CN113198444A - Low-temperature CO reduction denitration V/AC catalyst and preparation method and application thereof - Google Patents
Low-temperature CO reduction denitration V/AC catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN113198444A CN113198444A CN202110517938.0A CN202110517938A CN113198444A CN 113198444 A CN113198444 A CN 113198444A CN 202110517938 A CN202110517938 A CN 202110517938A CN 113198444 A CN113198444 A CN 113198444A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- temperature
- low
- denitration
- activated carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 105
- 230000009467 reduction Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 98
- 235000013162 Cocos nucifera Nutrition 0.000 claims abstract description 25
- 244000060011 Cocos nucifera Species 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 16
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims abstract description 13
- 239000003546 flue gas Substances 0.000 claims abstract description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 6
- 238000007598 dipping method Methods 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims description 12
- 239000012018 catalyst precursor Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052720 vanadium Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 7
- 230000003213 activating effect Effects 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000007605 air drying Methods 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 2
- 239000000779 smoke Substances 0.000 abstract description 2
- 230000004913 activation Effects 0.000 abstract 1
- 239000012299 nitrogen atmosphere Substances 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 22
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 19
- 238000006722 reduction reaction Methods 0.000 description 19
- 239000007789 gas Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 238000012512 characterization method Methods 0.000 description 10
- 238000011068 loading method Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 4
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 4
- 229940041260 vanadyl sulfate Drugs 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 125000000686 lactone group Chemical group 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Images
Classifications
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01D53/90—Injecting reactants
-
- 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
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/204—Carbon monoxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a low-temperature CO reduction denitration V/AC catalyst, a preparation method and application thereof, and belongs to the technical field of flue gas purification. The invention adds coconut shell activated carbon particles into nitric acid solution for activation to obtain AC carrier, and adds the AC carrier into VOSO4Dipping in the solution, and roasting at 450-550 ℃ in a nitrogen atmosphere to obtain low-temperature CO reduction denitrationV/AC catalyst. The low-temperature CO reduction denitration V/AC catalyst can be used as a low-temperature catalyst and CO is used as a reducing agent to remove NO in smokexThe low-temperature CO reduction denitration V/AC catalyst disclosed by the invention is simple in preparation method, good in vanadium oxide dispersibility, and has the characteristics of higher denitration rate, good nitrogen selectivity and the like.
Description
Technical Field
The invention relates to a low-temperature CO reduction denitration V/AC catalyst, a preparation method and application thereof, and belongs to the technical field of flue gas purification.
Background
The active carbon as a metal oxide catalyst carrier has the advantages of large specific surface area, rich pore-size structure, stable chemical property, good adsorption performance, high strength, easy regeneration and the like. The catalyst prepared by using the active carbon as the carrier is widely used in various fields of oil refining, chemical engineering, agriculture and the like. The surface physical and chemical properties of the activated carbon are different due to different materials, so that the performance of the prepared catalyst is greatly different.
Nitrogen Oxides (NO) produced by stationary and mobile sources in air pollutantsx) Causing many environmental problems such as acid rain and photochemical smog. Selective catalytic reduction of ammonia (NH) to date3SCR) denitration technology has become the removal of NOxOne of the most efficient approaches, but this technique has limitations, such as NH3Leakage, catalyst poisoning, pipe corrosion, and air preheater plugging. Therefore, it is necessary toSearch for a substitute NH3-a method of SCR.
Disclosure of Invention
The invention aims at NH in the prior flue gas denitration technology3The invention provides a low-temperature CO reduction denitration V/AC catalyst and a preparation method and application thereof, and aims to solve the problems of SCR (selective catalytic reduction) process, wherein the low-temperature CO reduction denitration V/AC catalyst takes cheap coconut shell activated carbon as a carrier and vanadium oxide mainly containing pentavalent vanadium as an active component to realize the effect of carrying out reduction on NO by taking CO as a reducing agent under the low-temperature conditionxRemoving; can solve the problem of the prior flue gas denitration NH3The SCR catalyst has the problems of low denitration rate, easy blockage of pore channels, easy poisoning and the like under the low-temperature condition.
A low-temperature CO reduction denitration V/AC catalyst comprises a nitric acid activated coconut shell activated carbon carrier and a vanadium oxide active component, wherein the mass ratio of vanadium element to coconut shell activated carbon is 5-15%; performing low-temperature catalytic CO reduction denitration by using a V/AC catalyst; if the mass ratio of the vanadium element is too large, the active component vanadium oxide can generate an agglomeration phenomenon to cause pore channel blockage and active sites to be covered, so that the denitration activity of the catalyst is reduced due to insufficient active sites;
the preparation method of the low-temperature CO reduction denitration V/AC catalyst comprises the following specific steps:
(1) adding coconut shell activated carbon into deionized water, performing ultrasonic treatment for 2-3 h at the temperature of 60-80 ℃, filtering, drying, then adding into a nitric acid solution, activating for 2-3 h at the temperature of 60-80 ℃, washing to be neutral by using deionized water, and performing forced air drying to obtain an activated carbon carrier AC;
(2) adding the activated carbon carrier AC obtained in the step (1) into VOSO4Dipping in the solution, performing ultrasonic treatment at the temperature of 60-80 ℃ for 2-3 h, performing solid-liquid separation, and drying the solid at the temperature of 100-110 ℃ for 12-24 h in an air atmosphere to obtain a V/AC catalyst precursor;
(3) and (3) under the protection of nitrogen, roasting the V/AC catalyst precursor in the step (2) at the temperature of 450-550 ℃ for 4-5 h to obtain the low-temperature CO reduction denitration V/AC catalyst.
The concentration of the nitric acid solution in the step (1) is 3-4 mol/L.
Based on the mass of the activated carbon carrier AC as 100 percent, the method comprises the following steps(2)VOSO4The mass fraction of the medium V element is 5-15%.
The catalyst is used as a low-temperature catalyst for denitration of NO in flue gasxThe application of (1): CO is used as a reducing agent, and the catalysis temperature is 100-220 ℃; CO is used as reducing gas, and the problem of NH which is a traditional reducing agent can be solved3The problem of easy escape.
The coconut shell activated carbon is activated by nitric acid, so that the surface functional groups of the coconut shell activated carbon can be greatly improved, the specific surface area is increased, and the pore volume and the pore diameter in the activated carbon are improved; the ultrasonic impregnation method can effectively ensure the dispersibility of the vanadium element on the surface of the catalyst and effectively reduce the clustering phenomenon of the vanadium oxide, thereby ensuring the characteristics of high denitration activity, good nitrogen selectivity and the like; adding the impregnated activated carbon in N2Roasting under the protection of atmosphere to convert the vanadyl sulfate precursor into pentavalent vanadium-based oxide.
The invention has the beneficial effects that:
(1) the invention takes cheap coconut shell activated carbon as a carrier and pentavalent vanadium as a main oxide as an active component to realize the reaction of NO under the low-temperature condition by taking CO as a reducing agentxRemoving; can solve the problem of NH in the prior flue gas denitration3The SCR catalyst has the problems of low denitration rate, easy blockage of pore channels, easy poisoning and the like under the low-temperature condition;
(2) the low-temperature CO reduction denitration V/AC catalyst has high denitration efficiency and good nitrogen selectivity, and NO is at the catalytic temperature of 100-220 DEG CxThe conversion rate of the catalyst can reach 99.3 percent;
(3) the method adopts nitric acid to activate the coconut shell activated carbon, improves the surface active functional groups of the coconut shell activated carbon, increases the specific surface area and improves the pore volume and pore diameter in the activated carbon; the active components of the AC carrier are activated by a nitric acid method and ultrasonically dipped, so that the dispersity of the vanadium oxide on the surface of the V/AC catalyst can be greatly improved;
(4) the invention adopts CO to replace the traditional NH3As a reducing gas, NH can be solved3Easy escape, pipeline blockage, environmental pollution and the like, and can also avoid NH3With SO in flue gas3The ammonium sulfate generated by the reaction corrodes downstream equipment, and the like.
Drawings
FIG. 1 is a SEM image of the V-supported catalyst (5V/AC) of example 1;
FIG. 2 is a SEM image of the V-supported catalyst (10V/AC) of example 2;
FIG. 3 is a SEM image of the V-supported catalyst (15V/AC) of example 3;
FIG. 4 is an XRD pattern of catalysts of different V loadings;
FIG. 5 is a graph of FTIR for catalysts of different V loadings;
FIG. 6 is a graph of denitration rates for catalysts with different V loadings.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: the low-temperature CO reduction denitration V/AC catalyst comprises a coconut shell activated carbon carrier activated by nitric acid and a V oxide active component, wherein the mass ratio of a V element in the V/AC catalyst to coconut shell activated carbon is 5%, the V/AC catalyst is marked as 5V/AC, and the particle size of the coconut shell activated carbon carrier is 20-40 meshes;
a preparation method of a low-temperature CO reduction denitration V/AC catalyst comprises the following specific steps:
(1) adding coconut shell activated carbon into deionized water, performing ultrasonic treatment at 80 ℃ for 2h, filtering, drying, adding into nitric acid solution, activating at 80 ℃ for 2h, washing with deionized water to neutrality, and air-blast drying to obtain activated carbon carrier AC;
(2) adding the activated carbon carrier AC obtained in the step (1) into VOSO4Soaking in the solution in the same volume, performing ultrasonic treatment at 80 ℃ for 2h, performing solid-liquid separation, and drying the solid at 100 ℃ for 24h in an air atmosphere to obtain a V/AC catalyst precursor; wherein the concentration of the vanadyl sulfate solution is 0.990 mol/L;
(3) under the protection of nitrogen, heating the V/AC catalyst precursor in the step (2) at a heating rate of 15 ℃/min to 550 ℃ and roasting for 4h to obtain a low-temperature CO reduction denitration V/AC catalyst;
the SEM characterization of the 5V/AC catalyst in this example is shown in fig. 1, and it can be seen that the activated carbon still maintains the pore size structure after loading 5% V, and the V oxide is in the form of blocks with different sizes and is attached to the surface of the activated carbon substrate;
the specific surface area, pore volume and pore diameter parameters of the 5V/AC catalyst in the example are shown in Table 1, and it can be seen from Table 1 that the pore diameter of the 5V/AC catalyst is approximately microporous, and the larger specific surface area is favorable for the adsorption of the catalyst to gas;
the XRD characterization of the 5V/AC catalyst of this example is shown in FIG. 4, and V oxide can be observed on the surface of the 5V/AC catalyst, and the analysis shows that: VOSO4Interaction of the precursor with the AC surface functional group to convert V+The V oxide is easy to migrate into the AC hole, the aggregation growth of the V oxide on the AC surface is slowed down, and the dispersibility of the active component of the V oxide on the AC is improved; the peaks at all angles are not sharp, which shows that the dispersibility of the V oxide in the AC load is good, and the V oxide plays a role in promoting the denitration reaction;
FTIR characterization of the 5V/AC catalyst of this example is shown in FIG. 5, where the 5V/AC catalyst is 3415.71cm-1Is located at 1017.34cm, and is the absorption peak of O-H stretching vibration in carboxyl and chemical adsorption water-1The absorption peak is a lactone group asymmetric vibration absorption peak, and meanwhile, a small amount of nitrogen-containing functional groups are found in FTIR characterization;
the 5V/AC catalyst prepared in the embodiment is placed in a fixed bed denitration reactor, denitration is carried out within the range of 100-220 ℃, and the loading amount of the catalyst is 4 g; n is used before the denitration experiment is started2Introducing into a fixed bed reactor for in-situ flushing, and discharging other gases in the reactor;
setting simulated smoke: NO 2.4ml/min, CO 16ml/min, O260ml/min, the balance gas is N 2500 ml/min; mixing and feeding into a fixed bed reactor, and reducing NO into N by CO under the action of a catalyst2(ii) a The gas after reaction is discharged into the atmosphere after the unreacted gas is absorbed by the alkaline solution; NO at inlet and outlet of fixed bed reactor evaluation devicexThe concentration is detected by a TESTO-340 flue gas analyzer of German Degraph instruments, and the denitration conversion rate is calculated by adopting the following formula:
in the formula, CinIs the gas inlet NOxConcentration, ppm; coutIs the gas outlet NOxConcentration, ppm.
The denitration rate curve of the 5V/AC catalyst is shown in figure 6 within the range of 100-220 ℃, and the 5V/AC catalyst has higher denitration rate under the condition of lower temperature of 100 ℃. The denitration rate curve of the 5V/AC catalyst is gradually reduced along with the increase of the temperature until 220 ℃ because the dosage of the catalyst is only 4 g.
Example 2: the low-temperature CO reduction denitration V/AC catalyst comprises a coconut shell activated carbon carrier activated by nitric acid and a V oxide active component, wherein the mass ratio of a V element in the V/AC catalyst to coconut shell activated carbon is 10%, the V/AC catalyst is marked as 10V/AC, and the particle size of the coconut shell activated carbon carrier is 20-40 meshes;
a preparation method of a low-temperature CO reduction denitration V/AC catalyst comprises the following specific steps:
(1) adding coconut shell activated carbon into deionized water, performing ultrasonic treatment at 75 ℃ for 2.5h, filtering, drying, adding into nitric acid solution, activating at 75 ℃ for 2.5h, washing with deionized water to neutrality, and air-drying to obtain activated carbon carrier AC;
(2) adding the activated carbon carrier AC obtained in the step (1) into VOSO4Soaking in the solution in the same volume, performing ultrasonic treatment at 75 ℃ for 2.5h, performing solid-liquid separation, and drying the solid at 105 ℃ for 18h in an air atmosphere to obtain a V/AC catalyst precursor; wherein the concentration of the vanadyl sulfate solution is 1.98 mol/mL;
(3) under the protection of nitrogen, heating the V/AC catalyst precursor in the step (2) at a heating rate of 12 ℃/min to 500 ℃ and roasting for 4.5h to obtain a low-temperature CO reduction denitration V/AC catalyst;
in the present example, the SEM characterization of the 10V/AC catalyst is shown in fig. 2, and after loading 10% V, a large block of V oxide is attached to the surface of the activated carbon matrix, and the activated carbon matrix remains unchanged;
the specific surface area, pore volume and pore diameter parameters of the 10V/AC catalyst of the present example are shown in Table 1, and it can be seen from Table 1 that the specific surface area and pore volume of the 10V/AC catalyst are all increased compared with the 5V/AC catalyst; the V oxide constructs more new structures along with the increase of the loading capacity, and the adsorption active sites are increased, so that the adsorption capacity of the catalyst on gas is facilitated;
the XRD characterization of the 10V/AC catalyst of this example is shown in fig. 4, and it can be seen from fig. 4 that V oxide can be observed on the surface of the 10V/AC catalyst, and the dispersibility of V oxide supported on the AC surface is better, so that it plays a role in promoting the denitration reaction;
the FTIR characterization of the 10V/AC catalyst of this example is shown in FIG. 5. from FIG. 5, it can be seen that the 10V/AC catalyst is 3415.82cm-1Is located at 1018.72cm, and is the absorption peak of O-H stretching vibration in carboxyl and chemical adsorption water-1The position is a lactone group asymmetric vibration absorption peak; meanwhile, a small amount of nitrogen-containing functional groups were also found in the FTIR characterization;
the 10V/AC catalyst prepared in the embodiment is placed in a fixed bed denitration reactor, denitration is carried out within the range of 100-220 ℃, and the loading amount of the catalyst is 4 g; n is used before the denitration experiment is started2Introducing the mixture into a fixed bed reactor for in-situ flushing, and discharging other gas interference in the reactor;
setting a simulated flue gas component and denitration rate calculation method as in example 1, wherein a denitration rate curve of the 10V/AC catalyst is shown in FIG. 6 within a temperature range of 100-220 ℃, and as can be seen from FIG. 6, the 10V/AC catalyst has a higher denitration rate at a lower temperature of 100 ℃; the denitration rate of the catalyst is higher than that of a 5V/AC catalyst at each temperature within the range of 100-220 ℃.
Example 3: the low-temperature CO reduction denitration V/AC catalyst comprises a coconut shell activated carbon carrier activated by nitric acid and a V oxide active component, wherein the mass ratio of a V element in the V/AC catalyst to coconut shell activated carbon is 15%, the V/AC catalyst is marked as 15V/AC, and the particle size of the coconut shell activated carbon carrier is 20-40 meshes;
a preparation method of a low-temperature CO reduction denitration V/AC catalyst comprises the following specific steps:
(1) adding coconut shell activated carbon into deionized water, performing ultrasonic treatment at 60 ℃ for 3h, filtering, drying, adding into a nitric acid solution, activating at 60 ℃ for 3h, washing with deionized water to neutrality, and drying by air blast to obtain an activated carbon carrier AC;
(2) adding the activated carbon carrier AC obtained in the step (1) into VOSO4Soaking in the solution in the same volume, performing ultrasonic treatment at 60 ℃ for 3h, performing solid-liquid separation, and drying the solid at 110 ℃ for 12h in an air atmosphere to obtain a V/AC catalyst precursor; wherein the concentration of the vanadyl sulfate solution is 2.97 mol/mL;
(3) under the protection of nitrogen, heating the V/AC catalyst precursor in the step (2) at a heating rate of 10 ℃/min to 450 ℃ and roasting for 5h to obtain a low-temperature CO reduction denitration V/AC catalyst;
the SEM representation of the 15V/AC catalyst in the example is shown in FIG. 3, and the surface tissue structure of the activated carbon matrix is covered after 15% of V is loaded, but the activated carbon matrix is kept unchanged;
the specific surface area, pore volume and pore diameter parameters of the 15V/AC catalyst of the embodiment are shown in Table 1,
TABLE 1V/AC catalyst pore parameters
| Catalyst numbering | Specific surface area (m)2/g) | Pore volume (cm)3/g) | Pore size (nm) |
| 5V/AC | 600.626 | 0.315 | 2.100 |
| 10V/AC | 678.011 | 0.344 | 2.029 |
| 15V/AC | 669.383 | 0.337 | 2.014 |
As can be seen from Table 1, the specific surface area and pore volume of the 15V/AC catalyst were both reduced compared to the 10V/AC catalyst, but increased compared to the 5V/AC catalyst. When the V loading reaches 15%, the V metal oxide covers the surface pore structure of the activated carbon, so that the value of the pore structure parameter is reduced, and the gas adsorption capacity of the activated carbon is reduced to a certain extent;
the XRD characterization of the 15V/AC catalyst of this example is shown in fig. 4, and it can be seen from fig. 4 that V oxide can be observed on the surface of the 15V/AC catalyst, and the V oxide has good dispersibility on the AC surface and also has a promoting effect on the denitration reaction;
FTIR characterization of the 15V/AC catalyst of this example is shown in FIG. 5. from FIG. 5, it can be seen that the 15V/AC catalyst is 3415.00cm-1Is located at 1018.43cm, and is the absorption peak of O-H stretching vibration in carboxyl and chemical adsorption water-1The position is a lactone group asymmetric vibration absorption peak;
placing the 15V/AC catalyst prepared in the embodiment in a fixed bed denitration reactor, and carrying out denitration at the temperature of 100-220 ℃, wherein the loading amount of the catalyst is 4 g; n is used before the denitration experiment is started2Introducing into a fixed bed reactor for in-situ flushing, and discharging other gases in the reactor;
the simulated flue gas components and the denitration rate calculation method are set in the same way as in example 1, the denitration rate curve of the 15V/AC catalyst is shown in FIG. 6 within the range of 100-220 ℃, and as can be seen from FIG. 6, the 15V/AC catalyst has a high denitration rate under the condition of a low temperature of 100 ℃. The denitration rate of the catalyst is lower than that of a 10V/AC catalyst under each temperature condition of 15V/AC within the temperature range of 100-220 ℃, but higher than that of a 5V/AC catalyst.
While the present invention has been described in detail with reference to the specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (6)
1. A low-temperature CO reduction denitration V/AC catalyst is characterized in that: the catalyst comprises a nitric acid activated coconut shell activated carbon carrier and a vanadium oxide active component, wherein the mass ratio of vanadium element to coconut shell activated carbon is 5-15%; and (3) carrying out low-temperature catalytic CO reduction denitration by using a V/AC catalyst.
2. The preparation method of the low-temperature CO reduction denitration V/AC catalyst disclosed by claim 1 is characterized by comprising the following specific steps of:
(1) adding coconut shell activated carbon into deionized water, performing ultrasonic treatment for 2-3 h at the temperature of 60-80 ℃, filtering, drying, then adding into a nitric acid solution, activating for 2-3 h at the temperature of 60-80 ℃, washing to be neutral by using deionized water, and performing forced air drying to obtain an activated carbon carrier AC;
(2) adding the activated carbon carrier AC obtained in the step (1) into VOSO4Dipping in the solution, performing ultrasonic treatment at the temperature of 60-80 ℃ for 2-3 h, performing solid-liquid separation, and drying the solid at the temperature of 100-105 ℃ for 12-24 h in an air atmosphere to obtain a V/AC catalyst precursor;
(3) and (3) under the protection of nitrogen, roasting the V/AC catalyst precursor in the step (2) at the temperature of 450-550 ℃ for 4-5 h to obtain the low-temperature CO reduction denitration V/AC catalyst.
3. The preparation method of the low-temperature CO reduction denitration V/AC catalyst according to claim 2, characterized by comprising the following steps: the concentration of the nitric acid solution in the step (1) is 3-4 mol/L.
4. The preparation method of the low-temperature CO reduction denitration V/AC catalyst according to claim 2, characterized by comprising the following steps: to move aboutThe mass of the charcoal carrier AC is 100 percent, and the step (2) is VOSO4The mass fraction of the medium V element is 5-15%.
5. The catalyst prepared by the method of claims 1-4 is used as a low-temperature catalyst in flue gas denitration.
6. Use according to claim 5, characterized in that: CO is used as a reducing agent, and the catalysis temperature is 100-220 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110517938.0A CN113198444A (en) | 2021-05-12 | 2021-05-12 | Low-temperature CO reduction denitration V/AC catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110517938.0A CN113198444A (en) | 2021-05-12 | 2021-05-12 | Low-temperature CO reduction denitration V/AC catalyst and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113198444A true CN113198444A (en) | 2021-08-03 |
Family
ID=77030906
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110517938.0A Pending CN113198444A (en) | 2021-05-12 | 2021-05-12 | Low-temperature CO reduction denitration V/AC catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113198444A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3727643A1 (en) * | 1987-08-19 | 1989-03-02 | Bayer Ag | METHOD FOR REDUCING NITROGEN OXIDS FROM EXHAUST GASES |
| CN101259408A (en) * | 2008-04-15 | 2008-09-10 | 中国科学院山西煤炭化学研究所 | Catalyst for removing flue gas NOx under low temperature and preparation and application |
| CN101391178A (en) * | 2008-10-24 | 2009-03-25 | 中国科学院山西煤炭化学研究所 | Method for removing mercury in flue gas using V2O5/carbon material catalyst |
| CN106345453A (en) * | 2016-08-26 | 2017-01-25 | 成都国化环保科技有限公司 | Carbon-based material low-temperature denitrification catalyst and preparation method thereof |
| CN108283883A (en) * | 2017-01-09 | 2018-07-17 | 青州日新特种材料有限公司 | NO in a kind of removing flue gasxMethod |
| CN108379983A (en) * | 2018-03-20 | 2018-08-10 | 燕山大学 | A kind of biomass incinerator exhaust gas treating method |
| CN112316946A (en) * | 2020-11-06 | 2021-02-05 | 昆明理工大学 | Low-temperature CO-SCR denitration Cu-Ni/AC catalyst and preparation method thereof |
| CN112316943A (en) * | 2020-11-13 | 2021-02-05 | 昆明理工大学 | Low-temperature CO-SCR denitration Cu2O/AC catalyst, preparation method and application thereof |
| CN112403488A (en) * | 2020-12-16 | 2021-02-26 | 南京师范大学 | Low-sulfur-resistant low-temperature carbon-based denitration catalyst and preparation method and application thereof |
-
2021
- 2021-05-12 CN CN202110517938.0A patent/CN113198444A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3727643A1 (en) * | 1987-08-19 | 1989-03-02 | Bayer Ag | METHOD FOR REDUCING NITROGEN OXIDS FROM EXHAUST GASES |
| US4910005A (en) * | 1987-08-19 | 1990-03-20 | Bayer Aktiengesellschaft | Process for the reduction of nitrogen oxides from exhaust gases |
| CN101259408A (en) * | 2008-04-15 | 2008-09-10 | 中国科学院山西煤炭化学研究所 | Catalyst for removing flue gas NOx under low temperature and preparation and application |
| CN101391178A (en) * | 2008-10-24 | 2009-03-25 | 中国科学院山西煤炭化学研究所 | Method for removing mercury in flue gas using V2O5/carbon material catalyst |
| CN106345453A (en) * | 2016-08-26 | 2017-01-25 | 成都国化环保科技有限公司 | Carbon-based material low-temperature denitrification catalyst and preparation method thereof |
| CN108283883A (en) * | 2017-01-09 | 2018-07-17 | 青州日新特种材料有限公司 | NO in a kind of removing flue gasxMethod |
| CN108379983A (en) * | 2018-03-20 | 2018-08-10 | 燕山大学 | A kind of biomass incinerator exhaust gas treating method |
| CN112316946A (en) * | 2020-11-06 | 2021-02-05 | 昆明理工大学 | Low-temperature CO-SCR denitration Cu-Ni/AC catalyst and preparation method thereof |
| CN112316943A (en) * | 2020-11-13 | 2021-02-05 | 昆明理工大学 | Low-temperature CO-SCR denitration Cu2O/AC catalyst, preparation method and application thereof |
| CN112403488A (en) * | 2020-12-16 | 2021-02-26 | 南京师范大学 | Low-sulfur-resistant low-temperature carbon-based denitration catalyst and preparation method and application thereof |
Non-Patent Citations (6)
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11331657B2 (en) | Method of preparing catalyst for low-temperature synergistic catalytic purification of NOx and HCN in flue gas, and use thereof | |
| CN101352681B (en) | Low-temperature SCR catalyst using nitrogen-dopped activated carbon as carrier and preparation technique thereof | |
| CN101856587B (en) | Fluidized activated carbon combined desulfurization and denitrification process | |
| CN101810996B (en) | Method for producing ammonium sulfate and ammonium nitrate by simultaneously desulfurizing and denitrating ammonia water and cobaltic ethylenediamine (II) | |
| CN110372875B (en) | Heteronuclear polymetallic organic framework material and preparation and application thereof in denitration and demercuration | |
| CN105032403A (en) | Catalyst used for low temperature desulphurization and denitration of flue gas and preparation method thereof | |
| CN102407113A (en) | Microwave catalyst and application method thereof | |
| CN112316946A (en) | Low-temperature CO-SCR denitration Cu-Ni/AC catalyst and preparation method thereof | |
| CN102151585B (en) | Melamine-supported denitration catalyst and preparation method thereof | |
| CN102335604A (en) | SCR (selective catalyctic reduction) low-temperature denitrification catalyst with nano core-shell structure and preparation method thereof | |
| CN112371126A (en) | Low-temperature CO-SCR denitration Cu-Fe/AC catalyst and preparation method and application thereof | |
| CN112316943A (en) | Low-temperature CO-SCR denitration Cu2O/AC catalyst, preparation method and application thereof | |
| CN113198484A (en) | Low-temperature CO-SCR denitration Fe-Ce/AC catalyst and preparation method and application thereof | |
| CN101428237A (en) | Urea supported carbon based denitration catalyst, preparation and application method thereof | |
| CN111097288A (en) | Low-temperature dry desulfurization-catalytic denitration integrated process and equipment | |
| CN103506121A (en) | Low-temperature denitration catalyst with iron loaded on carbon nanotube and preparation method thereof | |
| CN112718018B (en) | Lanthanum cobaltite perovskite catalyst treated by acetic acid and preparation method thereof | |
| CN106732547B (en) | Demercuration catalyst for low-temperature oxidation of zero-valent mercury in coal-fired flue gas and preparation method thereof | |
| CN111054209B (en) | Low-temperature SCR denitration process based on ethylene reducing agent | |
| CN108579756A (en) | One main laminaria shape Mn-Fe bimetallic oxide load Cs eO2Catalyst and preparation method and application | |
| CN113198444A (en) | Low-temperature CO reduction denitration V/AC catalyst and preparation method and application thereof | |
| CN111921523B (en) | Medium-low temperature SCO denitration catalyst and preparation method thereof | |
| CN210905625U (en) | Particle coke catalytic denitration efficiency improving device based on advanced oxidation method | |
| CN114471559B (en) | Cu/AC catalyst for CO-SCR denitration and Zn poisoning resistance as well as preparation method and application thereof | |
| CN107088361B (en) | Low-temperature water-dropping absorption type catalytic denitration method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210803 |
|
| RJ01 | Rejection of invention patent application after publication |