CN115945198B - Preparation method and application of low-temperature ammonium bisulfate-resistant layered iron-vanadium composite oxide denitration catalyst - Google Patents
Preparation method and application of low-temperature ammonium bisulfate-resistant layered iron-vanadium composite oxide denitration catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 108
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 title claims abstract description 38
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 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 claims abstract description 34
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
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- 238000005119 centrifugation Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 54
- 238000012360 testing method Methods 0.000 claims description 23
- 239000002243 precursor Substances 0.000 claims description 18
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 15
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- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 4
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 29
- 230000000694 effects Effects 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
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Abstract
The invention discloses a preparation method and application of a low-temperature ammonium bisulfate-resistant layered iron-vanadium composite oxide denitration catalyst, and belongs to the field of air pollution control. The preparation method of the catalyst comprises the following steps: adding ammonium metavanadate into deionized water, dissolving under the conditions of magnetic stirring and heating, dripping ferric nitrate nonahydrate or a mixed solution of ferric nitrate and nitric acid into the ammonium metavanadate solution, maintaining the stirring and heating state until the reaction is finished, and performing centrifugation, washing, drying and calcination treatment to obtain the layered iron-vanadium composite oxide denitration catalyst. The catalyst obtained by the invention is applied to ammonia selective catalytic reduction (NH) 3 SCR) denitration reaction shows better medium-low temperature catalytic activity and high N 2 The selectivity and the high low-temperature ammonium bisulfate resistance are high.
Description
Technical Field
The invention relates to a preparation method and application of a low-temperature ammonium bisulfate-resistant layered iron-vanadium composite oxide denitration catalyst, and belongs to the field of air pollution control.
Background
Nitrogen Oxides (NO) x ) Is bigOne of the main pollutants of the gas is a main precursor of air pollutants such as haze, photochemical smog and the like, and can cause serious harm to the ecological environment and human health. Currently, ammonia selective catalytic reduction (NH 3 SCR) technology is the mainstream denitration technology of mobile and fixed sources, traditional commercial V 2 O 5 -WO 3 /TiO 2 The catalyst has a higher working temperature window (300-400 ℃), and is mainly suitable for coal-fired power plants. However, the specific gravity of non-electric industries such as steel, cement, coking, glass, ceramics and the like in China is gradually increased, the smoke temperature is relatively low and is mainly between 150 ℃ and 300 ℃, and the traditional high temperature V is adopted at the moment 2 O 5 -WO 3 /TiO 2 The denitration efficiency of the catalyst is low. In addition, the flue gas contains a certain amount of SO 2 And H 2 O，SO 2 Can be oxidized into SO by a catalyst 3 Which is in combination with H in the flue gas 2 O and NH 3 Inevitably reacts to form ammonium bisulfate (NH) 4 HSO 4 ) It has certain viscosity at low temperature and can cover the surface of catalyst to deactivate the catalyst. If the flue gas is reheated to meet the conditions of use of the catalyst, additional energy consumption is generated. Therefore, the development of the high-efficiency low-temperature ammonium bisulfate-resistant catalyst can effectively save unnecessary energy consumption and has important significance for flue gas denitration in the non-electric industry.
In the common denitration catalyst active components, compared with other metal oxides (such as manganese oxide, copper oxide, cerium oxide and the like), the ferric oxide and the vanadium oxide are not easy to chemically adsorb sulfur dioxide, or the thermal stability of generated metal sulfate is relatively low, so that the deactivation caused by the formation of the metal sulfate can be effectively avoided. In recent years, iron-vanadium composite oxide denitration catalysts are gradually paid attention to by researchers due to certain low-temperature denitration potential. Yongglong Li et al (W.L. Yongglong Li, ran Yan, jian Liang, tao Dong, yangyang Mi, peng Wu, zheng Wang, hongen Peng, taicheng An, applied Catalysis B: environmental 268 (2020))find3 DOM-Fe 9.0 V 1.0 The catalyst has a wide active temperature window and shows excellent NH 3 SCR performance, in the temperature range 220-412 DEG CInside, NO x The conversion rate can reach more than 80 percent. Jinching Mu et al (X.L. Jinching Mu, xinyang Wang, shining Fan, zhifan Yin, zeyu Li, moses O. Tade ́, shaomin Liu, the Journal of Physical Chemistry C (2020) 21396-21406.) synthesized a series of vanadium doped Fe by homogeneous precipitation 2 O 3 The catalyst, through research, found that Fe0 .75 V 0.25 O δ The catalyst achieves 100% NO at 200 DEG C x Conversion rate. However, the iron-vanadium composite oxide denitration catalyst is easy to poison by low-temperature deposition of ammonium bisulfate, and the improvement of the low-temperature ammonium bisulfate resistance is worth deeply exploring.
Disclosure of Invention
Aiming at the defect of low-temperature ammonium bisulfate resistance of the existing denitration catalyst, the invention provides a preparation method and application of a low-temperature ammonium bisulfate resistance layered iron-vanadium composite oxide denitration catalyst.
The invention constructs a layered iron-vanadium metal oxide denitration catalyst based on the inhibition effect of iron oxide and vanadium oxide on sulfur dioxide adsorption, and can promote dissociation of ammonium bisulfate by means of hydrogen bond formed between a large amount of proton acceptor oxygen in the layered oxide and ammonium bisulfate ions. Meanwhile, the oxide catalyst with the layered structure can provide a transmission channel and a storage space for dissociated ammonium ions, can avoid continuous accumulation of dissociated ammonium ions on the surface of the catalyst, accelerates realization of equilibrium between generation and decomposition kinetics of ammonium bisulfate, and further improves the low-temperature ammonium bisulfate resistance of the catalyst.
The invention provides a preparation method of a low-temperature ammonium bisulfate-resistant layered iron vanadium composite oxide denitration catalyst, which comprises the steps of preparing a solution, carrying out hydrothermal treatment, centrifuging, washing and drying by taking ferric nitrate nonahydrate, ammonium metavanadate and nitric acid as raw materials and deionized water as a solvent to prepare a layered ferric vanadate precursor material, and roasting the precursor to obtain layered Fe x V 1-x O y (x=0.20 to 0.33, y=2.10 to 2.30).
The method specifically comprises the following steps:
(1) Preparation of ammonium metavanadate solution
And adding deionized water into the round-bottom flask, heating to 85-95 ℃, adding ammonium metavanadate powder into the flask, and magnetically stirring for 5-15 min to completely dissolve the ammonium metavanadate powder to form an ammonium metavanadate solution.
(2) Preparing a mixed solution of ferric nitrate and nitric acid
Weighing ferric nitrate nonahydrate solid into a beaker, adding deionized water, and stirring for 15-20 min by using a magnetic stirrer to completely dissolve the ferric nitrate nonahydrate solid for later use;
transferring concentrated nitric acid into a beaker by using a liquid transferring gun, adding deionized water to dilute the concentrated nitric acid to form dilute nitric acid (0.16-0.20 mol/L), and mixing the dilute nitric acid with ferric nitrate solution to form mixed solution for later use;
(3) Preparation of layered iron vanadate precursor
Adding the prepared mixed solution of ferric nitrate and nitric acid into the prepared ammonium metavanadate solution, and continuously stirring for 0.5-7 h at 85-95 ℃ until the reaction is complete;
(4) Centrifugal washing
Cooling the reacted suspension to room temperature, removing most of supernatant by a liquid-transferring gun after the sediment is settled to the bottom of the flask, transferring the residual solution and the sediment into a centrifuge tube for centrifugation, keeping the rotation speed at 3000-5000 rpm for 5-15 min, and removing the upper liquid of the centrifuge tube after centrifugation; then adding ethanol, ultrasonically washing for 5-15 min, centrifuging and separating again, and repeating the ethanol washing, centrifuging and separating processes for 1-3 times;
(5) Drying
The precipitate after centrifugation and washing is kept in a centrifuge tube, and is transferred to an oven with the temperature of 60-80 ℃ for drying, and the drying time is 12 h, so that a layered ferric vanadate precursor is obtained for standby;
(6) Roasting
Putting the ferric vanadate precursor obtained in the step (5) into a muffle furnace for 1-5 ℃ for min -1 And (3) the temperature rising rate is increased to 350 ℃ and kept for 2-8 hours, so as to prepare the layered iron-vanadium composite oxide flue gas denitration catalyst.
In the above method, in the step (1), the concentration of ammonium metavanadate in the mixed solution is controlled to be 0.01-0.09 mol L -1 。
In the above method, in the step (2), the concentration of ferric nitrate in the mixed solution of ferric nitrate and nitric acid is controlled to be 0.05-0.3 mol L -1 The pH value of the solution is controlled between 0.5 and 2.5.
In the above method, in step (3)c(V 5+ ) : c(Fe 3+ ) Controlling the ratio of the components to be 1:1-5:1, whereinc(V 5+ )Refers to the concentration of vanadium ion substances in the ammonium metavanadate solution,c(Fe 3+ ) Refers to the mass concentration of iron ion substances in the mixed solution of ferric nitrate and nitric acid.
The invention provides a layered iron-vanadium composite oxide denitration catalyst prepared by the preparation method.
The invention provides a layered iron-vanadium composite oxide denitration catalyst in NH 3 -use in SCR reactions.
For the above application, layered Fe x V 1-x O y Catalyst for NH 3 During SCR reaction, the catalyst is firstly subjected to grinding treatment, and the specific operation is as follows: and (3) placing the roasted layered iron-vanadium composite oxide denitration catalyst in a mortar, grinding for 1-5 min, taking out the catalyst to a 40-60 mesh sieve, and sieving the catalyst to obtain 40-60 mesh particles.
The invention adopts a fixed bed reactor to carry out NH 3 -SCR reactivity test. The specific application process is as follows: catalytic reaction tests were performed in a fixed bed continuous flow quartz reactor. The composition of the reaction gas is as follows: [ NO ]]=500 ppm，[NH 3 ]=500 ppm，5 vol% O 2 ，[SO 2 ]=200 ppm (when used), 10 vol% H 2 O (when in use), N 2 As balance gas, the total flow of the gas is 120 mL min -1 . The catalyst used had a volume of 0.2. 0.2 mL and a volume space velocity of 36,000 h -1 The testing temperature is 90-360 ℃, the activity data is collected after the reaction reaches equilibrium, and the product is detected and analyzed by a Fourier infrared smoke analyzer (MKS-6030E). NO (NO) x Conversion and N 2 The selectivity is calculated by the following formula:
[NO x ]represents NO x Concentration [ NO ]]Represents the concentration of NO, [ N ] 2 O]Represents N 2 O concentration, [ NH ] 3 ]Representing NH 3 The concentration, in, represents the reactor inlet concentration, and out represents the reactor outlet concentration.
The invention has the beneficial effects that:
(1) The invention takes the iron-vanadium dual-active component as the research basis, based on the weak chemical adsorption of iron oxide and vanadium oxide to sulfur dioxide, a layered iron-vanadium composite oxide denitration catalyst is constructed, and the prepared layered iron-vanadium composite oxide denitration catalyst has more than 80 percent of NO in the range of 210-330 DEG C x The removal rate is kept high at the same time 2 Selectivity.
(2) The catalyst designed by the invention has a layered structure, can promote the formation of hydrogen bonds between ammonium ions in ammonium bisulfate and proton acceptor oxygen in the catalyst so as to weaken ionic bonds in ammonium bisulfate, and is beneficial to promoting the decomposition of ammonium bisulfate.
(3) The denitration catalyst prepared by the invention is subjected to in-situ ABS test at 200 ℃, and 10 vol% of H is simultaneously introduced into the SCR test atmosphere 2 O and 200 ppm SO 2 The catalyst shows better stability within the test time range of 24 h and has good in-situ ABS resistance.
Drawings
Fig. 1 is an X-ray diffraction pattern of the preparation of iron vanadate precursor, iron vanadium composite oxide catalyst and commercial VWTi catalyst according to examples 1, 2 and 3 of the present invention. The (I) is ferric vanadate precursor (a) Fe 0.33 V 0.67 O 2.17 -P，(b) Fe 0.25 V 0.75 O 2.25 -P，(c) Fe 0.2 V 0.8 O 2.3 -P; (II) is an iron-vanadium composite oxide catalyst and a commercial VWTi catalyst (a) Fe 0.33 V 0.67 O 2.17 -C, (b) Fe 0.25 V 0.75 O 2.25 C, (C) is Fe 0.2 V 0.8 O 2.3 -C, (d) VWTi；
FIG. 2 shows the preparation of iron-vanadium composite according to examples 1, 2 and 3 of the present inventionOxide catalyst and commercial VWTi catalyst Scanning Electron Microscope (SEM) images, wherein (a) (b) Fe 0.33 V 0.67 O 2.17 -C，(c) (d) Fe 0.25 V 0.75 O 2.25 -C，(e) (f) Fe 0.2 V 0.8 O 2.3 -C, (g) (h) VWTi. (a) (c) and (e) are 5-thousand-magnification SEM images, (b) and (d) and (f) are 10-thousand-magnification SEM images, and (g) and (h) are 1-thousand and 1-thousand-magnification SEM images, respectively;
FIG. 3 shows the preparation of iron-vanadium composite oxide catalyst N according to examples 1, 2 and 3 of the present invention 2 Adsorption/desorption isotherms. A nitrogen adsorption/desorption curve and a pore size distribution diagram; wherein (a) Fe 0.33 V 0.67 O 2.17 -C，(b) Fe 0.25 V 0.75 O 2.25 -C, (c) Fe 0.2 V 0.8 O 2.3 -C，(d) VWTi；
FIG. 4 is a schematic diagram of the preparation of the iron vanadium composite oxide catalyst and the commercial VWTi catalyst NH in examples 1, 2 and 3 3 SCR Performance evaluation (I) NO x Conversion and (II) N 2 Selectivity map. Wherein (a) Fe 0.33 V 0.67 O 2.17 -C, (b) Fe 0.25 V 0.75 O 2.25 -C, (c) Fe 0.2 V 0.8 O 2.3 -C, (d) VWTi (test conditions [ NH ] 3 ]=[NO]=500 ppm，5 vol% O 2 ，N 2 Balance gas, ghsv=36,000 h -1 ）；
FIG. 5 is an in situ NH. Resistant iron vanadium composite oxide catalyst and commercial VWTi catalyst prepared in examples 1, 2 and 3 4 HSO 4 Performance test chart. Wherein (a) Fe 0.33 V 0.67 O 2.17 -C, (b) Fe 0.25 V 0.75 O 2.25 -C, (c) Fe 0.2 V 0.8 O 2.3 -C, (d) VWTi (test conditions: [ NH ] 3 ]=[NO]=500 ppm，[SO 2 ]=200 ppm，5vol% O 2 ，10 vol% H 2 O，N 2 Balance gas, ghsv=36,000 h -1 ，200 ℃）。
Description of the embodiments
The present invention is further illustrated by, but not limited to, the following examples.
Example 1
(1) Weighing ammonium metavanadate 0.234 and g into a beaker, adding 100.0 and mL deionized water into the beaker, placing the beaker in a water bath kettle, keeping the temperature at 90 ℃, and stirring the beaker by a magnetic stirrer for 10 min to completely dissolve the beaker for later use;
(2) Weighing ferric nitrate nonahydrate 0.808. 0.808 g into a beaker, adding dilute nitric acid solution into the beaker to ensure that the concentration of the ferric nitrate is 0.2 mol L -1 Controlling the pH value of the solution to be about 1 for standby;
(3) Adding the mixed solution of ferric nitrate and dilute nitric acid into the prepared ammonium metavanadate solution, continuously reacting for 1 h under the stirring action of 90 ℃ and 500 r/min, standing the obtained suspension for sedimentation for 1 h, removing the supernatant, centrifuging and washing the rest precipitate (washing with deionized water for 2 times and washing with ethanol for 1 time), drying the washed precipitate in a 60 ℃ oven for 12 h times, and grinding to obtain ferric vanadate precursor (marked as Fe) 0.33 V 0.67 O 2.17 -P) for use;
(4) Placing the material obtained in the step (3) into a muffle furnace, and programming the temperature from room temperature to 350 ℃ to keep 5 h, wherein the temperature raising rate is 2 ℃ for min -1 Naturally cooling to room temperature to obtain catalyst powder (marked as Fe 0.33 V 0.67 O 2.17 And C), tabletting and screening to obtain 40-60 mesh catalyst particles for later use.
Example 2
(1) Weighing ammonium metavanadate 0.351 and g into a beaker, adding 100.0 and mL deionized water into the beaker, placing the beaker in a water bath kettle, keeping the temperature at 90 ℃, and stirring the beaker by a magnetic stirrer for 10 min to completely dissolve the beaker for later use;
(2) Weighing ferric nitrate nonahydrate 0.404. 0.404 g into a beaker, adding 10.0. 10.0 mL deionized water into the beaker to prepare the ferric nitrate nonahydrate with the concentration of 0.1 mol L -1 Is used for standby;
(3) Adding the prepared ferric nitrate solution into the prepared ammonium metavanadate solution, continuously reacting at 90deg.C under 500 r/min stirring for 1 h, standing the obtained suspension for settling for 1 h, removing supernatant, and collecting the rest solutionCentrifuging and washing the precipitate (deionized water for 2 times and ethanol for 1 time), drying the washed precipitate in oven at 60deg.C for 12 h, and grinding to obtain ferric vanadate precursor (marked as Fe) 0.25 V 0.75 O 2.25 -P) for use;
(4) Placing the material obtained in the step (3) into a muffle furnace, and programming the temperature from room temperature to 350 ℃ to keep 5 h, wherein the temperature raising rate is 2 ℃ for min -1 Naturally cooling to room temperature to obtain catalyst powder (marked as Fe 0.25 V 0.75 O 2.25 And C), tabletting and screening to obtain 40-60 mesh catalyst particles for later use.
Example 3
(1) Weighing ammonium metavanadate 0.936 g into a beaker, adding 100.0 mL deionized water into the beaker, placing the beaker in a water bath kettle at a constant temperature of 95 ℃, and stirring the beaker for 10 min by using a magnetic stirrer to completely dissolve the ammonium metavanadate;
(2) Weighing ferric nitrate nonahydrate 0.808. 0.808 g into a beaker, adding 10.0. 10.0 mL deionized water into the beaker to prepare the ferric nitrate nonahydrate with the concentration of 0.1 mol L -1 Is used for standby;
(3) Adding the prepared ferric nitrate solution into the prepared ammonium metavanadate solution, continuously reacting at 95 ℃ under the stirring action of 500 r/min for 6 h, standing the obtained suspension for sedimentation of 1 h, removing supernatant, centrifuging and washing the rest precipitate (deionized water for 2 times and ethanol for 1 time), drying the washed precipitate in a 60 ℃ oven for 12 h times, and grinding to obtain ferric vanadate precursor (marked as Fe) 0.2 V 0.8 O 2.3 -P) for use;
(4) Placing the material obtained in the step (3) into a muffle furnace, and programming the temperature from room temperature to 350 ℃ to keep 5 h, wherein the temperature raising rate is 2 ℃ for min -1 Naturally cooling to room temperature to obtain catalyst powder (marked as Fe 0.2 V 0.8 O 2.3 And C), tabletting and screening to obtain 40-60 mesh catalyst particles for later use.
The ferric vanadate precursors prepared in the steps (3) and (4) in the examples 1, 2 and 3 are catalyzed by the iron-vanadium composite oxideChemical agent and commercial V 2 O 5 -WO 3 /TiO 2 The catalyst (labeled VWTi, purchased from Cormetech corporation) was subjected to X-ray diffraction analysis, and the diffraction patterns thereof are shown in fig. 1, respectively. Diffraction peaks of ferric vanadate precursor shown in curves (a), (b) and (c) of figure 1 (I) and pure phase Fe 5 V 15 O 39 (OH) 9 ∙ 9H 2 O (JCPDS Card No. 46-1334) with a monoclinic structure, at 8.3 o A stronger diffraction peak appears nearby and corresponds to the (002) crystal face, which shows that the ferric vanadate precursor has the characteristic of a layered structure. After calcination at 350℃the monoclinic structure remains unchanged, as shown by curves (a), (b), (c) in FIG. 1 (II), but at 8.3 o The intensity of the diffraction peak of the nearby (002) crystal face is reduced and the diffraction peak is shifted to 10.4 in the high-angle direction o In the vicinity, it was revealed that the interlayer spacing in the c-axis direction was reduced mainly due to the loss of structural water during calcination, but the layered structure of the calcined iron-vanadium composite oxide catalyst was still retained to some extent. VWTi catalyst as shown in curve (d) of FIG. 1 (II), the catalyst exhibited typical anatase TiO 2 No characteristic peaks of the lamellar structure were observed in the crystalline phase.
The iron-vanadium composite oxide catalyst prepared in step (4) of examples 1, 2 and 3 and the commercial VWTi catalyst were observed under a scanning electron microscope, and the results are shown in fig. 2. As can be seen from fig. 2 (a, c, e) at 5 ten thousand times magnification, the prepared iron-vanadium composite oxide catalyst has a lamellar structure macroscopically, lamellar layers are mutually staggered, the lamellar thickness is nano-scale, and the lamellar width is micro-scale. Fig. 2 (b, d, f) is a scanning electron micrograph at a further magnification of 10 tens of thousands of times, and the features of the layered structure of the catalyst can be seen more clearly. FIG. 2 (g, h) is a scanning electron micrograph of a commercial VWTi catalyst at 1 thousand and 1 thousand magnifications, the micrometer rod of FIG. 2 (g) is glass fiber added to increase the strength of the commercial catalyst, and the bulk material having no obvious structural features shown in FIG. 2 (h) is V 2 O 5 -WO 3 /TiO 2 The compound of the catalyst powder and other additives can be seen that the catalyst has no obvious lamellar structure。
Performing nitrogen adsorption/desorption tests on the iron-vanadium composite oxide catalyst prepared in the step (4) in the examples 1, 2 and 3 and the commercial VWTi catalyst, wherein the specific test process comprises the following steps: firstly, pretreating a sample to be tested for preparing 0.2. 0.2 g in a degassing workstation, and specifically testing the sample to be tested by the following steps: 200. degassing the sample at 4 h in a vacuum state at a temperature of DEG C to remove weakly adsorbed impurities and water on the surface of the sample; then N 2 Adsorption and desorption tests were performed in a liquid nitrogen environment at-196 ℃. The specific surface area of each catalyst was calculated by means of the Brunauer-Emmett-Teller (BET) method, while the Barrett-Joyner-Halenda (BJH) method was used for pore volume and pore size analysis of the catalyst. The nitrogen adsorption/desorption isotherm and the pore size distribution are shown in figure 3, and the nitrogen adsorption/desorption isotherm is an IV type isotherm accompanied with an H3 type hysteresis loop, which shows that the catalyst has mesoporous structure characteristics. Corresponding Fe of curves (a), (b) and (c) 0.33 V 0.67 O 2.17 -C, Fe 0.25 V 0.75 O 2.25 -C, Fe 0.2 V 0.8 O 2.3 The BET specific surface area of the catalyst C is 55 m 2 g -1 、36 m 2 g -1 、35 m 2 g -1 The average pore sizes were 14 nm, 16 nm, 15 nm, respectively. The BET specific surface area of the commercial VWTi catalyst corresponding to curve (d) is 83 m 2 g -1 The average pore size was 12 nm.
Application example 1: NH of catalyst 3 SCR Performance evaluation
NH-iron-vanadium composite oxide catalysts prepared in examples 1, 2 and 3 3 SCR denitration performance test and comparison with commercial VWTi catalyst. Before the experiment, the catalyst is subjected to tabletting treatment and is ground and sieved to 40-60 meshes. The catalyst particles after 0.20. 0.20 mL screening are taken to be placed in a groove in the middle of a quartz reaction tube, and a proper amount of quartz cotton is filled on the groove and the groove. The temperature test interval of the layered iron-vanadium composite oxide catalyst with different Fe/V ratios is 90-330 ℃, the temperature test interval of the VWTi is 90-480 ℃, and the temperature rising rate is 3 ℃ min -1 . The results are shown in FIG. 4, and the activation temperature (T) 50 ) As low as 161 ℃ and within the temperature range of 213-330 DEG CThe surrounding denitration efficiency can reach more than 80 percent, and the N of the catalyst can be controlled in the temperature range (90-330 ℃) of the whole test interval 2 The selectivity is kept above 85%, and the catalyst shows good middle-low temperature denitration catalytic activity and good N 2 Selectivity. In contrast, commercial VWTi catalysts exhibit good N over the test temperature range (90-480 ℃) 2 The catalyst has high denitration activity at 300 ℃ or above, but has lower denitration activity below 300 ℃ than that of the iron-vanadium composite oxide catalyst, and has poor medium-low temperature denitration catalytic performance.
Application example 2: catalyst in situ NH resistance 4 HSO 4 Evaluation of Performance
In situ NH resistance of the iron-vanadium composite oxide catalysts prepared in examples 1, 2 and 3 4 HSO 4 Performance test, additional 10 vol% H was introduced into the SCR test atmosphere at 200℃ 2 O and 200 ppm SO 2 Simulation of NH under actual conditions 4 HSO 4 The in situ formation has an effect on catalyst stability and is compared to commercial VWTi catalysts. As shown in FIG. 5, the curves (a), (b) and (c) correspond to Fe 0.33 V 0.67 O 2.17 -C, Fe 0.25 V 0.75 O 2.25 -C, Fe 0.2 V 0.8 O 2.3 The catalyst C was fed with 10 vol% H 2 O and 200 ppm SO 2 The denitration activity showed a relatively obvious attenuation after one hour, but gradually attenuated in the following 23 h, the activity retention rates after the test is completed were 71%,79% and 71%, respectively, and the denitration activity showed better catalytic stability under the test conditions. In addition, the activity of the catalyst can be improved to different degrees after the regeneration treatment, wherein Fe with lower iron content 0.2 V 0.8 O 2.3 The denitration activity of the catalyst can be almost restored to the initial state, and the denitration activity is almost restored to the initial state in the other two Fe 0.33 V 0.67 O 2.17 -C and Fe 0.25 V 0.75 O 2.25 In the C sample, with increasing iron content, the recovery capacity of the activity after regeneration decreases, indicating the generation of irreversible deactivation, which is mainly related to the chemisorption between iron oxide and sulfur dioxide. In contrast, commercial VWTi catalysts were not evident during the test procedureActivity decays (6%) but its denitration activity is at a lower level (35%) under the test conditions. Thus, it can be seen that the iron-vanadium composite oxide catalyst has better in-situ NH resistance under the test condition 4 HSO 4 Performance and practical application potential.
Claims (7)
1. A process for preparing the low-temp ammonium bisulfate resistant composite oxide denitration catalyst of layered iron-vanadium oxide includes such steps as preparing solution, hydrothermal treating, centrifugal separation, washing and baking, and features that the layered iron-vanadium oxide precursor is prepared from nine-water ferric nitrate, ammonium metavanadate and nitric acid as raw materials and deionized water as solvent x V 1-x O y ，x=0.20~0.33，y=2.10~2.30；
The preparation method of the low-temperature ammonium bisulfate-resistant layered iron-vanadium composite oxide denitration catalyst comprises the following steps:
(1) Preparation of ammonium metavanadate solution
Adding deionized water into a round-bottom flask, heating to 85-95 ℃, adding ammonium metavanadate powder into the flask, and magnetically stirring for 5-15 min to completely dissolve the ammonium metavanadate powder to form an ammonium metavanadate solution;
(2) Preparing a mixed solution of ferric nitrate and nitric acid
Weighing ferric nitrate nonahydrate solid into a beaker, adding deionized water, and stirring for 15-20 min by using a magnetic stirrer to completely dissolve the ferric nitrate nonahydrate solid for later use;
transferring concentrated nitric acid into a beaker by using a liquid transferring gun, adding deionized water to dilute the concentrated nitric acid to form 0.16-0.20 mol/L dilute nitric acid, and mixing the dilute nitric acid with ferric nitrate solution to form mixed solution for later use;
(3) Preparation of layered iron vanadate precursor
Adding the prepared mixed solution of ferric nitrate and dilute nitric acid into the prepared ammonium metavanadate solution, and continuously stirring for 0.5-7 h at 85-95 ℃ until the reaction is complete;
(4) Centrifugal washing
Cooling the reacted suspension to room temperature, removing most of supernatant by a liquid-transferring gun after the sediment is settled to the bottom of the flask, transferring the residual solution and the sediment into a centrifuge tube for centrifugation, keeping the rotation speed at 3000-5000 rpm for 5-15 min, and removing the upper liquid of the centrifuge tube after centrifugation; then adding ethanol, ultrasonically washing for 5-15 min, centrifuging and separating again, and repeating the ethanol washing, centrifuging and separating processes for 1-3 times;
(5) Drying
The precipitate after centrifugal washing is kept in a centrifuge tube, and is transferred to an oven with the temperature of 60-80 ℃ for drying, and the drying time is 12 h, so that a layered ferric vanadate precursor is obtained for standby;
(6) Roasting
Putting the ferric vanadate precursor obtained in the step (5) into a muffle furnace for 1-5 ℃ for min -1 And (3) the temperature rising rate is increased to 350 ℃ and kept for 2-8 hours, so as to prepare the layered iron-vanadium composite oxide denitration catalyst.
2. The method for preparing the low-temperature ammonium bisulfate resistant layered iron-vanadium composite oxide denitration catalyst according to claim 1, which is characterized by comprising the following steps: in the step (1), the mass concentration of ammonium metavanadate in the ammonium metavanadate solution is controlled to be 0.01-0.09 mol L -1 The method comprises the steps of carrying out a first treatment on the surface of the In the step (2), the concentration of the ferric nitrate in the mixed solution of the ferric nitrate and the dilute nitric acid is controlled to be 0.05 to 0.3 mol L -1 The pH value of the solution is controlled between 0.5 and 2.5.
3. The method for preparing the low-temperature ammonium bisulfate resistant layered iron-vanadium composite oxide denitration catalyst according to claim 1, which is characterized by comprising the following steps: in the step (3), thec(V 5+ ) : c(Fe 3+ ) Controlling the ratio of the components to be 1:1-5:1, whereinc(V 5+ ) Refers to the concentration of vanadium ion substances in the ammonium metavanadate solution,c(Fe 3+ ) Refers to the concentration of iron nitrate or the mixture of iron nitrate and nitric acid.
4. A low temperature ammonium bisulfate resistant layered iron vanadium composite oxide denitration catalyst prepared by the preparation method of any one of claims 1 to 3.
5. A low-temperature ammonium bisulfate-resistant layered iron-vanadium composite oxide denitration catalyst as set forth in claim 4 in NH 3 -use in SCR reactions.
6. The use according to claim 5, characterized in that: during application, the layered iron-vanadium composite oxide denitration catalyst is pressed into tablets, ground and placed into a 40-60 mesh sieve for sieving, and then 40-60 mesh denitration catalyst particles are obtained.
7. The use according to claim 5, characterized in that: the reaction conditions were as follows: [ NO ]]=500 ppm，[NH 3 ]=500 ppm，5 vol% O 2 ，[SO 2 ]=200 ppm，10 vol% H 2 O，N 2 As balance gas, the total flow of the gas is 120 mL min -1 The catalyst particles with 40-60 meshes are adopted to have the volume of 0.2-mL and the volume space velocity of 36,000 h -1 The test temperature range is 90-360 ℃; collecting gas concentration data after the reaction reaches equilibrium, NO x Conversion and N 2 The selectivity is calculated by the following formula:
；
；
[NO x ]represents NO x Concentration [ NO ]]Represents the concentration of NO, [ N ] 2 O]Represents N 2 O concentration, [ NH ] 3 ]Representing NH 3 The concentration, in, represents the reactor inlet concentration, and out represents the reactor outlet concentration.
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