CN114534731A - Preparation method and application of hydrotalcite-based carbon-doped copper-magnesium-aluminum composite oxide catalyst - Google Patents
Preparation method and application of hydrotalcite-based carbon-doped copper-magnesium-aluminum composite oxide catalyst Download PDFInfo
- Publication number
- CN114534731A CN114534731A CN202210084049.4A CN202210084049A CN114534731A CN 114534731 A CN114534731 A CN 114534731A CN 202210084049 A CN202210084049 A CN 202210084049A CN 114534731 A CN114534731 A CN 114534731A
- Authority
- CN
- China
- Prior art keywords
- sdso
- hydrotalcite
- solution
- catalyst
- cumgal
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 title claims abstract description 33
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 33
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- -1 copper-magnesium-aluminum Chemical compound 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 57
- 239000000243 solution Substances 0.000 claims abstract description 35
- 239000012266 salt solution Substances 0.000 claims abstract description 21
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000000694 effects Effects 0.000 claims abstract description 13
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 13
- 239000011593 sulfur Substances 0.000 claims abstract description 13
- 238000012360 testing method Methods 0.000 claims abstract description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 238000011156 evaluation Methods 0.000 claims abstract description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims abstract description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims abstract description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 238000004448 titration Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000009830 intercalation Methods 0.000 claims description 8
- 230000002687 intercalation Effects 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000012495 reaction gas Substances 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- 238000003915 air pollution Methods 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 15
- 238000003760 magnetic stirring Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000007833 carbon precursor Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000009795 derivation Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910018565 CuAl Inorganic materials 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- UNRNJMFGIMDYKL-UHFFFAOYSA-N aluminum copper oxygen(2-) Chemical compound [O-2].[Al+3].[Cu+2] UNRNJMFGIMDYKL-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 230000002195 synergetic effect Effects 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
- 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
- B01J23/78—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 alkali- or alkaline earth metals
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (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)
- Catalysts (AREA)
Abstract
The invention discloses a hydrotalcite-based carbon doped copper-magnesium-aluminum composite oxide catalyst, and a preparation method and application thereof, and belongs to the technical field of air pollution control. The catalyst is prepared by dropwise adding a mixed salt solution of copper nitrate, magnesium nitrate, aluminum nitrate and NaOH aqueous alkali into a solution containing Sodium Dodecyl Sulfate (SDSO), controlling the synthetic pH within the range of 9.0-10.0, and carrying out one-step in-situ synthesis on a CuMgAl hydrotalcite precursor intercalated by SDSO; firstly, roasting the catalyst in a nitrogen atmosphere, and then roasting the catalyst in an air atmosphere to prepare a hydrotalcite-based carbon-doped copper-magnesium-aluminum composite oxide denitration catalyst (CuMgAl-SDSO-LDO); the denitration activity test and the sulfur resistance evaluation show that the CuMgAl-SDSO-LDO catalyst has high NH in a low-temperature region (150 ℃ F. and 270 ℃ C.)3SCR activity, good N2Selectivity isAnd stronger sulfur resistance.
Description
Technical Field
The invention relates to a catalyst and a preparation method thereof, in particular to a hydrotalcite-based carbon-doped copper-magnesium-aluminum composite oxide catalyst which can be used for low-temperature NH3-SCR reaction, belonging to the technical field of air pollution prevention and control.
Background
Nitrogen Oxides (NO)x) Is a global air pollutant, NO, with serious adverse effects on the environment, climate and human healthxHas become an important task for relevant industrial production units. Among the numerous denitration techniques, ammonia selective catalytic reduction (NH)3SCR) is the most widely used flue gas denitration technology at home and abroad at present due to the advantages of high removal efficiency, large gas treatment capacity, easy control of reaction conditions and the like. For low temperature denitration processes, the choice of catalyst is crucial. The copper-based oxide catalyst prepared by the derivation of the hydrotalcite-like compound has relatively good dispersibility, but still needs to be further improved, and earlier researches (CN201810940161.7) indicate that the preparation of the nano hybrid precursor is realized by coupling and assembling the copper-aluminum hydrotalcite-like compound and CNTs, and the dispersibility of the active center of the copper-aluminum composite oxide catalyst and CuO are solved to a great extentxThe problem of species coordination distribution. However, the carbon nanotube needs to be modified in the early stage of the preparation method, the carbon tube modification process is too complicated, and the cost of the carbon nanotube is relatively high. LDH has excellent interlayer anion exchange performance, so that the method has important significance on simply preparing the hydrotalcite-based carbon-doped copper aluminum oxide catalyst by interlayer intercalation with a low-cost carbon source in one step.
Disclosure of Invention
The invention provides a hydrotalcite-based carbon-doped copper-magnesium-aluminum composite oxide denitration catalyst with sulfur resistance and a preparation method and application thereof, wherein the catalyst is prepared by means of hydrotalcite-like structure and one-step in-situ derivation of a carbon material between hydrotalcite-like layers in a manner of intercalation of an organic carbon precursor between the layers, so that high coupling of hydrotalcite-like and the carbon material is realized, and proper roasting atmosphere and roasting temperature are optimized.
The Sodium Dodecyl Sulfate (SDSO) selected by the invention is a common anionic surfactant, and is widely applied to the fields of washing, chemical engineering and the like due to the advantages of stable property, wide sources of preparation raw materials, low production cost and the like. Based on excellent structural performance of interchangeability of hydrotalcite-like interlayer anions, sodium dodecyl sulfate and CuMgAl hydrotalcite-like are effectively assembled, anion dodecyl sulfonate is successfully inserted into the interlayer of the CuMgAl hydrotalcite-like, and hydrotalcite-based carbon-doped copper-magnesium-aluminum composite oxide low-temperature NH with excellent catalytic performance is successfully prepared by controlling proper roasting atmosphere and roasting temperature3-an SCR denitration catalyst.
The invention provides a hydrotalcite-based carbon-doped copper-magnesium-aluminum composite oxide denitration catalyst, which is prepared by dropwise adding aluminum nitrate, a mixed salt solution of magnesium nitrate and copper nitrate and NaOH aqueous alkali into a solution containing sodium dodecyl sulfate, controlling the synthetic pH to be within 9.0-10.0, and preparing a sodium dodecyl sulfate intercalated CuMgAl hydrotalcite precursor (CuMgAl-SDSO-LDH) through hydrothermal crystallization, suction filtration washing and drying; then roasting the catalyst in a nitrogen atmosphere and then in an air atmosphere to prepare a highly dispersed hydrotalcite-based carbon-doped copper-magnesium-aluminum composite oxide (CuMgAl-SDSO-LDO) denitration catalyst; the denitration activity test and the sulfur resistance evaluation find that the CuMgAl-SDSO-LDO catalyst has high NH in a low-temperature region (150 ℃ F. and 270 ℃ C.)3-SCR activity, N2Selectivity and strong sulfur resistance.
The invention provides a preparation method of the hydrotalcite-based carbon doped copper-magnesium-aluminum composite oxide denitration catalyst, which comprises the following steps:
(1) preparing mixed salt solution
Respectively preparing 1.0 mol as L by using a volumetric flask-10.5 mol of the aqueous solution of copper nitrate trihydrate-10.5 mol of magnesium nitrate hexahydrate solution-1The aqueous aluminum nitrate nonahydrate solution of (1). Respectively weighing three prepared salt solutions, mixing the three prepared salt solutions into a beaker, stirring the mixture for 10 to 20 min to form a transparent solution, and transferring the transparent solution into a first dropping funnel for later use, wherein (Cu)2++Mg2+) With Al3+The ratio of the amount of the substances is 3:1 to 4: 1;
(2) preparing sodium hydroxide solution
NaOH is dissolved in deionized water to prepare the solution with the concentration of 1.0 mol as much as L-1Transferring the NaOH aqueous solution into a second dropping funnel for later use;
(3) preparing sodium dodecyl sulfate solution
Adding 6.5-13.0 g of sodium dodecyl sulfate into 120-240 ml of deionized water to obtain a sodium dodecyl sulfate solution;
(4) preparation of sodium dodecyl sulfonate intercalated CuMgAl hydrotalcite precursor
Taking the sodium dodecyl sulfate solution prepared in the step (3) to the solvent N2In the four-mouth round-bottom flask, be fixed in the magnetic force water bath with the round-bottom flask in, slowly instil into above-mentioned round-bottom flask with solution in dropping funnel one and dropping funnel two under magnetic stirring, the dropwise add speed of control mixed salt solution is 2~ 3 ml for a minute-1Adjusting the dropping speed of the sodium hydroxide solution to maintain the pH value of the solution at 9-10; after titration, raising the temperature of the magnetic water bath to 65 ℃ for crystallization for 12-48 h; and carrying out suction filtration, washing and drying to obtain an SDSO intercalated CuMgAl hydrotalcite precursor CuMgAl-SDSO-LDH.
(5) Preparation of CuMgAl-SDSO-LDO denitration catalyst
And (4) roasting the precursor obtained in the step (4) for 4-6 h in a nitrogen atmosphere, and roasting in the air for 3-5 h to obtain the CuMgAl-SDSO-LDO denitration catalyst.
The above process, said step (1), adding Mg2+With Al3+The ratio of the amount of the substance is 1:1 to 2: 1.
In the method, in the step (4), the volume ratio of the added sodium dodecyl sulfate solution to the mixed salt solution is 0.5-1: 1.
in the method, in the step (5), the flow rate of the introduced nitrogen is controlled to be 60 ml during the aging period-1～100 ml▪min-1. The temperature programming rate is 2-10 ℃ for a minute-1. The calcination temperature was set at 400-600 ℃ under a nitrogen atmosphere.
In the method, in the step (5), the roasting temperature set in the roasting in the air is 350-500 ℃.
The invention provides a method for preparing the denitration catalyst in NH3-use in SCR.
The specific application process is as follows: the catalytic reaction tests were carried out in a fixed bed continuous flow quartz reactor. The catalyst has a particle size of 40-60 meshes and the dosage of 400 mg. The reaction gas composition is: 500 ppm NO, 500 ppm NH3，100 ppm SO2 (Sulfur resistant), 5% O2，N2As balance gas, the space velocity of the reaction gas is 45000 h-1. The catalytic reaction was carried out at 150 ℃ and 270 ℃ and the activity data were collected after the reaction reached equilibrium.
The invention has the beneficial effects that:
(1) the problem that active components are easy to agglomerate is effectively solved by inserting SDSO into CuMgAl-LDH interlamination to construct a hydrotalcite-based carbon-doped copper-magnesium-aluminum composite oxide catalyst.
(2) The method of the invention provides high-dispersion CuO on the surface of the catalystxThe optimized construction and the sulfur resistance performance enhancement are integrated, and the low-temperature NH of the CuAl-based oxide catalyst is realized3-performance enhancement of SCR.
(3) The structure and the crystalline phase of the active center are regulated and controlled through the synergistic effect between the carbon source and the CuMgAl-LDO, so that NH is increased3-SCR activity.
(4) The successful retention of carbon can obviously enhance the sulfur resistance of the CuMgAl-LDO catalyst and slow SO2The poisoning effect on the catalyst ensures the application under the actual condition.
(5) The coupling assembly of the hydrotalcite-like compound and the carbon material is realized by a mode of interlayer intercalation polymerization of the organic carbon precursor.
Drawings
FIG. 1 is an X-ray diffraction pattern (XRD) of the precursor and final product obtained in example 1: (A) is a precursor CuMgAl-SDSO-LDH before roasting; (B) the CuMgAl-SDSO-LDO is finally obtained after roasting.
FIG. 2 is a graph of HR-TEM lattice fringes of the CuMgAl-SDSO-LDO catalyst of example 2.
FIG. 3 is a Transmission Electron Microscope (TEM) image of the CuMgAl-SDSO-LDO of example 3.
FIG. 4 is NH of CuMgAl-SDSO-LDO catalyst of example 43-SCR activity test results: a is N2Selectivity; b, NO conversion rate.
FIG. 5 shows the results of the sulfur resistance test of the CuMgAl-SDSO-LDO catalyst of example 1.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
Example 1:
(1) respectively taking 30 ml of liquid with the concentration of 0.5 mol as much as L -130 ml of 0.5 mol of aluminum nitrate nonahydrate aqueous solution is generated-1The magnesium nitrate hexahydrate aqueous solution and 30 ml of aqueous solution with the concentration of 1.0 mol are generated-1Adding the copper nitrate trihydrate aqueous solution into a beaker, stirring for 10 min by using a magnetic stirrer to uniformly mix the copper nitrate trihydrate aqueous solution and the magnetic stirrer, and transferring the prepared salt solution into a dropping funnel for standby;
(2) taking 300 ml of gas with the concentration of 1.00 mol as-1Transferring the aqueous solution of sodium hydroxide into a dropping funnel for standby;
(3) taking 90 ml of fluid with the concentration of 0.2 mol as much as L-1The sodium dodecyl sulfate solution is put into a four-neck flask, a sodium hydroxide aqueous solution and a mixed salt solution are simultaneously dripped into the solution under magnetic stirring, the pH value in the titration process is monitored in real time by an acidimeter, and the titration speed is controlled to keep the pH value of the system between 9.0 and 10.0 in the whole reaction process; after the dripping is finished, continuously stirring in a magnetic stirring water bath for 30 min, and then raising the temperature of the water bath to 65 ℃ for crystallization for 24 h;
(4) and (3) carrying out suction filtration on a product after reaction, washing the product to be neutral by using deionized water, and drying the product in an oven at 80 ℃ for 12 hours. Then fully grinding to obtain the SDSO intercalation CuMgAl hydrotalcite precursor (CuMgAl-SDSO-LDH).
(5) Placing the obtained CuMgAl-SDSO-LDH into a tube furnace, introducing nitrogen to protect, and roasting for 5h (the nitrogen flow rate is 60 ml) from room temperature programmed temperature to 500 DEG C-1The programmed heating rate is 2 ℃ for min-1) Then, the sample is transferred into a muffle furnace and is roasted for 4 hours from room temperature to 400 ℃ by temperature programming (the temperature programming rate is 2 ℃ for min-1) Finally obtaining the hydrotalcite-based carbon-doped CuMgAl composite oxide denitration catalyst (CuMgAl-SDSO-LDO).
The crystal structures of the precursor and the final product are characterized and analyzed by means of an X-ray diffractometer (XRD), and as shown in figure 1, the successful synthesis of CuMgAl-SDSO-LDH and the phase composition of the roasted product thereof are proved.
Example 2:
(1) respectively taking 30 ml of liquid with the concentration of 0.5 mol as much as L -160 ml of 0.5 mol of aluminum nitrate nonahydrate aqueous solution is generated-1Is prepared from a magnesium nitrate hexahydrate aqueous solution and 15 ml of L with the concentration of 1.0 mol-1The copper nitrate trihydrate aqueous solution is put into a four-mouth flask, stirred for 10 min by a magnetic stirrer to be uniformly mixed, and the prepared salt solution is transferred into a dropping funnel for standby;
(2) taking 300 ml of gas with the concentration of 1.00 mol as-1Transferring the aqueous solution of sodium hydroxide into a dropping funnel for standby;
(3) taking 45 ml of liquid with the concentration of 0.4 mol as much as L-1Placing a sodium dodecyl sulfate solution in a four-neck flask, dripping a sodium hydroxide aqueous solution and a mixed salt solution into the solution simultaneously under magnetic stirring, monitoring the pH value in the titration process in real time by using an acidimeter, and controlling the titration speed to keep the pH value of the system between 9.0 and 10.0 in the whole reaction process; after the dripping is finished, continuously stirring in a magnetic stirring water bath for 30 min, and then raising the temperature of the water bath to 65 ℃ for crystallization for 24 h;
(4) and after the reaction kettle is naturally cooled, performing suction filtration on a product after reaction, washing the product to be neutral by using deionized water, and drying the product in an oven at 80 ℃ for 12 hours. Then fully grinding to obtain the SDSO intercalation CuMgAl hydrotalcite precursor (CuMgAl-SDSO-LDH).
(5) The obtained CuMgAl-DSO-Placing the LDH in a tube furnace, introducing nitrogen for protection, and roasting for 5h (the nitrogen flow rate is 60 ml) from room temperature programmed temperature to 500 DEG C-1The programmed heating rate is 10 ℃ for min-1) Will thenThe sample is transferred to a muffle furnace and is roasted for 4 hours from room temperature to 400 ℃ by temperature programming (the temperature programming rate is 2 ℃ for min-1) Finally obtaining the hydrotalcite-based carbon-doped CuMgAl composite oxide denitration catalyst (CuMgAl-SDSO-LDO).
The catalyst was characterized by high power transmission electron microscopy, as shown in figure 2, demonstrating the presence of carbon and copper oxides.
Example 3:
(1) respectively taking 30 ml of liquid with the concentration of 0.5 mol as much as L -160 ml of 0.5 mol of aluminum nitrate nonahydrate aqueous solution is generated-1The magnesium nitrate hexahydrate aqueous solution and 30 ml of aqueous solution with the concentration of 1.0 mol are generated-1The copper nitrate trihydrate aqueous solution is put into a four-mouth flask, stirred for 10 min by a magnetic stirrer to be uniformly mixed, and the prepared salt solution is transferred into a dropping funnel for standby;
(2) taking 300 ml of gas with the concentration of 1.00 mol as-1Transferring the aqueous solution of sodium hydroxide into a dropping funnel for standby;
(3) taking 60 ml of liquid with the concentration of 0.4 mol as-1The sodium dodecyl sulfate solution is put into a beaker, a sodium hydroxide aqueous solution and a mixed salt solution are simultaneously dripped into the solution under magnetic stirring, the pH value in the titration process is monitored in real time by an acidimeter, and the titration speed is controlled to keep the pH value of the system between 9.0 and 10.0 in the whole reaction process; after the dripping is finished, continuously stirring in a magnetic stirring water bath for 30 min, and then raising the temperature of the water bath to 65 ℃ for crystallization for 12 h;
(4) and (3) carrying out suction filtration on a product after reaction, washing the product to be neutral by using deionized water, and drying the product in an oven at 80 ℃ for 12 hours. Then fully grinding to obtain the SDSO intercalation CuMgAl hydrotalcite precursor (CuMgAl-SDSO-LDH).
(5) Placing the obtained CuMgAl-SDSO-LDH into a tube furnace, introducing nitrogen to protect the CuMgAl-SDSO-LDH, and roasting the CuMgAl-SDSO-LDH for 5 hours (the nitrogen flow rate is 80 ml) from room temperature to 600 ℃ in a programmed heating way-1The programmed heating rate is 5 ℃ for min-1) Then, the sample is transferred into a muffle furnace and is roasted for 4 hours from room temperature to 400 ℃ by temperature programming (the temperature programming rate is 2 ℃ for min-1) To finally obtain hydrotalciteA base carbon doped CuMgAl composite oxide (CuMgAl-SDSO-LDO) denitration catalyst.
The catalyst was characterized by means of transmission electron microscopy, as shown in FIG. 3, demonstrating the high dispersion of the product.
Example 4:
(1) respectively taking 30 ml of liquid with the concentration of 0.5 mol as much as L -130 ml of 0.5 mol of aluminum nitrate nonahydrate aqueous solution is generated-160 ml of magnesium nitrate hexahydrate aqueous solution with the concentration of 1.0 mol-1The copper nitrate trihydrate aqueous solution is put into a four-mouth flask, stirred for 10 min by a magnetic stirrer to be uniformly mixed, and the prepared salt solution is transferred into a dropping funnel for standby;
(2) taking 300 ml of gas with the concentration of 1.00 mol as-1Transferring the aqueous solution of sodium hydroxide into a dropping funnel for standby;
(3) 60 ml of sludge with the concentration of 0.4 mol is taken-1The sodium dodecyl sulfate solution is put into a beaker, the sodium hydroxide aqueous solution and the mixed salt solution are simultaneously dripped into the solution under magnetic stirring, the pH value in the titration process is monitored in real time by an acidimeter, and the titration speed is controlled to keep the pH value of the system between 9.0 and 10.0 in the whole reaction process; after the dripping is finished, continuously stirring in a magnetic stirring water bath for 30 min, and then raising the temperature of the water bath to 65 ℃ for crystallization for 48 h;
(4) and (3) carrying out suction filtration on the product after reaction, washing the product to be neutral by using deionized water, and then drying the product in an oven at the temperature of 80 ℃ for 12 hours. Then fully grinding to obtain the SDSO intercalation CuMgAl hydrotalcite precursor (CuMgAl-SDSO-LDH).
(5) Placing the obtained CuMgAl-SDSO-LDH into a tube furnace, introducing nitrogen to protect, and roasting for 5h (the nitrogen flow rate is 80 ml) from room temperature programmed temperature to 500 DEG C-1The programmed heating rate is 5 ℃ for min-1) Then, the sample is transferred into a muffle furnace and is roasted for 4 hours from room temperature to 400 ℃ by temperature programming (the temperature programming rate is 2 ℃ for min-1) Finally obtaining the hydrotalcite-based carbon-doped CuMgAl composite oxide (CuMgAl-SDSO-LDO) denitration catalyst.
NH to catalyst of the invention3-SCR active feedThe tests show that the hydrotalcite-based carbon-doped CuMgAl composite oxide denitration catalyst prepared by the method has high NH as shown in FIG. 43SCR activity, good N2And (4) selectivity.
Example 5: NH of catalyst3Evaluation of SCR Performance
Application of the CuMgAl-SDSO-LDO catalyst prepared in example 4 to NH3SCR reaction, the results of which are shown in FIG. 4. The catalyst shows good low-temperature catalytic performance, the NO conversion rate can reach 90% at 210 ℃, and N is2The selectivity can be maintained around 80% over the temperature range tested.
The specific reaction conditions are as follows: the catalytic reaction tests were carried out in a fixed bed continuous flow quartz reactor. The catalyst has a particle size of 40-60 meshes and the dosage of 400 mg. The reaction gas composition is: 500 ppm NO, 500 ppm NH3，5% O2，N2As balance gas, the space velocity of the reaction gas is 45000 h-1. The catalytic reaction was carried out at 150 ℃ and 270 ℃ and the activity data were collected after the reaction reached equilibrium. Product analysis by MultiGas 6030 FTIR (MKS) detection, NO conversion and N2The selectivity is calculated by the following formula:
example 6: catalyst SO resistance2Evaluation of Performance
SO-resistance of the CuMgAl-SDSO-LDO catalyst prepared in example 12The results of the performance evaluation are shown in FIG. 5. The catalyst has excellent sulfur resistance when the sulfur content is 100 PPM SO2When the catalyst is added, the NO conversion rate can still be maintained to be more than 70%.
The specific reaction conditions are as follows: the test apparatus and catalyst amounts were the same as in example 5. The composition of the reaction gas was 500 ppm NO, 500 ppm NH3，5% O2，100 ppm SO2，N2 As balance gas, the space velocity of the reaction gas is 45000 h-1The reaction temperature was 210 ℃.
Claims (8)
1. A hydrotalcite-based carbon-doped copper-magnesium-aluminum composite oxide catalyst is characterized in that: the catalyst is prepared by dropwise adding a mixed salt solution of aluminum nitrate, magnesium nitrate and copper nitrate and NaOH aqueous solution into a four-neck flask containing an SDSO solution, controlling the synthetic pH within the range of 9-10, and performing hydrothermal crystallization, suction filtration, washing and drying to obtain an SDSO intercalation CuMgAl hydrotalcite-like precursor; then roasting the catalyst in a nitrogen atmosphere and then roasting the roasted catalyst in an air atmosphere to prepare a hydrotalcite-based carbon-doped copper-magnesium-aluminum composite oxide CuMgAl-SDSO-LDO denitration catalyst; wherein the mass concentration of the SDSO is 0.2-0.4 mol/L.
2. A method for preparing the hydrotalcite-based carbon-doped copper magnesium aluminum composite oxide catalyst according to claim 1, which is characterized by comprising the following steps:
(1) preparing mixed salt solution
Respectively preparing 1.0 mol as L by using a volumetric flask-10.5 mol of the aqueous solution of copper nitrate trihydrate-10.5 mol of magnesium nitrate hexahydrate solution-1The aqueous aluminum nitrate nonahydrate solution of (a); respectively weighing three prepared salt solutions, mixing the three prepared salt solutions into a beaker, stirring the mixture for 10 to 20 min to form a transparent solution, and transferring the transparent solution into a first dropping funnel for later use, wherein (Cu)2++Mg2+) With Al3+The mass ratio of the substances is 2:1 to 4: 1; mg (magnesium)2+And Cu2+The ratio of the amount of the substances is 1:2 to 2: 1;
(2) preparing sodium hydroxide solution
NaOH is dissolved in deionized water to prepare the solution with the concentration of 1.0 mol as much as L-1Transferring the NaOH aqueous solution into a second dropping funnel for standby;
(3) preparing sodium dodecyl sulfate solution
Adding 6.5-13.0 g of sodium dodecyl sulfate into 120-240 ml of deionized water to obtain a sodium dodecyl sulfate solution;
(4) preparation of SDSO intercalated CuMgAl hydrotalcite-like precursor
Taking the sodium dodecyl sulfate solution prepared in the step (3) to the solvent N2In the four-neck round-bottom flask, the round-bottom flask is fixed in a magnetic water bath, and is stirred by magnetic forceIn slowly dripping into above-mentioned round bottom flask with solution in dropping funnel one and dropping funnel two down, the dropwise add speed of control mixed salt solution is 2~ 3 ml for a min-1Adjusting the dropping speed of the sodium hydroxide solution to maintain the pH value of the solution at 9-10; after titration, raising the temperature of the magnetic water bath to 65 ℃ for crystallization for 12-48 h; carrying out suction filtration, washing and drying to obtain an SDSO intercalated CuMgAl hydrotalcite precursor CuMgAl-SDSO-LDH;
(5) preparation of CuMgAl-SDSO-LDO denitration catalyst
And (4) roasting the precursor obtained in the step (4) for 4-6 h in a nitrogen atmosphere, and roasting in the air for 3-5 h to obtain the CuMgAl-SDSO-LDO denitration catalyst.
3. The preparation method of the hydrotalcite-based carbon-doped copper-magnesium-aluminum composite oxide denitration catalyst according to claim 2, characterized in that: in the step (1), Mg is added2+With Al3+The ratio of the amount of the substance is 1:1 to 2: 1.
4. The preparation method of the hydrotalcite-based carbon-doped copper-magnesium-aluminum composite oxide denitration catalyst according to claim 2, characterized in that: in the step (4), the volume ratio of the added SDSO solution to the mixed salt solution is 0.5-1: 1.
5. the preparation method of the hydrotalcite-based carbon-doped copper-magnesium-aluminum composite oxide denitration catalyst according to claim 2, characterized in that: in the step (4), the whole precursor preparation process is carried out at N2Is carried out in an atmosphere.
6. The preparation method of the hydrotalcite-based carbon-doped copper-magnesium-aluminum composite oxide denitration catalyst according to claim 2, characterized in that: in the step (5), the flow rate of the introduced nitrogen is controlled to be 60 ml during-1～100 ml▪min-1(ii) a The temperature programming rate is 2-10 ℃ for a minute-1(ii) a The roasting temperature set under the nitrogen atmosphere is 400-600 ℃; the roasting temperature is set to 350-500 ℃ in the air.
7. The denitration catalyst of the hydrotalcite-based carbon-doped copper-magnesium-aluminum composite oxide of claim 1 in NH3-use in SCR.
8. Use according to claim 7, characterized in that: the specific application process is as follows: in a fixed bed continuous flow quartz reactor; the granularity of the catalyst is 40-60 meshes, and the dosage is 400 mg; the reaction gas composition is: 500 ppm NO, 500 ppm NH3，100 ppm SO2，5% O2，N2As balance gas, the space velocity of the reaction gas is 45000 h-1(ii) a The catalytic reaction is carried out at the temperature of 150 ℃ and 270 ℃, and activity data are collected after the reaction reaches balance;
the denitration activity test and the sulfur resistance evaluation show that the CuMgAl-SDSO-LDO catalyst has high NH at the temperature of 150 ℃ and 270 DEG C3SCR activity, good N2Selectivity and strong sulfur resistance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210084049.4A CN114534731B (en) | 2022-01-25 | 2022-01-25 | Preparation method and application of hydrotalcite-based carbon doped copper-magnesium-aluminum composite oxide catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210084049.4A CN114534731B (en) | 2022-01-25 | 2022-01-25 | Preparation method and application of hydrotalcite-based carbon doped copper-magnesium-aluminum composite oxide catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114534731A true CN114534731A (en) | 2022-05-27 |
| CN114534731B CN114534731B (en) | 2023-10-31 |
Family
ID=81672576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210084049.4A Active CN114534731B (en) | 2022-01-25 | 2022-01-25 | Preparation method and application of hydrotalcite-based carbon doped copper-magnesium-aluminum composite oxide catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114534731B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010111849A1 (en) * | 2009-04-02 | 2010-10-07 | 北京化工大学 | Solid basic catalyst for synthesizing alkanolamide compounds and preparation method thereof |
| CN102000572A (en) * | 2010-10-15 | 2011-04-06 | 大连理工大学 | Method for preparing denitration catalyst by performing selective catalytic reduction on CuMgAl composite oxide |
| US20120230899A1 (en) * | 2009-09-30 | 2012-09-13 | Kil Sang Chang | Mixed metal oxide catalyst for decomposition of nitrogen oxides |
| CN106629682A (en) * | 2016-12-27 | 2017-05-10 | 江汉大学 | Method for preparing hollow graphene nanospheres through confined catalysis |
| CN107091863A (en) * | 2017-05-26 | 2017-08-25 | 黑龙江大学 | A kind of three-layer laminated NiZnAl multichip semiconductors metal oxide composite and its preparation method and application |
| CN108906050A (en) * | 2018-08-17 | 2018-11-30 | 太原理工大学 | A kind of carbon nano tube-doped Copper-Aluminum compound metal oxide denitrating catalyst and its preparation method and application |
| CN111215075A (en) * | 2018-11-25 | 2020-06-02 | 中国科学院大连化学物理研究所 | Catalyst for eliminating ethylene coupling nitrous oxide produced by oxidative dehydrogenation of ethane and preparation and application thereof |
-
2022
- 2022-01-25 CN CN202210084049.4A patent/CN114534731B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010111849A1 (en) * | 2009-04-02 | 2010-10-07 | 北京化工大学 | Solid basic catalyst for synthesizing alkanolamide compounds and preparation method thereof |
| US20120230899A1 (en) * | 2009-09-30 | 2012-09-13 | Kil Sang Chang | Mixed metal oxide catalyst for decomposition of nitrogen oxides |
| CN102000572A (en) * | 2010-10-15 | 2011-04-06 | 大连理工大学 | Method for preparing denitration catalyst by performing selective catalytic reduction on CuMgAl composite oxide |
| CN106629682A (en) * | 2016-12-27 | 2017-05-10 | 江汉大学 | Method for preparing hollow graphene nanospheres through confined catalysis |
| CN107091863A (en) * | 2017-05-26 | 2017-08-25 | 黑龙江大学 | A kind of three-layer laminated NiZnAl multichip semiconductors metal oxide composite and its preparation method and application |
| CN108906050A (en) * | 2018-08-17 | 2018-11-30 | 太原理工大学 | A kind of carbon nano tube-doped Copper-Aluminum compound metal oxide denitrating catalyst and its preparation method and application |
| CN111215075A (en) * | 2018-11-25 | 2020-06-02 | 中国科学院大连化学物理研究所 | Catalyst for eliminating ethylene coupling nitrous oxide produced by oxidative dehydrogenation of ethane and preparation and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114534731B (en) | 2023-10-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108906050B (en) | Carbon nanotube doped copper-aluminum composite metal oxide denitration catalyst and preparation method and application thereof | |
| CN103663529B (en) | A kind of is that the method for nano-calcium carbonate slurry, product and application are prepared in calcium source with waste gypsum | |
| CN108927170B (en) | Preparation method and application of low-temperature flue gas denitration catalyst based on CoMnAl hydrotalcite-like compound | |
| CN106166491B (en) | A kind of mesoporous La0.8Sr0.2CoO3Load nano Ce O2Catalyst and its preparation method and application | |
| CN108927169B (en) | Preparation method and application of hydrotalcite-based CoMnFe composite metal oxide denitration catalyst | |
| CN102502770B (en) | Flower-like copper oxide catalyst and preparation method and application thereof | |
| CN101584981A (en) | Low-temperature preparation method of ceria nano-crystalline microsphere of graduation structure | |
| CN110302840B (en) | MnO (MnO)2Preparation method and application of/Cu-Al-BTC ternary metal organic framework material | |
| CN109012687B (en) | MnO (MnO)2Preparation method and application of/CoAl-LDO (low-temperature flue gas denitration catalyst) | |
| Feng et al. | Biogenic synthesis and catalysis of porous CeO2 hollow microspheres | |
| CN108993516B (en) | Composite oxide catalyst with nickel-titanium hydrotalcite as precursor and preparation method and application thereof | |
| CN104069861B (en) | A kind of mesoporous iron-based composite oxide catalysts, preparation method and the application in ammonia selective catalysis nitrogen oxides reduction thereof | |
| WO2023035532A1 (en) | Preparation method for la1-xmn1+xo3 | |
| CN105833887A (en) | BiOCl/beta-FeOOH composite nanomaterial and preparation method thereof | |
| CN101774533B (en) | Preparation method for gamma-alumina nanotube with prior exposure of (111) face | |
| CN108128784A (en) | The preparation method of Cu-Ce-La-SSZ-13 molecular sieve catalysts | |
| CN107185555B (en) | Preparation method of copper-doped cerium sulfide-based nanocrystalline denitration catalyst | |
| CN114558580A (en) | Preparation method of hydrotalcite-based CoNiV composite oxide catalyst and application of hydrotalcite-based CoNiV composite oxide catalyst in removal of escaped ammonia | |
| CN106345515B (en) | A kind of preparation method of Ce-Zn-Co-Cu mixing and dopings ZSM-5 zeolite molecular sieve | |
| CN102786080B (en) | Indium tin oxide compound and preparation method thereof and photocatalytic applications | |
| CN114534731A (en) | Preparation method and application of hydrotalcite-based carbon-doped copper-magnesium-aluminum composite oxide catalyst | |
| CN105032471B (en) | A kind of visible light-responded nano-TiO2The preparation of/Zeolite composite materials | |
| CN114477221B (en) | ZK-5 molecular sieve and preparation method and application thereof | |
| CN113634246B (en) | Rare earth vanadate catalyst for reducing nitrogen oxides | |
| CN107583653A (en) | Liquid-phase precipitation method prepares method and the application of cobaltosic oxide composite photo-catalyst |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |