60-80 ℃ to be dried, and finally conducting third roasting.
In the preparation method of the present invention, in order to obtain the catalyst of the present invention, in a preferred case, in the step (1), the weight ratio of the waste steel slag, the attapulgite, the activated carbon, the nano iron powder and the forming agent solution is controlled to be 60-80:10-20:5-10:5-10:5-10.
In the preferred case, in step (1), the particle size of the used waste steel slag, attapulgite, activated carbon and nano iron powder is 60-80 mesh.
In the preparation method of the present invention, in the step (1), the molding agent solution is a polyvinyl alcohol solution.
The concentration of the polyvinyl alcohol solution in the present invention is preferably 5 to 10% by weight, and may be specifically 5% by weight, 6% by weight, 7% by weight, 8% by weight, 9% by weight or 10% by weight.
In the preparation method of the present invention, in the step (1), the granulation method may be a granulation method common in the art, and in a specific embodiment, a roll forming method may be used for granulation.
In the preparation method according to the present invention, in the step (1), the conditions of the calcination include: the temperature is 1100-1300 ℃ and the time is 2-4h, specifically, the temperature can be 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃ or 1300 ℃ and the time can be 2h, 2.5h, 3h, 3.5h or 4h.
In the preparation method of the invention, in the step (2), the lanthanum salt is lanthanum nitrate hexahydrate, the amount of water used is not particularly required, and the lanthanum nitrate hexahydrate can be completely dissolved.
In the preparation method of the invention, in the step (3), the ytterbium salt is ytterbium chloride hexahydrate.
In the preparation method of the invention, in the step (3), the erbium salt is erbium chloride hexahydrate, and in the step, the water used in the step is not particularly required, so that ytterbium chloride hexahydrate and erbium chloride hexahydrate can be completely dissolved.
In the preparation method of the present invention, in the step (4), after the porous ceramic support is mixed with the active component precursor solution, the mixture is stirred to a drying temperature of 60 ℃, 65 ℃,70 ℃, 75 ℃ or 80 ℃.
In the preparation method according to the present invention, in the step (4), the conditions for the first firing include: the temperature is 400-500 ℃ and the time is 2-4h, specifically, the temperature can be 400 ℃, 420 ℃, 440 ℃, 460 ℃, 480 ℃ or 500 ℃ and the time can be 2h, 2.5h, 3h, 3.5h or 4h.
In the preparation method of the present invention, in the step (4), the concentration of the hydrochloric acid solution is 20 to 30 wt%, specifically may be 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, or 30 wt%.
In the preparation method according to the present invention, in the step (4), the conditions for the second firing include: the temperature is 500-600deg.C, the time is 2-3h, specifically, the temperature can be 500 deg.C, 510 deg.C, 520 deg.C, 530 deg.C, 540 deg.C, 550 deg.C, 570 deg.C, 580 deg.C, 5090 deg.C or 600 deg.C, the time can be 2h, 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h, 2.9h or 3h.
In step (4) of the present invention, after mixing the product obtained by the second calcination with the promoter precursor solution, stirring to a drying temperature of 60 ℃,65 ℃, 70 ℃, 75 ℃ or 80 ℃.
In step (4) of the present invention, in step (4), the conditions for the third firing include: the temperature is 400-600deg.C, the time is 2-4h, specifically, the temperature can be 400 deg.C, 450 deg.C, 500 deg.C, 550 deg.C or 600 deg.C, and the time can be 2h, 2.5h, 3h, 3.5h or 4h.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) The SCR denitration catalyst prepared by the invention not only can realize high added value utilization of industrial waste, but also can improve specific surface area and porosity by utilizing a pore channel structure rich in the catalyst, and promote migration and adsorption of reaction gas in the catalytic reaction process;
(2) The heat generated in the reaction process is rapidly led out by utilizing the excellent heat conducting property of the nano iron powder, the reaction efficiency is quickened, the NO x removal efficiency is improved, and the catalyst can also show good NO x removal efficiency under the low-temperature condition;
(3) The SCR denitration catalyst disclosed by the invention has high NO x removal efficiency under a low-temperature condition, can be applied to the tail end of flue gas treatment, avoids reheating flue gas, is suitable for denitration treatment of industrial flue gas tail gas, and has the advantages of wide sources of raw materials, high mechanical strength, low cost, strong poisoning resistance and wide market prospect.
The present invention will be described in detail by way of examples, but the scope of the present invention is not limited thereto.
The waste steel slag used in the following examples and comparative examples was obtained from national engineering, inc. of middle smelting, attapulgite was purchased from Shanghai source leaf Biotechnology, inc., product number S28335, activated carbon was purchased from national pharmaceutical Cluster chemical Co., CAS number 7440-44-0, nano iron powder was purchased from Shanghai Jizhuito Biochemical technology, inc., CAS number 7439-89-6, polyvinyl alcohol was purchased from national pharmaceutical Cluster chemical Co., ltd, CAS number 9002-89-5;
The particle sizes of the waste steel slag, the attapulgite, the activated carbon and the nano iron powder used in the following examples and comparative examples were all 60 to 80 mesh.
Example 1
(1) Catalyst support preparation
Weighing 60g of waste steel slag, 10g of attapulgite, 5g of activated carbon and 5g of nano iron powder, uniformly mixing, adding 5g of polyvinyl alcohol solution with concentration of 5wt%, rapidly and fully stirring, granulating by adopting a rolling forming method after uniformly mixing, transferring into a muffle furnace, and calcining for 4 hours at 1100 ℃ in an air atmosphere to prepare a porous ceramic carrier;
(2) Preparation of active component precursor solution
1.0492G of lanthanum nitrate hexahydrate is weighed and dissolved in 5mL of deionized water, and the solution is stirred uniformly to obtain an active component precursor solution;
(3) Preparation of promoter precursor solution
0.3278G of ytterbium chloride hexahydrate and 0.0665g of erbium chloride hexahydrate are dissolved in 5mL of deionized water, and the solution is uniformly stirred to obtain a promoter precursor solution;
(4) Preparation of the catalyst
Weighing 10g of the porous ceramic carrier prepared in the step (1), mixing with the active component precursor ion solution prepared in the step (2), transferring to a constant temperature stirrer, stirring to dryness at 60 ℃, placing in a muffle furnace, performing first roasting (with the temperature of 400 ℃ for 4 hours) in an air atmosphere, cooling the product obtained by the first roasting, placing in 5mL of hydrochloric acid solution with the concentration of 20 wt%, mixing, adsorbing for 1 hour, transferring to the muffle furnace, performing second roasting (with the temperature of 500 ℃ for 3 hours) in the air atmosphere, cooling the product obtained by the second roasting, adding to the cocatalyst precursor solution prepared in the step (3), uniformly mixing, transferring to the constant temperature stirrer, stirring to dryness at 60 ℃, and finally transferring to the muffle furnace, performing third roasting (with the temperature of 400 ℃ for 4 hours) in the air atmosphere, thereby obtaining the porous ceramic SCR denitration catalyst A1, wherein the active component is lanthanum oxychloride and the cocatalyst is ytterbium oxide.
Example 2
(1) Catalyst support preparation
Weighing 80g of waste steel slag, 20g of attapulgite, 10g of activated carbon and 10g of nano iron powder, uniformly mixing, adding 10g of 10 wt% concentration polyvinyl alcohol solution, rapidly and fully stirring, granulating by adopting a rolling forming method after uniformly mixing, transferring to a muffle furnace, and calcining for 2 hours at 1300 ℃ in an air atmosphere to prepare a porous ceramic carrier;
(2) Preparation of active component precursor solution
Weighing 3.1475g of lanthanum nitrate hexahydrate, dissolving in 5mL of deionized water, and uniformly stirring to obtain an active component precursor solution;
(3) Preparation of promoter precursor solution
1.0488G of ytterbium chloride hexahydrate and 0.5322g of erbium chloride hexahydrate are dissolved in 5mL of deionized water, and the solution is uniformly stirred to obtain a promoter precursor solution;
(4) Preparation of the catalyst
Weighing 10g of the porous ceramic carrier prepared in the step (1), mixing with the active component precursor ion solution prepared in the step (2), transferring to a constant temperature stirrer, stirring to dryness at 80 ℃, placing in a muffle furnace, performing first roasting (with the temperature of 500 ℃ for 2 h) in an air atmosphere, cooling the product obtained by the first roasting, placing in 5mL of 30 wt% hydrochloric acid solution, mixing, adsorbing for 1h, transferring to the muffle furnace, performing second roasting (with the temperature of 600 ℃ for 2 h) in the air atmosphere, cooling the product obtained by the second roasting, adding to the cocatalyst precursor solution prepared in the step (3), uniformly mixing, transferring to the constant temperature stirrer, stirring to dryness at 80 ℃, and finally transferring to the muffle furnace, and performing third roasting (with the temperature of 600 ℃ for 2 h) in the air atmosphere, thereby obtaining the porous ceramic SCR denitration catalyst A2, wherein the active component is lanthanum oxychloride and the cocatalyst is ytterbium oxide.
Example 3
(1) Catalyst support preparation
Weighing 70g of waste steel slag, 15g of attapulgite, 7.5g of active carbon and 7.5g of nano iron powder, uniformly mixing, adding 7.5g of 7.5 wt% concentration polyvinyl alcohol solution, rapidly and fully stirring, granulating by adopting a rolling forming method after uniformly mixing, transferring into a muffle furnace, and calcining for 2 hours at 1200 ℃ in the air atmosphere to prepare a porous ceramic carrier;
(2) Preparation of active component precursor solution
2.0983G of lanthanum nitrate hexahydrate is weighed and dissolved in 5mL of deionized water, and the solution is stirred uniformly to obtain an active component precursor solution;
(3) Preparation of promoter precursor solution
0.7284G of ytterbium chloride hexahydrate and 0.2587g of erbium chloride hexahydrate are dissolved in 5mL of deionized water, and the solution is uniformly stirred to obtain a promoter precursor solution;
(4) Preparation of the catalyst
Weighing 10g of the porous ceramic carrier prepared in the step (1), mixing with the active component precursor ion solution prepared in the step (2), transferring to a constant temperature stirrer, stirring to dryness at 70 ℃, placing in a muffle furnace, performing first roasting (the temperature is 450 ℃ for 3 h) in an air atmosphere, cooling the product obtained by the first roasting, placing in 5mL of 30 wt% hydrochloric acid solution, mixing, adsorbing for 1.5h, transferring to the muffle furnace, performing second roasting (the temperature is 550 ℃ for 2.5 h) in the air atmosphere, cooling the product obtained by the second roasting, adding into the cocatalyst precursor solution prepared in the step (3), uniformly mixing, transferring to the constant temperature stirrer, stirring to dryness at 70 ℃, and finally transferring to the muffle furnace, and performing third roasting (the temperature is 500 ℃ for 3 h) in the air atmosphere to obtain the porous ceramic SCR denitration catalyst A3, wherein the active component is lanthanum oxychloride, and the cocatalyst is ytterbium oxide and erbium oxide.
Comparative example 1
The procedure of example 1 was followed, except that nano-iron powder was not used in step (1), to obtain a porous ceramic SCR denitration catalyst D1.
Comparative example 2
The procedure of example 1 was carried out in the same manner as in example 1, except that in step (4), the product obtained by the first calcination was not adsorbed by adding hydrochloric acid solution, but the product obtained by the first calcination was cooled and then directly subjected to the second calcination to obtain the porous ceramic SCR denitration catalyst D2.
Comparative example 3
The procedure of example 1 was followed, except that in step (3), 0.0665g of erbium chloride hexahydrate was directly dissolved in 5mL of deionized water without adding ytterbium chloride hexahydrate, and the resultant was stirred uniformly to obtain a promoter precursor solution, thereby obtaining a porous ceramic SCR denitration catalyst D3.
Test case
2ML of porous ceramic SCR denitration catalysts A1-A3 and D1-D3 are respectively taken and are put into a catalyst performance evaluation reaction device, wherein the inner diameter of a quartz tube in the device is 10mm, and reaction gas is introduced for activity evaluation, and the composition of the reaction gas is as follows: NH 3(500ppm)、NO(500ppm)、O2(10vol.％)、N2 is carrier gas, the flow rate of reaction gas is 400mL/min, the reaction test temperature range is 120-300 ℃, the specific content of outlet gas is detected respectively, the NO x removal efficiency is calculated according to the detection result, and the test result is shown in figures 1 and 2.
According to fig. 1 and 2, there are: a1, NO x removal efficiency is 85.4% at 120 ℃, NO x removal efficiency is more than 90% in 150-300 ℃, and the highest removal efficiency can reach 100%;
A2 has NO x removing efficiency of 89.5% at 120 ℃, NO x removing efficiency of 92% in 150-300 ℃ and highest 100%;
A3, the NO x removal efficiency is 87% at 120 ℃, and the NO x removal efficiency is more than 90% in the range of 150-300 ℃ and can reach 100% at most;
Because nano iron powder is not added in the step (1) during the preparation, the heat conduction performance is reduced, and the NO x removal efficiency is reduced;
In the step (4) during the preparation of D2, hydrochloric acid solution is not used, the active component in the finished catalyst is lanthanum oxide, but not lanthanum oxychloride, the oxidation-reduction performance is reduced, and the NO x removal efficiency is reduced at low temperature;
in the step (4) of preparing the D3, ytterbium chloride hexahydrate is not used, and the cocatalyst in the finished catalyst is erbium oxide, but not ytterbium-erbium composite oxide, so that the oxidation-reduction performance is reduced, and the NO x removal efficiency is reduced.
The results show that the porous ceramic SCR denitration catalyst obtained by the invention has low applicable temperature, high NO x removal efficiency, NO x removal efficiency of more than 85 percent at 120 ℃, NO x removal efficiency of more than 90 percent in 150-300 ℃ and up to 100 percent, and the porous ceramic SCR denitration catalyst has wide raw material sources, low price, simple preparation process and wide market application prospect.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. The porous ceramic SCR denitration catalyst is characterized by comprising a porous ceramic carrier, and an active component and a cocatalyst which are loaded on the surface of the porous ceramic carrier;
wherein the active component contains lanthanum oxychloride;
The promoter contains ytterbium oxide and erbium oxide;
the raw materials for preparing the porous ceramic carrier comprise waste steel slag, attapulgite, active carbon, nano iron powder and a forming agent.
2. The porous ceramic SCR denitration catalyst of claim 1, wherein the porous ceramic support, active component and promoter are present in a weight ratio of 100:5-15:2-8;
Preferably, the weight ratio of ytterbium oxide to erbium oxide is 1:0.2-0.5.
3. The porous ceramic SCR denitration catalyst of claim 1 or 2, wherein the shaping agent is polyvinyl alcohol.
4. A method for preparing a porous ceramic SCR denitration catalyst according to any one of claims 1 to 3, characterized in that the method comprises the steps of:
(1) Mixing waste steel slag, attapulgite, active carbon and nano iron powder with a forming agent solution, granulating, and calcining to obtain a porous ceramic carrier;
(2) Mixing lanthanum salt with water to obtain an active component precursor solution;
(3) Mixing ytterbium salt and erbium salt with water to obtain a promoter precursor solution;
(4) Mixing the porous ceramic carrier with the active component precursor solution, stirring at 60-80 ℃ to be dried, then conducting first roasting, cooling a product obtained by the first roasting, mixing with a hydrochloric acid solution, adsorbing for 1-2h, conducting second roasting, then mixing a product obtained by the second roasting with the cocatalyst precursor solution, stirring at 60-80 ℃ to be dried, and finally conducting third roasting.
5. The method according to claim 4, wherein in the step (1), the weight ratio of the waste steel slag, the attapulgite, the activated carbon, the nano iron powder and the forming agent solution is 60-80:10-20:5-10:5-10:5-10;
preferably, the molding agent solution is a polyvinyl alcohol solution;
preferably, the concentration of the polyvinyl alcohol solution is 5 to 10 wt%;
preferably, the conditions of the calcination include: the temperature is 1100-1300 ℃ and the time is 2-4h.
6. The method according to claim 4 or 5, wherein in the step (2), the lanthanum salt is lanthanum nitrate hexahydrate.
7. The method according to claim 4, wherein in the step (3), the ytterbium salt is ytterbium chloride hexahydrate;
Preferably, the erbium salt is erbium chloride hexahydrate.
8. The method according to claim 4, wherein in the step (4), the conditions for the first firing include: the temperature is 400-500 ℃ and the time is 2-4h;
preferably, the concentration of the hydrochloric acid solution is 20-30 wt%.
9. The method according to claim 4 or 8, wherein in step (4), the conditions for the second firing include: the temperature is 500-600 ℃ and the time is 2-3h.
10. The method according to claim 4 or 8, wherein in step (4), the conditions for the third firing include: the temperature is 400-600 ℃ and the time is 2-4h.
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