CN108993476B - Metal oxide-vanadate/TiO2Catalyst, preparation method and application thereof - Google Patents
Metal oxide-vanadate/TiO2Catalyst, preparation method and application thereof Download PDFInfo
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- CN108993476B CN108993476B CN201710417705.7A CN201710417705A CN108993476B CN 108993476 B CN108993476 B CN 108993476B CN 201710417705 A CN201710417705 A CN 201710417705A CN 108993476 B CN108993476 B CN 108993476B
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 80
- 239000002184 metal Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 95
- 150000003839 salts Chemical class 0.000 claims abstract description 47
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 43
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 43
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 24
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003546 flue gas Substances 0.000 claims abstract description 21
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 20
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000001768 cations Chemical class 0.000 claims abstract description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 14
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 229910052684 Cerium Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 235000006408 oxalic acid Nutrition 0.000 claims description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- -1 halide salt Chemical class 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 3
- WKCZSFRAGKIIKN-UHFFFAOYSA-N 2-(4-tert-butylphenyl)ethanamine Chemical compound CC(C)(C)C1=CC=C(CCN)C=C1 WKCZSFRAGKIIKN-UHFFFAOYSA-N 0.000 claims description 2
- PAJMKGZZBBTTOY-UHFFFAOYSA-N 2-[[2-hydroxy-1-(3-hydroxyoctyl)-2,3,3a,4,9,9a-hexahydro-1h-cyclopenta[g]naphthalen-5-yl]oxy]acetic acid Chemical compound C1=CC=C(OCC(O)=O)C2=C1CC1C(CCC(O)CCCCC)C(O)CC1C2 PAJMKGZZBBTTOY-UHFFFAOYSA-N 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- IHIXIJGXTJIKRB-UHFFFAOYSA-N trisodium vanadate Chemical compound [Na+].[Na+].[Na+].[O-][V]([O-])([O-])=O IHIXIJGXTJIKRB-UHFFFAOYSA-N 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052753 mercury Inorganic materials 0.000 abstract description 15
- 238000007254 oxidation reaction Methods 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 20
- 230000003647 oxidation Effects 0.000 description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 238000002474 experimental method Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229960000892 attapulgite Drugs 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 229910052625 palygorskite Inorganic materials 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000003245 coal Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical group 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910019381 CoVO4 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
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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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- 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
-
- 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
- B01D53/8665—Removing heavy metals or compounds thereof, e.g. mercury
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/60—Heavy metals or heavy metal compounds
- B01D2257/602—Mercury or mercury compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention relates to the field of flue gas denitration and demercuration, and discloses metal oxide-vanadate/TiO2The catalyst, its preparation method and application, the catalyst includes: TiO 22And supported on the TiO2Metal oxide and vanadate supported on the TiO2The vanadate and the metal oxide are formed from a vanadium source and a metal salt, and the cation of the vanadate is provided by the metal element in the metal salt. The invention provides a metal oxide-vanadate/TiO2The catalyst can be used for NO in coal-fired flue gasxAnd high efficiency removal of mercury, especially for NOxAnd Hg0Has high removing efficiency.
Description
Technical Field
The invention relates to the field of flue gas denitration and demercuration, in particular to a metal oxide-vanadate/TiO2Catalyst and method for preparing metal oxide-vanadate/TiO2Method for preparing catalyst and metal oxide-vanadate/TiO prepared by method2Catalyst and metal oxide-vanadate/TiO2The catalyst is applied to denitration and demercuration of flue gas.
Background
NOxIs to create a regionThe important precursors of sexual dust haze, acid rain, photochemical smog and the like are one of the main urban atmospheric pollutants. Mercury is also receiving more and more attention from the international society because of its extremely strong volatility, durability, strong toxicity and biological enrichment effect. Reinforced coal NOxAnd mercury control is imminent.
World wide NOxThe emission of mercury and mercury establish increasingly strict standards, the emission standard of atmospheric pollutants for thermal power plants (GBl3223-2011) issued by the Ministry of environmental protection in China is specified in 7.29.2011, and the emission limit of mercury and compounds of coal-fired boilers from 1.1.2015 is 30 mu g/m3. In addition, 23 months 8 in 2014, the three committees of the national institute of energy and power conservation, the ministry of environmental protection and the national energy agency jointly issue a coal and electricity energy conservation and emission reduction upgrading and transformation action plan (2014-2020), which puts new requirements on emission of coal-fired units and sets NO in the requirement rangexThe discharge amount is less than 50mg/Nm3. The method has stricter requirements on the flue gas denitration and demercuration technology, and the cost of thermal power generation is increased. Thus, the combined removal of multiple contaminants using existing contaminant control devices is the most cost effective method for cost reduction.
The mercury in coal combustion flue gas is usually elemental mercury (Hg)0) Bivalent mercury (Hg)2+) And particulate mercury (Hg)p) Three forms exist. Hg is a mercury vaporpAnd Hg2+Can be easily removed by the existing dedusting and Wet Flue Gas Desulfurization (WFGD) device of the coal-fired power plant. And Hg0High volatility, low water solubility, relatively stable form in atmospheric environment, and difficult removal. Therefore, how to efficiently remove Hg in coal-fired flue gas0Form conversion into Hg easy to remove2+Morphology, and thus mercury removal using existing pollutant control equipment, is a current focus of research.
At present, the commercial SCR catalyst mainly adopts a vanadium-based catalytic system, and has excellent denitration activity, thermal stability and SO resistance2Poisoning performance. At the same time, it is directed to Hg0The oxidation of (2) also has a certain promoting effect. Therefore, from a long-term perspective, research and development of a denitration and demercuration catalyst for removing NOxIs selectively reduced toN2While Hg is simultaneously introduced0Oxidation to better Hg of water solubility2+And then the combined removal is carried out through WFGD, so that the device layout of denitration, electrostatic dust removal and wet desulphurization of the existing coal-fired power plant is very accordant, and the device is an economic and reasonable technical means and can be widely applied to the purification of coal-fired flue gas.
In addition, various transition metals such as CuO/CeO2-TiO2、Fe2O3/γ-Al2O3Etc. also apply to Hg0However, the oxidation of (2) has limited the practical industrial application of the above catalyst due to various problems such as economical and technical problems. Therefore, how to combine the vanadium-based SCR catalyst with the transition metal has important significance for realizing the combined removal of multiple pollutants in the coal-fired flue gas.
CN102989467A discloses a NH system applicable to fixed sources and mobile sources3-titanium oxide supported iron vanadate catalyst for SCR combining the advantages of vanadium-based and iron-based catalysts, with excellent activity, selectivity, thermal stability and SO resistance2Poisoning performance. CN105771967A relates TO a metal oxide-vanadate/attapulgite catalyst prepared from metal oxide TOxWith vanadate RVO4Is prepared by loading attapulgite ATP together. The metal oxide TOxWherein T is Ce, Zr or Mn, and the vanadate RVO4R in the formula is Ce, Mn or Fe. In the prior art, metal oxide and vanadate are loaded on clay attapulgite jointly and are used for denitration and demercuration of flue gas and decoloration of dye wastewater.
Disclosure of Invention
The invention aims to provide NO for coal-fired flue gasxAnd high efficiency removal of mercury, especially for NOxAnd Hg0High efficiency removal of metal oxide-vanadate/TiO2A catalyst.
The prior art CN105771967A relates to a metal oxide-vanadate/attapulgite catalyst, and the prior art teaches that when the metal oxide is supported on a carrier such as titanium dioxide, silica and activated carbon to prepare a demercuration catalyst, the catalyst is easily poisoned,difficult to regenerate and costly. The inventors of the present invention found in their studies that the vanadate and the metal oxide are supported on the TiO by using titanium dioxide as a carrier and supporting the carrier on the TiO2The above vanadate and metal oxide are formed from a vanadium source and a metal salt, and the amount of the vanadium source and the metal salt is controlled to be 1: (0.1-15), the obtained catalyst can stably realize NO in coal-fired flue gasxAnd high efficiency removal of mercury. Based on this, the technical solution of the present invention has been completed.
In order to achieve the above object, the present invention provides, in a first aspect, a metal oxide-vanadate/TiO2A catalyst, comprising: TiO 22And supported on the TiO2Metal oxide and vanadate supported on the TiO2The vanadate and the metal oxide are formed by a vanadium source and a metal salt, and the cation of the vanadate is provided by a metal element in the metal salt, and the vanadium source and the metal salt are used in a molar ratio of 1: (0.1-15), wherein the metal salt is a salt formed by one or more elements selected from Ce, Co, Fe and La.
In a second aspect, the present invention provides a method for preparing a metal oxide-vanadate/TiO2A process for the catalysis comprising:
(1) preparing a mixed solution containing a vanadium source and a metal salt, wherein the molar ratio of the amount of the vanadium source calculated by vanadium element to the amount of the metal salt calculated by metal element contained in the vanadium source is 1: (0.1-15);
(2) will contain TiO2The carrier is soaked in the mixed solution obtained in the step (1);
(3) drying the slurry obtained in the step (2);
(4) roasting the intermediate obtained in the step (3),
wherein the metal salt is a salt formed from one or two or more elements selected from the group consisting of Ce, Co, Fe and La.
In a third aspect, the present invention provides a metal oxide-vanadate prepared by the method of the second aspectsalt/TiO2A catalyst.
In a fourth aspect, the present invention provides the metal oxide-vanadate/TiO of the first and third aspects2The catalyst is applied to denitration and demercuration of flue gas.
The invention provides a metal oxide-vanadate/TiO2The catalyst can be used for NO in coal-fired flue gasxAnd high efficiency removal of mercury, especially for NOxAnd Hg0Has high removing efficiency.
The invention can realize NO treatment on the premise of not increasing the flue gas purification facilities of the coal-fired power plantxAnd Hg0And simultaneously the removal is high-efficiency.
In addition, the catalyst provided by the invention has good thermal stability and excellent H resistance2O and SO-resistance2Poisoning performance, simple preparation process, low cost and other advantages.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
First, as previously mentioned, the present invention provides a metal oxide-vanadate/TiO2A catalyst, comprising: TiO 22And supported on the TiO2Metal oxide and vanadate supported on the TiO2The vanadate and the metal oxide are formed by a vanadium source and a metal salt, and the cation of the vanadate is provided by a metal element in the metal salt, and the vanadium source and the metal salt are used in a molar ratio of 1: (0.1-15), wherein the metal salt is a salt formed by one or more elements selected from Ce, Co, Fe and La.
In the present invention, in order to obtain a catalyst containing both a metal oxide and a vanadate, it is preferable that the molar ratio of the vanadium source in terms of vanadium element to the metal salt in terms of metal element is not 1.
More preferably, the molar ratio of the vanadium source in terms of vanadium element and the metal salt in terms of metal element is 1: (0.5-5).
Preferably, in the presence of metal oxide-vanadate/TiO2In the catalyst, the content of the metal oxide is more than 0 and less than or equal to 15 wt%, and more preferably 1-5 wt%, based on the total weight of the catalyst; the vanadate is contained in an amount of 0.2 to 5 wt%, more preferably 0.5 to 2 wt%.
According to a preferred embodiment, the vanadate is FeVO4And the metal oxide is Fe2O3. Metal oxide-vanadate/TiO thus formed2Catalyst pair NOxAnd Hg0The removal efficiency is higher.
Preferably, when the vanadate is FeVO4And the metal oxide is Fe2O3The FeVO is calculated by vanadium element4And said Fe calculated as Fe element2O3The content molar ratio of (1): (1.5-6); more preferably 1: (2-4).
For the TiO with carrier function of the invention2The source of (A) is not particularly limited, and may be TiO conventionally used in the art2. But in order to further improve the NO of the catalyst pair thus obtainedxAnd Hg0Preferably said TiO, is2Is selected from anatase TiO2And commercial TiO2-WO3One or two of them.
Preferably, the vanadium source is selected from one or more of ammonium metavanadate, sodium metavanadate, potassium metavanadate, sodium orthovanadate and sodium pyrovanadate (also called sodium metavanadate). Particularly preferably, the source of vanadium is ammonium metavanadate.
Then, as previously mentioned, the present invention provides a method for preparing a metal oxide-vanadate/TiO2A process for the catalysis comprising:
(1) preparing a mixed solution containing a vanadium source and a metal salt, wherein the molar ratio of the amount of the vanadium source calculated by vanadium element to the amount of the metal salt calculated by metal element contained in the vanadium source is 1: (0.1-15);
(2) will contain TiO2The carrier is soaked in the mixed solution obtained in the step (1);
(3) drying the slurry obtained in the step (2);
(4) roasting the intermediate obtained in the step (3),
wherein the metal salt is a salt formed from one or two or more elements selected from the group consisting of Ce, Co, Fe and La.
Preferably, the vanadium source and the metal salt are used in such amounts that the content of the metal oxide in the catalyst prepared by the method of the present invention is greater than 0 and equal to or less than 15 wt%, and the content of the vanadate is 0.2 to 5 wt%, based on the total weight of the catalyst.
More preferably, the molar ratio of the amount of the vanadium source in terms of vanadium element to the amount of the metal salt in terms of metal element contained therein is 1: (0.2 to 10), and particularly preferably 1: (0.5-5).
In the present invention, the metal salt is AbYaWherein A is one or more elements selected from Ce, Co, Fe and La, Y is anion, a is valence state of A, and b is valence state of anion Y; the vanadate is A3(VO4)a(ii) a The metal oxide is M2OmM is V or A, and M is the valence state of M. When the metal salt AbYaWhen the ratio of the molar amount of the A element to the molar amount of the vanadium source in terms of the vanadium element is more than 1, the form of the obtained catalyst is A2Oa-A3(VO4)a/TiO2That is, the metal element in the metal oxide and the cation in the vanadate of the obtained catalyst are both provided by the metal element in the metal salt; when the metal salt AbYaWhen the ratio of the molar amount of the A element to the molar amount of the vanadium source in terms of the vanadium element is less than 1, the catalyst obtained is in the form of V2O5-A3(VO4)a/TiO2That is, the metal element in the metal oxide of the resulting catalyst is provided by the vanadium source and the cation in the vanadate is provided by the metal element in the metal salt.
Preferably, in the preparation method of the present invention, the sum of the amounts of the vanadium source and the metal salt is added to the TiO-containing compound2The weight ratio of the using amount of the carrier is (0.03-0.6): 1.
according to a preferred embodiment, the metal salt is a salt of the element Fe. More preferably, the molar ratio of the amount of vanadium source in terms of vanadium element to the amount of salt of Fe element in terms of Fe element contained therein is 1: (1.5-6); more preferably 1: (2-4).
Preferably, in step (1), the preparation of the mixed solution is performed in the presence of oxalic acid and/or monoethanolamine. The oxalic acid and the monoethanolamine are present to facilitate the dissolution of vanadium salt, the amount of the oxalic acid and the monoethanolamine is not particularly limited, and those skilled in the art can add a proper amount as required.
Preferably, the metal salt is one or more of a halide salt, a nitrate salt and a sulfate salt formed of one or more elements selected from Ce, Co, Fe and La. More preferably, the metal salt is a nitrate.
Preferably, in step (2), the impregnation conditions include: dipping for 1-5 h at 75-180 ℃.
Preferably, in step (3), the drying conditions include: the temperature is 80-150 ℃, and the time is 3-48 h.
According to a preferred embodiment, the catalyst is prepared for the simultaneous removal of NOxAnd Hg0Preferably the firing is performed in an air atmosphere and the firing step comprises: roasting the intermediate obtained in the step (3) at 100-150 ℃ for 0.5-2 h, then roasting at 240-380 ℃ for 0.5-1.5 h, and then roasting at 420-550 ℃ for 2-5 h.
In step (2), the impregnation is preferably carried out under heating with stirring so that the moisture in the mass of step (2) is removed by evaporation.
Again, the present invention provides the metal oxide-vanadate/TiO prepared by the aforementioned method2A catalyst.
Furthermore, the present invention also provides the aforementioned metal oxide-vanadate/TiO2The catalyst is applied to denitration and demercuration of flue gas.
Metal oxide-vanadate/TiO of the invention2The catalyst can be applied to the flue gas purification of coal-fired power plants, including the control of nitrogen oxides and mercury, and can be beneficial to environmental protection.
The scheme of the invention also has the following specific advantages:
metal oxide-vanadate/TiO of the invention2The catalyst has the outstanding advantages of high activity, strong selectivity, good stability and the like; metal oxide-vanadate/TiO of the invention2The preparation method of the catalyst is simple, and the catalyst is prepared in NH3-SCR and Hg0Excellent H resistance in oxidation2O and SO-resistance2Poisoning performance, and is suitable for practical application.
The present invention will be described in detail below by way of examples.
In the following examples, various raw materials used are commercially available without specific description.
The catalysts prepared in the following examples were evaluated for the efficiency of denitration and demercuration by the following methods:
putting a quantitative catalyst into a miniature fixed bed reactor, and introducing simulated flue gas into the reactor, wherein the simulated flue gas comprises the following components: 3% vol.O2，300ppm NO，300ppm NH3，500ppm SO2，8％H2O，20～75ug/m3Hg0Equilibrium gas N2The airspeed is 30000-150000 h-1The reaction temperature is 280-300 ℃.
Example 1
1. Cerium nitrate and 0.0425g of ammonium metavanadate were mixed in the presence of oxalic acid so that the molar ratio of Ce to V was 0.5;
2.5 g of TiO was added to the mixed solution obtained in step 12-WO3The carrier is stirred and soaked for 5 hours at the temperature of 75 ℃, and simultaneously, the water is removed by evaporation;
3. drying the slurry obtained in the step 2 at 110 ℃ for 3 h;
4. in the air atmosphere, the intermediate obtained in the step 3 is firstly roasted at 120 ℃ for 1h, then roasted at 300 ℃ for 1h, and then roasted at 500 ℃ for 3h to obtain V2O5-CeVO4/TiO2A catalyst.
The results show that the catalyst of this example is such that NOxThe conversion rate of the catalyst reaches 89.87-97.52%, and Hg is0The oxidation efficiency reaches 73.65-98.61%.
In addition, after 12 hours of continuous experiments, the conversion rate and the oxidation efficiency of the catalyst of the embodiment are both maintained to be more than 96-98% of the original level.
Comparative example 1
This comparative example was carried out using a preparation method similar to that of example 1, except that only ammonium metavanadate was added in step (1) of this comparative example, without using cerium nitrate, specifically:
1. in the presence of oxalic acid, 0.0425g of ammonium metavanadate is added;
2.5 g of TiO was added to the solution obtained in step 12-WO3The carrier is stirred and soaked for 5 hours at the temperature of 75 ℃, and simultaneously, the water is removed by evaporation;
3. drying the slurry obtained in the step 2 at 110 ℃ for 3 h;
4. in the air atmosphere, the intermediate obtained in the step 3 is firstly roasted at 120 ℃ for 1h, then roasted at 300 ℃ for 1h, and then roasted at 500 ℃ for 3h to obtain V2O5/TiO2A catalyst.
The results show that the catalyst of this comparative example results in NOxThe conversion rate of the catalyst reaches 85.71-95.37%, Hg0The oxidation efficiency of the catalyst reaches 21.65-69.47%.
And the conversion rate and the oxidation efficiency of the catalyst of the comparative example are reduced to more than 89-93% of the original level after 12 hours of continuous experiments.
Example 2
1. Lanthanum nitrate and 0.0425g of ammonium metavanadate were mixed in the presence of oxalic acid so that the molar ratio of La to V was 2;
2.5 g of TiO was added to the mixed solution obtained in step 12-WO3The carrier is stirred and soaked for 1h at 180 ℃, and simultaneously, the water is removed by evaporation;
3. drying the slurry obtained in the step 2 at 80 ℃ for 24 hours;
4. in the air atmosphere, the intermediate obtained in the step 3 is firstly roasted at 140 ℃ for 0.5h, then roasted at 280 ℃ for 1.5h, and then roasted at 550 ℃ for 2.5h to obtain La2O3-LaVO4/TiO2A catalyst.
The results show that the catalyst of this example is such that NOxThe conversion rate of the catalyst reaches 85.3-97.6 percent, and Hg0The oxidation efficiency reaches 72.64-90.35%.
In addition, after 12 hours of continuous experiments, the conversion rate and the oxidation efficiency of the catalyst of the embodiment are both maintained to be more than 93-95% of the original level.
Comparative example 2
This comparative example was carried out in a similar manner to example 2, except that:
in this comparative example, ammonium metavanadate was used in an amount of 0.0425g, and lanthanum nitrate was used in an amount such that the molar ratio of La to V was 18.
The results show that the catalyst of this comparative example results in NOxThe conversion rate of the catalyst is 15.76-45.28%, Hg0The oxidation efficiency of (A) is 25.41-35.92%.
And the conversion rate and the oxidation efficiency of the catalyst of the comparative example are reduced to more than 83-85% of the original level after 12 hours of continuous experiments.
Example 3
1. Cobalt nitrate and 0.0425g of ammonium metavanadate were mixed in the presence of oxalic acid so that the molar ratio of Co to V was 2.4;
2.5 g of TiO was added to the mixed solution obtained in step 12-WO3The carrier is stirred and soaked for 3 hours at the temperature of 150 ℃, and simultaneously, the water is removed by evaporation;
3. drying the slurry obtained in the step 2 at 110 ℃ for 3 h;
4. in the air atmosphere, the intermediate obtained in the step 3The body is calcined at 100 ℃ for 2h, then at 340 ℃ for 1h, and then at 520 ℃ for 2.5h to obtain Co2O3-CoVO4/TiO2A catalyst.
The results show that the catalyst of this example is such that NOxThe conversion rate of the catalyst reaches 84.02-98.73%, Hg0The oxidation efficiency reaches 74.03-95.48%.
In addition, after 12 hours of continuous experiments, the conversion rate and the oxidation efficiency of the catalyst of the embodiment are both maintained to be more than 95-97% of the original level.
Comparative example 3
This comparative example was carried out in a similar manner to example 3, except that:
the support in this comparative example was 5g of silica.
The results show that the catalyst of this comparative example results in NOxThe conversion rate of the catalyst is 32.64-56.65%, Hg0The oxidation efficiency of the catalyst reaches 10.37-34.20%.
And the conversion rate and the oxidation efficiency of the catalyst of the comparative example are reduced to more than 60-70% of the original level after 12 hours of continuous experiments.
Example 4
1. Mixing ferric nitrate and 0.0425g ammonium metavanadate in the presence of oxalic acid so that the molar ratio of Fe to V is 3;
2.5 g of TiO was added to the mixed solution obtained in step 12-WO3The carrier is stirred and soaked for 3 hours at the temperature of 150 ℃, and simultaneously, the water is removed by evaporation;
3. drying the slurry obtained in the step 2 at 150 ℃ for 2 h;
4. in the air atmosphere, the intermediate obtained in the step 3 is firstly roasted at 130 ℃ for 1h, then roasted at 280 ℃ for 1.5h, and then roasted at 500 ℃ for 3h to obtain Fe2O3-FeVO4/TiO2A catalyst.
The results show that the catalyst of this example is such that NOxThe conversion rate of the catalyst reaches 90.13-99.62%, Hg0The oxidation efficiency reaches 79.94-98.64%.
In addition, after 12 hours of continuous experiments, the conversion rate and the oxidation efficiency of the catalyst of the embodiment are both maintained to be more than 98-99% of the original level.
Example 5
This example was carried out in a similar manner to example 1, except that:
the calcination step in this example was:
roasting the intermediate obtained in the step 3 at 500 ℃ for 5 hours in air atmosphere to obtain V2O5-CeVO4/TiO2A catalyst.
The results show that the catalyst of this example is such that NOxThe conversion rate of the catalyst reaches 80.62-93.46%, Hg0The oxidation efficiency reaches 56.38-75.61%.
In addition, after 12 hours of continuous experiments, the conversion rate and the oxidation efficiency of the catalyst of the embodiment are both maintained to be more than 94-95% of the original level.
Example 6
This example was carried out in a similar manner to example 2, except that:
in this example, ammonium metavanadate was used in an amount of 0.0425g, and lanthanum nitrate was used in an amount such that the molar ratio of La to V was 5.
The results show that the catalyst of this example is such that NOxThe conversion rate of the catalyst is 78.73-92.67%, Hg0The oxidation efficiency reaches 47.52-70.34%.
In addition, after the catalyst of the embodiment is subjected to continuous experiments for a long time of 12 hours, the conversion rate and the oxidation efficiency are both maintained to be more than 93-95% of the original level.
It can be seen from the results of the above examples and comparative examples that the catalyst provided by the present invention can simultaneously achieve denitration and demercuration effects, and the denitration and demercuration effects are significantly better than those of the prior art, and the service life of the catalyst is significantly longer.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. Metal oxide-vanadate/TiO2A catalyst, comprising: TiO 22And supported on the TiO2Metal oxide and vanadate supported on the TiO2The vanadate and the metal oxide are formed by a vanadium source and a metal salt, and the cation of the vanadate is provided by a metal element in the metal salt, and the vanadium source and the metal salt are used in a molar ratio of 1: (0.5-5), wherein the metal salt is a salt formed by one or more elements selected from Ce, Co, Fe and La; based on the total weight of the catalyst, the content of the metal oxide is 1-5 wt%, and the content of the vanadate is 0.5-2 wt%;
preparation of the metal oxide-vanadate/TiO2A process for the catalysis comprising:
(1) preparing a mixed solution containing a vanadium source and metal salt;
(2) will contain TiO2The carrier is soaked in the mixed solution obtained in the step (1);
(3) drying the slurry obtained in the step (2);
(4) and (4) roasting the intermediate obtained in the step (3).
2. The catalyst of claim 1, wherein the vanadate is FeVO4And the metal oxide is Fe2O3。
3. The catalyst of claim 2, wherein the FeVO is calculated as vanadium element4And said Fe calculated as Fe element2O3The content molar ratio of (1): (2-4).
4. The catalyst according to claim 1, wherein the vanadium source is one or more selected from the group consisting of ammonium metavanadate, sodium metavanadate, potassium metavanadate, sodium orthovanadate and sodium pyrovanadate.
5. The catalyst of claim 4, wherein the source of vanadium is ammonium metavanadate.
6. The catalyst of claim 1, wherein the sum of the amounts of the vanadium source and the metal salt is equal to the amount of the TiO-containing compound2The weight ratio of the using amount of the carrier is (0.03-0.6): 1.
7. the catalyst of claim 6, wherein the metal salt is a salt of elemental Fe.
8. The catalyst according to claim 1, wherein, in step (1), the preparation of the mixed solution is carried out in the presence of oxalic acid and/or monoethanolamine.
9. The catalyst according to claim 1, wherein in step (1), the metal salt is one or more of a halide salt, a nitrate salt and a sulfate salt formed from one or more elements selected from Ce, Co, Fe and La.
10. The catalyst of claim 1, wherein in step (3), the drying conditions comprise: the temperature is 80-150 ℃, and the time is 3-48 h.
11. The catalyst of claim 1, wherein the calcining is performed under an air atmosphere and the calcining step comprises: roasting the intermediate obtained in the step (3) at 100-150 ℃ for 0.5-2 h, then roasting at 240-380 ℃ for 0.5-1.5 h, and then roasting at 420-550 ℃ for 2-5 h.
12. The metal oxide-vanadate/TiO of any one of claims 1 to 112The catalyst is applied to denitration and demercuration of flue gas.
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| CN109759078B (en) * | 2019-01-21 | 2023-02-03 | 北京工业大学 | Gamma-Fe load 2 O 3 Preparation method of molded SCR catalyst |
| CN111821997B (en) * | 2019-04-18 | 2022-12-09 | 清华大学 | Mercury-removing and denitration efficient catalyst and preparation method and application thereof |
| CN110215917B (en) * | 2019-04-19 | 2022-09-20 | 北京工业大学 | Supported vanadium acid metal M salt SCR catalyst and preparation method thereof |
| CN110624560B (en) * | 2019-09-17 | 2020-08-04 | 吉林师范大学 | FeVO for photo-Fenton combined catalysis4/TiO2Porous catalyst membrane layer material and preparation method thereof |
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