CN112108155A - Preparation method of integral manganese oxide nitric oxide catalyst, product and application thereof - Google Patents
Preparation method of integral manganese oxide nitric oxide catalyst, product and application thereof Download PDFInfo
- Publication number
- CN112108155A CN112108155A CN202011116948.5A CN202011116948A CN112108155A CN 112108155 A CN112108155 A CN 112108155A CN 202011116948 A CN202011116948 A CN 202011116948A CN 112108155 A CN112108155 A CN 112108155A
- Authority
- CN
- China
- Prior art keywords
- electrode
- solution
- nickel
- manganese
- stirring
- 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
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 96
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 78
- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000151 deposition Methods 0.000 claims abstract description 35
- 230000008021 deposition Effects 0.000 claims abstract description 35
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 33
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000004070 electrodeposition Methods 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 150000002500 ions Chemical class 0.000 claims abstract description 11
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 172
- 229910052759 nickel Inorganic materials 0.000 claims description 86
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 64
- 239000006260 foam Substances 0.000 claims description 58
- 229910052697 platinum Inorganic materials 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 32
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 31
- 229940075397 calomel Drugs 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 22
- 229940071125 manganese acetate Drugs 0.000 claims description 20
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 18
- 238000000746 purification Methods 0.000 claims description 18
- 239000011572 manganese Substances 0.000 claims description 13
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000005520 cutting process Methods 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 10
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 150000002697 manganese compounds Chemical class 0.000 claims description 6
- 235000011056 potassium acetate Nutrition 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 5
- 239000001639 calcium acetate Substances 0.000 claims description 5
- 235000011092 calcium acetate Nutrition 0.000 claims description 5
- 229960005147 calcium acetate Drugs 0.000 claims description 5
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 5
- 239000011654 magnesium acetate Substances 0.000 claims description 5
- 235000011285 magnesium acetate Nutrition 0.000 claims description 5
- 229940069446 magnesium acetate Drugs 0.000 claims description 5
- 239000001632 sodium acetate Substances 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- -1 manganese acetate compound Chemical class 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 34
- 239000007789 gas Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229960004109 potassium acetate Drugs 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229960004249 sodium acetate Drugs 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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
- 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
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Physics & Mathematics (AREA)
- Electrochemistry (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of an integral ion-doped manganese oxide nitric oxide catalyst, a product and application thereof. The pH value of the precursor solution is adjusted by ammonia water, the deposition rate of the catalyst is improved, the falling rate is reduced by the interaction between the active component growing in situ and the carrier, the stability of the catalyst is improved, the adopted electrochemical deposition method is simple and easy to operate, the appearance and the performance of the catalyst are easily changed by changing preparation parameters, and the stability of the catalyst is improved by adding doping ions.
Description
Technical Field
The invention relates to a preparation method of an integral catalyst, in particular to a preparation method of an integral ion-doped manganese oxide nitric oxide catalyst, a product and an application thereof, and specifically relates to an ion-doped manganese-based integral nitric oxide purification catalyst and a preparation method thereof.
Background
The industry is an important content of the modernization and an important driving force for promoting the modernization, and plays an important role in national economy. However, in industrial production, many environmental problems are generated, and the environmental problems seriously affect the production and life of people, so how to effectively reduce the environmental pollution in the industrial production process becomes a problem to be solved.
Nitric oxide and nitrogen dioxide are air pollutants mainly generated in industrial production, and nitrogen oxides can cause photochemical smog, greenhouse effect, ozone damage and other environmental problems, and are toxic and harmful to human health, so that the elimination of nitrogen oxides is very necessary. Nitrogen dioxide or other nitrogen oxides, which are readily absorbed by alkaline solutions, are effective methods for reducing nitrogen oxides using catalysts.
The traditional catalyst is mostly in powder or particle shape, active sites on the surface of a catalytic material are easily covered due to the aggregation state of powder, and the activity of the catalyst is reduced due to the aggregation of the material, while the monolithic catalyst combines the catalytic active material with a carrier, so that the problems of low utilization efficiency, difficult recovery and the like of the powder catalyst are effectively solved, and the monolithic catalyst is combined with the carrier and is not easily aggregated in the reaction process, so that the monolithic catalyst becomes one of the most potential research directions in the current heterogeneous catalysis field.
The preparation method of the monolithic catalyst comprises the following steps: the electrochemical deposition method adopted by the invention is in-situ growth preparation, the preparation process is simple and easy to operate, the morphology of the catalyst and the binding force between the catalyst and a carrier are easily changed by changing preparation parameters, and the like, and the electrochemical deposition method has considerable advantages as a novel preparation method.
Disclosure of Invention
The invention aims to provide a preparation method of an integral ion-doped manganese oxide nitric oxide catalyst.
Yet another object of the present invention is to: provides a monolithic ion-doped manganese oxide nitric oxide catalyst product prepared by the method.
Yet another object of the present invention is to: provides an application of the product.
The purpose of the invention is realized by the following scheme: a preparation method of an integral ion-doped manganese oxide nitric oxide catalyst utilizes an electrodeposition method, takes manganese acetate and different ions as a precursor solution, and in-situ grows active component manganese oxide on an integral foam nickel substrate, and comprises the following steps:
(1) cutting the foamed nickel into a rectangle of 1cm multiplied by 5 cm;
(2) mixing ammonia water and ultrapure water according to a volume ratio of 1:9 to prepare dilute ammonia water;
(3) dissolving manganese acetate in deionized water, preparing 0.2M manganese compound solution, stirring for 30 minutes on a magnetic stirrer, then respectively adding potassium acetate, sodium acetate, magnesium acetate and/or calcium acetate to enable the concentration of doped ions in the solution to be 0.1M, then stirring for 30 minutes, dropwise adding 1ml of dilute ammonia water obtained in the second step, and stirring for 60 minutes again to obtain solution A;
(4) putting 40ml of the solution A into a small beaker, respectively connecting a platinum electrode and a calomel electrode with a counter electrode and a reference electrode of an electrochemical workstation, and connecting the cut foam nickel with a working electrode;
(5) simultaneously immersing a foamed nickel electrode, a platinum electrode and a calomel electrode into a small beaker filled with the solution A, setting the deposition voltage to be 1.5V and the deposition time to be 600s by adopting a constant-voltage electrodeposition method, and starting deposition;
(6) taking off the foam nickel deposited with manganese, placing the foam nickel in a glass dish, and drying the foam nickel in a drying oven at 70 ℃ for 12 hours;
(7) and (3) putting the dried foam nickel into a muffle furnace, roasting for 4 hours at the temperature of 300 ℃, wherein the heating rate is 2 ℃/min, and thus obtaining the integral manganese oxide nitric oxide purification catalyst.
The invention also provides an integral ion-doped manganese oxide nitric oxide catalyst prepared by the method.
The invention also provides an application of the integral ion-doped manganese oxide nitric oxide catalyst as a catalyst in nitric oxide purification.
The integral ion-doped manganese oxide nitric oxide catalyst is tested for nitric oxide purification performance in a fixed bed device under the following test conditions: the total flow of gas is 300ml/min, the reaction is carried out at a constant temperature of 50 ℃, the initial concentration of NO is 10ppm, the rest is zero gas, the dosage of the catalyst is 0.1g, and the effect is excellent.
By utilizing an electrodeposition method, manganese acetate is taken as a precursor, potassium acetate, calcium acetate, magnesium acetate and sodium acetate are taken as doping elements, and an active component manganese oxide grows in situ on an integral foam nickel substrate. The pH value of the precursor solution is adjusted by ammonia water, the deposition rate of the catalyst is improved, the falling rate is reduced by the interaction between the active component growing in situ and the carrier, the stability of the catalyst is improved, the adopted electrochemical deposition method is simple and easy to operate, the appearance and the performance of the catalyst are easily changed by changing preparation parameters, and the stability of the catalyst is improved by adding doping ions. The monolithic manganese oxide nitric oxide catalyst obtained by the method has the characteristics of low shedding rate, good activity, easiness in preparation and the like, and has a good application prospect.
The invention has the following advantages:
1. the used materials are manganese and nickel, while the common catalyst is noble metal elements such as platinum, palladium and the like, so that the cost is reduced, and the industrial scale production is improved.
2. Compared with the original codeposition and hydrothermal methods, the preparation method is an electrodeposition method, and the morphology, the performance and the like of the catalyst can be controlled more easily by controlling preparation parameters.
3. The ammonia water is added into the precursor solution, which is beneficial to the generation of intermediate products, thereby improving the deposition rate of manganese.
4. The doping ions are added, so that the electrochemical deposition efficiency is improved, the time cost is saved, the appearance and the particle size of the catalyst are changed by doping the ions, and the performance of the catalyst is improved.
5. The integral catalyst has higher mass transfer efficiency, low bed pressure and better mechanical property.
Detailed Description
The following examples illustrate the invention in detail: the present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments.
Example 1:
an integral ion-doped manganese oxide nitric oxide catalyst is prepared by an electrodeposition method, wherein manganese acetate and different ions are mixed to serve as a precursor solution, and an active component manganese oxide grows in situ on an integral foam nickel substrate, and the method comprises the following steps:
(1) cutting the foamed nickel into a rectangle of 1cm multiplied by 5 cm;
(2) mixing ammonia water and ultrapure water according to a volume ratio of 1:9 to prepare dilute ammonia water;
(3) measuring 40ml of 0.2M manganese acetate in a 50ml beaker, stirring for 30 minutes, then adding 0.1M potassium acetate, stirring for 30 minutes, dropwise adding 1ml of dilute ammonia water in the second step, stirring for 60 minutes again, and marking as a solution A;
(4) putting 40ml of the solution A into a 50ml small beaker, respectively connecting a platinum electrode and a calomel electrode with a counter electrode and a reference electrode of an electrochemical workstation, and connecting the cut foam nickel with a working electrode;
(5) simultaneously immersing the foamed nickel, the platinum electrode and the calomel electrode into a small beaker filled with the solution A, keeping the heights of the foamed nickel, the platinum electrode and the calomel electrode uniform, setting the deposition voltage to be 1.5V and the deposition time to be 600s by adopting a constant-voltage electrodeposition method, and starting deposition;
(6) taking off the foam nickel deposited with manganese, placing the foam nickel in a glass dish, and drying the foam nickel in a drying oven at 70 ℃ for 12 hours;
(7) and (3) putting the dried foam nickel into a muffle furnace, roasting for 4 hours at the temperature of 300 ℃, wherein the heating rate is 2 ℃/min, and the integral manganese oxide nitric oxide purification catalyst is marked as Mn/NF-K.
Example 2:
a monolithic ion-doped manganese oxide nitric oxide catalyst is prepared by the following steps in the same way as the step of the example 1:
(1) cutting the foamed nickel into a rectangle of 1cm multiplied by 5 cm;
(2) mixing ammonia water and ultrapure water according to a volume ratio of 1:9 to prepare dilute ammonia water;
(3) measuring 40ml of 0.2M manganese acetate precursor solution into a 50ml beaker, stirring for 30 minutes to dissolve manganese acetate into deionized water, stirring the manganese acetate compound solution prepared into 0.2M manganese compound solution on a magnetic stirrer for 30 minutes, then adding 0.1M calcium acetate solution to ensure that the concentration of doped ions is equal to the middle concentration, stirring for 30 minutes, dropwise adding 1ml of dilute ammonia water obtained in the second step, and stirring for 60 minutes again to obtain solution A;
(4) putting 40ml of the solution A into a 50ml small beaker, respectively connecting a platinum electrode and a calomel electrode with a counter electrode and a reference electrode of an electrochemical workstation, and connecting the cut foam nickel with a working electrode;
(5) simultaneously immersing the foamed nickel, the platinum electrode and the calomel electrode into a small beaker filled with the solution A, keeping the heights of the foamed nickel, the platinum electrode and the calomel electrode uniform, setting the deposition voltage to be 1.5V and the deposition time to be 600s by adopting a constant-voltage electrodeposition method, and starting deposition;
(6) taking off the foam nickel deposited with manganese, placing the foam nickel in a glass dish, and drying the foam nickel in a drying oven at 70 ℃ for 12 hours;
(7) and (3) putting the dried foamed nickel into a muffle furnace, roasting for 4 hours at the temperature of 300 ℃, wherein the heating rate is 2 ℃/min, and the integral manganese oxide nitric oxide purification catalyst is marked as Mn/NF-Ca.
Example 3:
a monolithic ion-doped manganese oxide nitric oxide catalyst is prepared by the following steps in the same way as the step of the example 1:
(1) cutting the foamed nickel into a rectangle of 1cm multiplied by 5 cm;
(2) mixing ammonia water and ultrapure water according to a volume ratio of 1:9 to prepare dilute ammonia water;
(3) measuring 40ml of manganese acetate precursor solution in a 50ml beaker, stirring for 30 minutes, then adding 0.1M magnesium acetate, stirring for 30 minutes, dropwise adding 1ml of dilute ammonia water in the second step, and stirring for 60 minutes again to obtain solution A;
(4) putting 40ml of the solution A into a 50ml small beaker, respectively connecting a platinum electrode and a calomel electrode with a counter electrode and a reference electrode of an electrochemical workstation, and connecting the cut foam nickel with a working electrode;
(5) simultaneously immersing the connected nickel foam, the platinum electrode and the calomel electrode into a small beaker filled with the solution A, keeping the heights of the nickel foam, the platinum electrode and the calomel electrode uniform, setting the deposition voltage to be 1.5V and the deposition time to be 600s by adopting a constant-voltage electrodeposition method, and starting deposition;
(6) taking off the foam nickel deposited with manganese, placing the foam nickel in a glass dish, and drying the foam nickel in a drying oven at the temperature of 60 ℃ for 12 hours;
(7) and (3) putting the dried foamed nickel into a muffle furnace, roasting for 4 hours at the temperature of 300 ℃, wherein the heating rate is 2 ℃/min, and the integral manganese oxide nitric oxide purification catalyst is marked as Mn/NF-Mg.
Example 4:
a monolithic ion-doped manganese oxide nitric oxide catalyst is prepared by the following steps in the same way as the step of the example 1:
(1) cutting the foamed nickel into a rectangle of 1cm multiplied by 5 cm;
(2) mixing ammonia water and ultrapure water according to a volume ratio of 1:9 to prepare dilute ammonia water;
(3) dissolving manganese acetate in deionized water to prepare a 0.2M manganese compound solution, measuring 40ml of manganese acetate precursor solution in a 50ml beaker, stirring the solution on a magnetic stirrer for 30 minutes, then adding a 0.1M sodium acetate solution, stirring for 30 minutes, dropwise adding 1ml of dilute ammonia water obtained in the second step, and stirring for 60 minutes again to obtain a solution A;
(4) putting 40ml of the solution A into a small beaker, respectively connecting a platinum electrode and a calomel electrode with a counter electrode and a reference electrode of an electrochemical workstation, and connecting the cut foam nickel with a working electrode;
(5) simultaneously immersing the connected nickel foam, the platinum electrode and the calomel electrode into a small beaker filled with the solution A, keeping the heights of the nickel foam, the platinum electrode and the calomel electrode uniform, setting the deposition voltage to be 1.5V and the deposition time to be 600s by adopting a constant-voltage electrodeposition method, and starting deposition;
(6) taking off the foam nickel deposited with manganese, placing the foam nickel in a glass dish, and drying the foam nickel in a drying oven at the temperature of 60 ℃ for 12 hours;
(7) and (3) putting the dried foam nickel into a muffle furnace, roasting for 4 hours at the temperature of 300 ℃, wherein the heating rate is 2 ℃/min, and the integral manganese oxide nitric oxide purification catalyst is marked as Mn/NF-Na.
Comparative example 1:
40ml of the precursor solution (0.2M manganese sulfate) was measured in a 50ml beaker, stirred for 30 minutes, then 0.1M potassium acetate was added, stirred for 30 minutes, then 1ml of dilute ammonia (ammonia: deionized water =1: 9) was added dropwise to the measured solution, and stirred for 60 minutes.
And sequentially connecting the foamed nickel, the platinum electrode and the saturated calomel electrode with a working electrode, a counter electrode and a reference electrode of an electrochemical workstation, then simultaneously putting the connected foamed nickel, platinum electrode and calomel electrode into a 50ml beaker filled with 40ml of manganese precursor solution, and keeping the heights of the foamed nickel, platinum electrode and calomel electrode uniform. Constant voltage electrodeposition is selected, the deposition voltage is set to be 1.5V, and the deposition time is 600 s.
And (3) drying the deposited material in a drying oven at 60 ℃ for 12 hours, and then placing the material in a muffle furnace for roasting, wherein the roasting temperature is 300 ℃, the roasting time is 4 hours, and the heating rate is 2 ℃/min. Obtaining the monolithic manganese oxide nitric oxide catalyst. Is recorded as Mn/NF.
Application example
The monolithic manganese oxide nitric oxide purification catalysts of examples 1-4 and comparative example 1 were used to test their nitric oxide purification performance in a fixed bed apparatus. The test conditions were as follows: the total flow of gas was 300ml/min, the reaction was carried out at a constant temperature of 50 ℃ with an initial concentration of NO of 10ppm and the remainder of zero gas, the amount of catalyst being 0.1 g.
The monolithic manganese oxide nitric oxide purification catalysts of examples 1-4 and comparative example 1 were used to test their nitric oxide purification performance in a fixed bed apparatus. The test conditions were as follows: the total flow of gases was 300ml/min, the reaction was carried out at a constant temperature of 50 ℃, the initial concentration of NO was 10ppm, the remainder was zero gas, the amount of catalyst was 0.1g, and the test results are shown in table 1 below:
Claims (7)
1. a preparation method of an integral ion-doped manganese oxide nitric oxide catalyst is characterized in that manganese acetate and different ions are mixed to serve as a precursor solution by an electrodeposition method, and manganese oxide serving as an active component grows in situ on an integral foam nickel substrate, and comprises the following steps:
(1) cutting the foamed nickel into a rectangle of 1cm multiplied by 5 cm;
(2) mixing ammonia water and ultrapure water according to a volume ratio of 1:9 to prepare dilute ammonia water;
(3) dissolving manganese acetate in deionized water, preparing 0.2M manganese compound solution, stirring for 30 minutes on a magnetic stirrer, then respectively adding potassium acetate, sodium acetate, magnesium acetate and/or calcium acetate to enable the concentration of doped ions in the solution to be 0.1M, then stirring for 30 minutes, dropwise adding 1ml of dilute ammonia water obtained in the second step, and stirring for 60 minutes again to obtain solution A;
(4) putting 40ml of the solution A into a small beaker, respectively connecting a platinum electrode and a calomel electrode with a counter electrode and a reference electrode of an electrochemical workstation, and connecting the cut foam nickel with a working electrode;
(5) simultaneously immersing a foamed nickel electrode, a platinum electrode and a calomel electrode into a small beaker filled with the solution A, setting the deposition voltage to be 1.5V and the deposition time to be 600s by adopting a constant-voltage electrodeposition method, and starting deposition;
(6) taking off the foam nickel deposited with manganese, placing the foam nickel in a glass dish, and drying the foam nickel in a drying oven at 70 ℃ for 12 hours;
(7) and (3) putting the dried foam nickel into a muffle furnace, roasting for 4 hours at the temperature of 300 ℃, wherein the heating rate is 2 ℃/min, and thus obtaining the integral manganese oxide nitric oxide purification catalyst.
2. The method for preparing the monolithic ion-doped manganese oxide nitric oxide catalyst according to claim 1, comprising the following steps:
(1) cutting the foamed nickel into a rectangle of 1cm multiplied by 5 cm;
(2) mixing ammonia water and ultrapure water according to a volume ratio of 1:9 to prepare dilute ammonia water;
(3) measuring 40ml of 0.2M manganese acetate in a 50ml beaker, stirring for 30 minutes, then adding 0.1M potassium acetate, stirring for 30 minutes, dropwise adding 1ml of dilute ammonia water in the second step, stirring for 60 minutes again, and marking as a solution A;
(4) putting 40ml of the solution A into a 50ml small beaker, respectively connecting a platinum electrode and a calomel electrode with a counter electrode and a reference electrode of an electrochemical workstation, and connecting the cut foam nickel with a working electrode;
(5) simultaneously immersing the foamed nickel, the platinum electrode and the calomel electrode into a small beaker filled with the solution A, keeping the heights of the foamed nickel, the platinum electrode and the calomel electrode uniform, setting the deposition voltage to be 1.5V and the deposition time to be 600s by adopting a constant-voltage electrodeposition method, and starting deposition;
(6) taking off the foam nickel deposited with manganese, placing the foam nickel in a glass dish, and drying the foam nickel in a drying oven at 70 ℃ for 12 hours;
(7) and (3) putting the dried foam nickel into a muffle furnace, roasting for 4 hours at the temperature of 300 ℃, wherein the heating rate is 2 ℃/min, and the integral manganese oxide nitric oxide purification catalyst is marked as Mn/NF-K.
3. The method for preparing the monolithic ion-doped manganese oxide nitric oxide catalyst according to claim 1, comprising the following steps:
(1) cutting the foamed nickel into a rectangle of 1cm multiplied by 5 cm;
(2) mixing ammonia water and ultrapure water according to a volume ratio of 1:9 to prepare dilute ammonia water;
(3) measuring 40ml of 0.2M manganese acetate precursor solution into a 50ml beaker, stirring for 30 minutes to dissolve manganese acetate into deionized water, stirring the manganese acetate compound solution prepared into 0.2M manganese compound solution on a magnetic stirrer for 30 minutes, then adding 0.1M calcium acetate solution to ensure that the concentration of doped ions is equal to the middle concentration, stirring for 30 minutes, dropwise adding 1ml of dilute ammonia water obtained in the second step, and stirring for 60 minutes again to obtain solution A;
(4) putting 40ml of the solution A into a 50ml small beaker, respectively connecting a platinum electrode and a calomel electrode with a counter electrode and a reference electrode of an electrochemical workstation, and connecting the cut foam nickel with a working electrode;
(5) simultaneously immersing the foamed nickel, the platinum electrode and the calomel electrode into a small beaker filled with the solution A, keeping the heights of the foamed nickel, the platinum electrode and the calomel electrode uniform, setting the deposition voltage to be 1.5V and the deposition time to be 600s by adopting a constant-voltage electrodeposition method, and starting deposition;
(6) taking off the foam nickel deposited with manganese, placing the foam nickel in a glass dish, and drying the foam nickel in a drying oven at 70 ℃ for 12 hours;
(7) and (3) putting the dried foamed nickel into a muffle furnace, roasting for 4 hours at the temperature of 300 ℃, wherein the heating rate is 2 ℃/min, and the integral manganese oxide nitric oxide purification catalyst is marked as Mn/NF-Ca.
4. The method for preparing the monolithic ion-doped manganese oxide nitric oxide catalyst according to claim 1, comprising the following steps:
(1) cutting the foamed nickel into a rectangle of 1cm multiplied by 5 cm;
(2) mixing ammonia water and ultrapure water according to a volume ratio of 1:9 to prepare dilute ammonia water;
(3) measuring 40ml of manganese acetate precursor solution in a 50ml beaker, stirring for 30 minutes, then adding 0.1M magnesium acetate, stirring for 30 minutes, dropwise adding 1ml of dilute ammonia water in the second step, and stirring for 60 minutes again to obtain solution A;
(4) putting 40ml of the solution A into a 50ml small beaker, respectively connecting a platinum electrode and a calomel electrode with a counter electrode and a reference electrode of an electrochemical workstation, and connecting the cut foam nickel with a working electrode;
(5) simultaneously immersing the connected nickel foam, the platinum electrode and the calomel electrode into a small beaker filled with the solution A, keeping the heights of the nickel foam, the platinum electrode and the calomel electrode uniform, setting the deposition voltage to be 1.5V and the deposition time to be 600s by adopting a constant-voltage electrodeposition method, and starting deposition;
(6) taking off the foam nickel deposited with manganese, placing the foam nickel in a glass dish, and drying the foam nickel in a drying oven at the temperature of 60 ℃ for 12 hours;
(7) and (3) putting the dried foamed nickel into a muffle furnace, roasting for 4 hours at the temperature of 300 ℃, wherein the heating rate is 2 ℃/min, and the integral manganese oxide nitric oxide purification catalyst is marked as Mn/NF-Mg.
5. The method for preparing the monolithic ion-doped manganese oxide nitric oxide catalyst according to claim 1, comprising the following steps:
(1) cutting the foamed nickel into a rectangle of 1cm multiplied by 5 cm;
(2) mixing ammonia water and ultrapure water according to a volume ratio of 1:9 to prepare dilute ammonia water;
(3) dissolving manganese acetate in deionized water to prepare a 0.2M manganese compound solution, measuring 40ml of manganese acetate precursor solution in a 50ml beaker, stirring the solution on a magnetic stirrer for 30 minutes, then adding a 0.1M sodium acetate solution, stirring for 30 minutes, dropwise adding 1ml of dilute ammonia water obtained in the second step, and stirring for 60 minutes again to obtain a solution A;
(4) putting 40ml of the solution A into a small beaker, respectively connecting a platinum electrode and a calomel electrode with a counter electrode and a reference electrode of an electrochemical workstation, and connecting the cut foam nickel with a working electrode;
(5) simultaneously immersing the connected nickel foam, the platinum electrode and the calomel electrode into a small beaker filled with the solution A, keeping the heights of the nickel foam, the platinum electrode and the calomel electrode uniform, setting the deposition voltage to be 1.5V and the deposition time to be 600s by adopting a constant-voltage electrodeposition method, and starting deposition;
(6) taking off the foam nickel deposited with manganese, placing the foam nickel in a glass dish, and drying the foam nickel in a drying oven at the temperature of 60 ℃ for 12 hours;
(7) and (3) putting the dried foam nickel into a muffle furnace, roasting for 4 hours at the temperature of 300 ℃, wherein the heating rate is 2 ℃/min, and the integral manganese oxide nitric oxide purification catalyst is marked as Mn/NF-Na.
6. A monolithic ion-doped manganese oxide nitric oxide catalyst, characterized by being prepared according to the method of any one of claims 1 to 5.
7. Use of the monolithic ion-doped manganese oxide nitric oxide catalyst of claim 6 as a catalyst in nitric oxide purification.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011116948.5A CN112108155A (en) | 2020-10-19 | 2020-10-19 | Preparation method of integral manganese oxide nitric oxide catalyst, product and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011116948.5A CN112108155A (en) | 2020-10-19 | 2020-10-19 | Preparation method of integral manganese oxide nitric oxide catalyst, product and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112108155A true CN112108155A (en) | 2020-12-22 |
Family
ID=73794426
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011116948.5A Pending CN112108155A (en) | 2020-10-19 | 2020-10-19 | Preparation method of integral manganese oxide nitric oxide catalyst, product and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112108155A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113426456A (en) * | 2021-07-19 | 2021-09-24 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of high-concentration nitric oxide monolithic manganese oxide catalyst, product and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108212153A (en) * | 2018-02-06 | 2018-06-29 | 华东师范大学 | A kind of manganese base composite oxidate catalyst of self-supporting modified with noble metals and its preparation method and application |
| CN109590014A (en) * | 2018-11-09 | 2019-04-09 | 四川大学 | A kind of integral diesel tail gas oxidation catalyst and preparation method thereof |
| CN111774068A (en) * | 2020-07-08 | 2020-10-16 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of integral manganese oxide nitric oxide purification catalyst, product and application thereof |
-
2020
- 2020-10-19 CN CN202011116948.5A patent/CN112108155A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108212153A (en) * | 2018-02-06 | 2018-06-29 | 华东师范大学 | A kind of manganese base composite oxidate catalyst of self-supporting modified with noble metals and its preparation method and application |
| CN109590014A (en) * | 2018-11-09 | 2019-04-09 | 四川大学 | A kind of integral diesel tail gas oxidation catalyst and preparation method thereof |
| CN111774068A (en) * | 2020-07-08 | 2020-10-16 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of integral manganese oxide nitric oxide purification catalyst, product and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113426456A (en) * | 2021-07-19 | 2021-09-24 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of high-concentration nitric oxide monolithic manganese oxide catalyst, product and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11174164B2 (en) | Honeycomb-like homo-type heterojunction carbon nitride composite material and preparation method thereof, and application in catalytic treatment of waste gas | |
| CN107362823B (en) | Catalytic material for degrading indoor formaldehyde at room temperature and preparation method thereof | |
| CN111774068A (en) | Preparation method of integral manganese oxide nitric oxide purification catalyst, product and application thereof | |
| CN108393085B (en) | Attapulgite-loaded cerium-doped MnTiOX ternary-component low-temperature denitration catalyst and preparation method thereof | |
| CN106450354B (en) | A kind of hydrothermal synthesis method of nitrogen-doped graphene Supported Co oxygen reduction reaction elctro-catalyst | |
| CN113649022B (en) | Catalyst for catalytic combustion of organic volatile waste gas and preparation method thereof | |
| CN108620113B (en) | Preparation method of nitrogen-doped carbon-cerium composite nanosheet | |
| CN113000046A (en) | Modified manganese-based mullite catalyst for synergistic purification of nitrogen oxides and volatile organic compounds, and preparation method and application thereof | |
| CN110270379A (en) | A kind of MnOx- MOF-Gr composite material and preparation method and application | |
| CN113385185A (en) | High-activity and selective perovskite type photo-thermal catalyst and preparation method and application thereof | |
| CN108479845B (en) | Denitration catalyst and preparation method thereof | |
| CN112108155A (en) | Preparation method of integral manganese oxide nitric oxide catalyst, product and application thereof | |
| CN103623832B (en) | Preparation method of rare-earth oxide material containing tourmaline | |
| CN110773224A (en) | Preparation method of alkali metal-resistant denitration catalyst | |
| CN114377684B (en) | MnCoO for removing CO under low-temperature condition x Catalyst and preparation method thereof | |
| CN107930652A (en) | A kind of MnOx FeOx CuSO4/TiO2Middle low-temperature SCR catalyst and preparation method thereof | |
| CN113398905A (en) | Based on netted TiO2MnO of support2Nanowire low-temperature denitration catalyst and preparation method thereof | |
| CN113186560A (en) | Ni-rich alloy3+Nickel cobaltate modified carbon ball electrode catalyst | |
| CN115555019B (en) | Noble metal doped perovskite type catalytic material and preparation method thereof | |
| CN112642450A (en) | Preparation method of phosphorus-doped carbon aerogel supported manganese cerium catalyst | |
| CN113426456A (en) | Preparation method of high-concentration nitric oxide monolithic manganese oxide catalyst, product and application thereof | |
| CN112569960A (en) | Preparation method of weak crystallization monolithic manganese oxide catalyst and product thereof | |
| CN115672310A (en) | Low-temperature SCR denitration catalyst with sulfur poisoning resistance and preparation method thereof | |
| CN111203228B (en) | Integral chromium oxide nitric oxide purifying catalyst and preparation method and application thereof | |
| CN109589910A (en) | The preparation method and application of barium cobalt-based properties of perovskite mixed-oxide oxygen carrier |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201222 |