CN114534731B - 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
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 27
- 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 26
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 26
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 26
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- -1 copper-magnesium-aluminum Chemical compound 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 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 41
- 239000012266 salt solution Substances 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 230000000694 effects Effects 0.000 claims abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- 239000011593 sulfur Substances 0.000 claims abstract description 12
- 238000012360 testing method Methods 0.000 claims abstract description 8
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims abstract description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 7
- 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
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- 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
- 239000003513 alkali Substances 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
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 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 19
- 239000007864 aqueous solution Substances 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
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 238000004448 titration Methods 0.000 claims description 10
- 102000020897 Formins Human genes 0.000 claims description 9
- 108091022623 Formins Proteins 0.000 claims description 9
- 238000003760 magnetic stirring Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 239000012495 reaction gas Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 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
- 239000010949 copper Substances 0.000 claims description 5
- 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 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000011777 magnesium 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
- 238000000967 suction filtration Methods 0.000 claims description 3
- 241000612118 Samolus valerandi Species 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000003915 air pollution Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 21
- 239000000047 product Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 4
- 230000002687 intercalation Effects 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000007833 carbon precursor Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910018565 CuAl Inorganic materials 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 229910021529 ammonia Inorganic materials 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 230000036541 health Effects 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
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 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
- 241000894007 species Species 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- 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
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- Health & Medical Sciences (AREA)
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- General Chemical & Material Sciences (AREA)
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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 and aluminum nitrate and an alkali solution of NaOH into a solution containing Sodium Dodecyl Sulfate (SDSO), controlling the synthesis pH to be 9.0-10.0, and synthesizing a CuMgAl hydrotalcite-like precursor intercalated with SDSO in situ by one step; firstly roasting the catalyst in nitrogen atmosphere and then roasting the catalyst in 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 area (150-270 ℃) 3 SCR Activity, good N 2 Selectivity and high 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 NH 3 -SCR reaction, which belongs to the technical field of atmospheric pollution control.
Background
Nitrogen Oxides (NO) x ) Is a global air pollutant with serious adverse effects on the environment, climate and human health, NO x Has become an important task for related industrial production units. Among the numerous denitration technologies, ammonia selective catalytic reduction technology (NH 3 SCR) is considered to be due to the advantages of high removal efficiency, large gas treatment capacity, easy control of reaction conditions and the likeThe flue gas denitration technology is most widely applied at home and abroad. For low temperature denitration process, the choice of catalyst is critical. The copper-based oxide catalyst prepared by hydrotalcite-like derivative has relatively good dispersibility and still needs to be further improved, and early research (CN 201810940161.7) indicates that the preparation of the nanometer hybrid precursor is realized by coupling and assembling copper-aluminum hydrotalcite-like and CNTs, so that the dispersibility of the active center of the copper-aluminum composite oxide catalyst and CuO are solved to a great extent x Problems of species coordination distribution. However, the preparation method requires modification of the carbon nanotubes in the early stage, the modification process of the carbon nanotubes is too complicated, and the cost of the carbon nanotubes is relatively high. LDHs have excellent interlayer anion exchange properties, and therefore, it is of great importance whether hydrotalcite-based carbon-doped copper-aluminum-based oxide catalysts can be simply prepared in one step by intercalation of a low-cost carbon source.
Disclosure of Invention
The invention provides a hydrotalcite-based carbon doped copper-magnesium-aluminum composite oxide denitration catalyst with sulfur resistance by means of a hydrotalcite-like structure, a method for in-situ derivatizing a carbon material in one step between hydrotalcite-like layers by means of intercalation of an organic carbon precursor, a method for preparing the same and application of the catalyst.
The Sodium Dodecyl Sulfate (SDSO) selected by the invention is a common anionic surfactant, and is widely applied to the fields of washing, chemical industry and the like due to the advantages of stable property, wide sources of preparation raw materials, low production cost and the like. Based on the excellent structural performance of the exchangeable anions among hydrotalcite-like layers, the invention effectively assembles the sodium dodecyl sulfonate and the CuMgAl hydrotalcite-like, so that the anion dodecyl sulfonate is successfully inserted among the layers of the CuMgAl hydrotalcite-like, and the hydrotalcite-based carbon doped copper-magnesium-aluminum composite oxide with excellent catalytic performance is successfully prepared at low temperature NH by controlling proper roasting atmosphere and roasting temperature 3 -an SCR denitration catalyst.
The invention provides a hydrotalcite-based carbon-doped copper-magnesium-aluminum composite oxide denitration catalyst, which is prepared by mixing aluminum nitrate, magnesium nitrate and copper nitrateAdding the salt solution and NaOH alkali solution into the solution containing sodium dodecyl sulfate dropwise, controlling the synthesis pH to be in the range of 9.0-10.0, and obtaining the intercalation CuMgAl hydrotalcite precursor (CuMgAl-SDSO-LDH) of sodium dodecyl sulfate through hydrothermal crystallization, suction filtration washing and drying; then roasting the mixture in nitrogen atmosphere and then in air atmosphere to prepare the 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 (150-270 ℃) 3 -SCR activity, N 2 Selectivity 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
1.0 mol L of Bunge were prepared separately using a volumetric flask -1 0.5 mol L of copper nitrate trihydrate -1 0.5 mol L of magnesium nitrate hexahydrate -1 Aluminum nitrate nonahydrate aqueous solution of (2). Respectively weighing three prepared salt solutions, mixing into a beaker, stirring for 10-20 min to form a transparent solution, and transferring the transparent solution into a dropping funnel I for standby, wherein (Cu 2+ +Mg 2+ ) With Al 3+ The ratio of the amounts of the substances is 3:1-4:1;
(2) Preparing sodium hydroxide solution
Dissolving NaOH in deionized water to obtain solution with concentration of 1.0 mol -1 Transferring the aqueous solution of NaOH into a second dropping funnel for standby;
(3) Preparing sodium dodecyl sulfonate solution
Adding 6.5-13.0. 13.0 g sodium dodecyl sulfonate into deionized water containing 120-ml-240 ml to obtain sodium dodecyl sulfonate solution;
(4) Preparation of sodium dodecyl sulfonate intercalated CuMgAl hydrotalcite-like precursor
Taking the sodium dodecyl sulfate solution prepared in the step (3) to N 2 In the four-neck round-bottom flask, the round-bottom flask is fixed in a magnetic water bath kettle, and dripping is carried out under the magnetic stirringSlowly dripping the solutions in the first funnel and the second dropping funnel into the round bottom flask, and controlling the dropping speed of the mixed salt solution to be 2-3 ml min -1 The pH value of the solution is maintained to be 9-10 by adjusting the dropping speed of the sodium hydroxide solution; after the titration is finished, the temperature of the magnetic water bath kettle is increased to 65 ℃ for crystallization 12-48 h; and filtering, washing and drying to obtain the SDSO intercalated CuMgAl hydrotalcite-like precursor CuMgAl-SDSO-LDH.
(5) Preparation of CuMgAl-SDSO-LDO denitration catalyst
And (3) roasting the precursor obtained in the step (4) under the nitrogen atmosphere for 4-6 h, and roasting in air for 3-5 h to obtain the CuMgAl-SDSO-LDO denitration catalyst.
In the above method, in the step (1), the added Mg 2+ With Al 3+ The ratio of the amounts of the substances is 1:1-2:1.
In the above 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 above method, in the step (5), the flow rate of the introduced nitrogen is controlled to be 60 ml min -1 ～100 ml▪min -1 . The temperature programming rate is 2-10 ℃ for min -1 . The calcination temperature was set to 400-600 ℃ under nitrogen atmosphere.
In the above method, in the step (5), the baking temperature set by baking in air is 350-500 ℃.
The invention provides the denitration catalyst in NH 3 -application in SCR.
The specific application process is as follows: catalytic reaction tests were performed in a fixed bed continuous flow quartz reactor. The granularity of the catalyst is 40-60 meshes, and the dosage is 400 mg. The composition of the reaction gas is as follows: 500 ppm NO,500 ppm NH 3 ，100 ppm SO 2 (sulfur resistance), 5% O 2 ，N 2 As balance gas, the space velocity of the reaction gas is 45000 h -1 . The catalytic reaction is carried out at 150-270 ℃, and the activity data is collected after the reaction reaches equilibrium.
The invention has the beneficial effects that:
(1) The hydrotalcite-based carbon doped copper-magnesium-aluminum composite oxide catalyst constructed by inserting SDSO into CuMgAl-LDH interlayer derivatization effectively relieves the problem of easy agglomeration of active components.
(2) The method of the invention provides the high dispersion CuO on the surface of the catalyst x An integrated solution way for optimizing construction and sulfur resistance strengthening of the CuAl-based oxide catalyst and realizing low-temperature NH (NH) 3 Performance enhancement of SCR.
(3) The structure and the crystal phase of the active center are regulated and controlled through the synergistic effect between the carbon source and the CuMgAl-LDO, thereby improving NH 3 -SCR activity.
(4) The successful retention of carbon can obviously enhance the sulfur resistance of the CuMgAl-LDO catalyst and slow down SO 2 The poisoning effect on the catalyst ensures the application under the actual condition.
(5) The coupling assembly of hydrotalcite-like compound and carbon material is realized by means of interlayer intercalation polymerization of 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; and (B) is CuMgAl-SDSO-LDO obtained after final roasting.
FIG. 2 is a pattern of the 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 a NH of the CuMgAl-SDSO-LDO catalyst of example 4 3 SCR activity test results: AN 2 Selectivity (1); and B, NO conversion rate.
FIG. 5 is the results of sulfur resistance testing of the CuMgAl-SDSO-LDO catalyst of example 1.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
Example 1:
(1) 30 ml L is 0.5 mol -1 30 ml concentration of 0.5 mol L -1 Magnesium nitrate hexahydrate of (a)The solution and 30 ml had a concentration of 1.0 mol L -1 The copper nitrate trihydrate aqueous solution is added into a beaker, and is stirred by a magnetic stirrer for 10 min to be uniformly mixed, and the prepared salt solution is transferred into a dropping funnel for standby;
(2) 300 ml is taken to have a concentration of 1.00 mol L -1 Transferring the aqueous solution of sodium hydroxide into a dropping funnel for later use;
(3) 90 ml is taken to have a concentration of 0.2 mol L -1 Sodium dodecyl sulfonate solution is put into a four-mouth flask, sodium hydroxide aqueous solution and mixed salt solution are dripped into the solution at the same time under magnetic stirring, pH value in the titration process is monitored in real time by an acidometer, and the titration speed is controlled to keep the pH value of the system in the whole reaction process between 9.0 and 10.0; continuously stirring in a magnetic stirring water bath for 30 min after the dripping is finished, and then raising the temperature of the water bath to 65 ℃ for crystallization 24 h;
(4) The product after the reaction was suction filtered and washed to neutrality with deionized water and dried in an 80 ℃ oven for 12 h. And then fully grinding to obtain the SDSO intercalated CuMgAl hydrotalcite-like precursor (CuMgAl-SDSO-LDH).
(5) Placing the obtained CuMgAl-SDSO-LDH into a tube furnace, introducing nitrogen, and calcining at 500 deg.C for 5 hr (nitrogen flow rate 60 ml min) -1 The temperature programming rate is 2 ℃ to min -1 ) The sample was then transferred to a muffle furnace and baked 4 h (at a rate of 2 ℃ C. For min) from room temperature to 400 ℃ C. At a programmed temperature -1 ) Finally, the hydrotalcite-based carbon doped CuMgAl composite oxide denitration catalyst (CuMgAl-SDSO-LDO) is obtained.
The present invention, which is characterized by means of X-ray diffractometry (XRD) for the crystal structure of the precursor and the final product, demonstrates the successful synthesis of CuMgAl-SDSO-LDH and the phase composition of its calcined product, as shown in FIG. 1.
Example 2:
(1) 30 ml L is 0.5 mol -1 The concentration of 60 ml in the aqueous aluminum nitrate nonahydrate solution is 0.5 mol L -1 Magnesium nitrate hexahydrate in an aqueous solution and 15 ml having a concentration of 1.0 mol L -1 Is of the formula (I)Mixing copper nitrate aqueous solution into a four-neck flask, stirring for 10 min by using a magnetic stirrer to uniformly mix, and transferring the prepared salt solution into a dropping funnel for standby;
(2) 300 ml is taken to have a concentration of 1.00 mol L -1 Transferring the aqueous solution of sodium hydroxide into a dropping funnel for later use;
(3) 45 ml is taken to have a concentration of 0.4 mol L -1 Sodium dodecyl sulfonate solution is put into a four-mouth flask, sodium hydroxide aqueous solution and mixed salt solution are dripped into the solution at the same time under magnetic stirring, pH value in the titration process is monitored in real time by an acidometer, 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; continuously stirring in a magnetic stirring water bath for 30 min after the dripping is finished, and then raising the temperature of the water bath to 65 ℃ for crystallization 24 h;
(4) After the reaction kettle is naturally cooled, the reacted product is subjected to suction filtration and washed to be neutral by deionized water, and then is dried in an oven at 80 ℃ for 12 h. And then fully grinding to obtain the SDSO intercalated CuMgAl hydrotalcite-like precursor (CuMgAl-SDSO-LDH).
(5) The obtained CuMgAl-DSO - LDH was placed in a tube furnace and calcined at 5h (nitrogen flow rate 60 ml min) with nitrogen blanket at a programmed temperature from room temperature to 500 ℃ -1 The temperature programming rate is 10 ℃ for min -1 ) The sample was then transferred to a muffle furnace and baked 4 h (at a rate of 2 ℃ C. For min) from room temperature to 400 ℃ C. At a programmed temperature -1 ) Finally, the hydrotalcite-based carbon doped CuMgAl composite oxide denitration catalyst (CuMgAl-SDSO-LDO) is obtained.
The present invention characterizes the catalyst by means of a high power transmission electron microscope, as shown in fig. 2, demonstrating the presence of carbon and copper oxides.
Example 3:
(1) 30 ml L is 0.5 mol -1 The concentration of 60 ml in the aqueous aluminum nitrate nonahydrate solution is 0.5 mol L -1 Magnesium nitrate hexahydrate in an aqueous solution and 30 ml having a concentration of 1.0 mol L -1 Copper nitrate trihydrate aqueous solution in a four-necked flask and stirred by a magnetic stirrer for 10 min to be uniformEvenly mixing, and transferring the prepared salt solution into a dropping funnel for standby;
(2) 300 ml is taken to have a concentration of 1.00 mol L -1 Transferring the aqueous solution of sodium hydroxide into a dropping funnel for later use;
(3) 60 ml is taken to have a concentration of 0.4 mol L -1 Sodium dodecyl sulfonate solution is added into a beaker, sodium hydroxide aqueous solution and mixed salt solution are simultaneously dripped into the solution under magnetic stirring, pH value in the titration process is monitored in real time by an acidometer, and the titration speed is controlled to keep the pH value of the system in the whole reaction process between 9.0 and 10.0; continuously stirring in a magnetic stirring water bath for 30 min after the dripping is finished, and then raising the temperature of the water bath to 65 ℃ for crystallization 12 h;
(4) The product after the reaction was suction filtered and washed to neutrality with deionized water and dried in an 80 ℃ oven for 12 h. And then fully grinding to obtain the SDSO intercalated CuMgAl hydrotalcite-like precursor (CuMgAl-SDSO-LDH).
(5) Placing the obtained CuMgAl-SDSO-LDH into a tube furnace, introducing nitrogen, and calcining at 600deg.C for 5 hr (nitrogen flow rate 80 ml min) -1 The temperature programming rate is 5 ℃ for min -1 ) The sample was then transferred to a muffle furnace and baked 4 h (at a rate of 2 ℃ C. For min) from room temperature to 400 ℃ C. At a programmed temperature -1 ) Finally, the hydrotalcite-based carbon doped CuMgAl composite oxide (CuMgAl-SDSO-LDO) denitration catalyst is obtained.
The present invention characterizes the catalyst by means of a transmission electron microscope, as shown in fig. 3, demonstrating the high dispersibility of the product.
Example 4:
(1) 30 ml L is 0.5 mol -1 30 ml concentration of 0.5 mol L -1 Magnesium nitrate hexahydrate and 60 ml at a concentration of 1.0 mole L -1 The copper nitrate trihydrate aqueous solution is added into a four-neck flask, stirred by a magnetic stirrer for 10 min to be uniformly mixed, and the prepared salt solution is transferred into a dropping funnel for standby;
(2) 300 ml is taken to have a concentration of 1.00 mol L -1 Transferring the aqueous solution of sodium hydroxide into a dropping funnel for later use;
(3) 60 ml is taken to have a concentration of 0.4 mol L -1 Sodium dodecyl sulfonate solution is added into a beaker, sodium hydroxide aqueous solution and mixed salt solution are simultaneously dripped into the solution under magnetic stirring, pH value in the titration process is monitored in real time by an acidometer, and the titration speed is controlled to keep the pH value of the system in the whole reaction process between 9.0 and 10.0; continuously stirring in a magnetic stirring water bath for 30 min after the dripping is finished, and then raising the temperature of the water bath to 65 ℃ for crystallization 48 h;
(4) The product after the reaction was suction filtered and washed to neutrality with deionized water and dried in an 80 ℃ oven for 12 h. And then fully grinding to obtain the SDSO intercalated CuMgAl hydrotalcite-like precursor (CuMgAl-SDSO-LDH).
(5) Placing the obtained CuMgAl-SDSO-LDH into a tube furnace, introducing nitrogen, and calcining at 500 deg.C for 5 hr (nitrogen flow rate 80 ml min) -1 The temperature programming rate is 5 ℃ for min -1 ) The sample was then transferred to a muffle furnace and baked 4 h (at a rate of 2 ℃ C. For min) from room temperature to 400 ℃ C. At a programmed temperature -1 ) Finally, the hydrotalcite-based carbon doped CuMgAl composite oxide (CuMgAl-SDSO-LDO) denitration catalyst is obtained.
NH on catalyst according to the invention 3 The SCR activity is tested, as shown in figure 4, and the result shows that the hydrotalcite-based carbon doped CuMgAl composite oxide denitration catalyst prepared by the method has high NH 3 SCR Activity, good N 2 Selectivity.
Example 5: NH of catalyst 3 SCR Performance evaluation
Application of the CuMgAl-SDSO-LDO catalyst prepared in example 4 to NH 3 SCR reaction, the results of which are shown in FIG. 4. The catalyst has good low-temperature catalytic performance, the NO conversion rate can reach 90% at 210 ℃, and N 2 The selectivity can be maintained at about 80% over the temperature range tested.
The specific reaction conditions are as follows: catalytic reaction tests were performed in a fixed bed continuous flow quartz reactor. Catalyst particle size40-60 mesh, and the dosage is 400 mg. The composition of the reaction gas is as follows: 500 ppm NO,500 ppm NH 3 ，5% O 2 ，N 2 As balance gas, the space velocity of the reaction gas is 45000 h -1 . The catalytic reaction is carried out at 150-270 ℃, and the activity data is collected after the reaction reaches equilibrium. The products were analyzed by MultiGas 6030 FTIR (MKS) detection, NO conversion and N 2 The selectivity is calculated by the following formula:
example 6: SO-resistant catalyst 2 Evaluation of Performance
SO resistance on the CuMgAl-SDSO-LDO catalyst prepared in example 1 2 The results of the performance evaluation are shown in figure 5. The catalyst has excellent sulfur resistance performance when 100 PPM SO 2 When added, the NO conversion can still be maintained above 70%.
Specific reaction conditions are as follows: the test apparatus was the same as the catalyst amount used in example 5. The composition of the reaction gas is 500 ppm NO,500 ppm NH 3 ，5% O 2 ，100 ppm SO 2 ，N 2 As balance gas, the space velocity of the reaction gas is 45000 h -1 The reaction temperature was 210 ℃.
Claims (7)
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 an alkali solution of NaOH into a four-neck flask containing an SDSO solution, controlling the synthesis pH to be 9-10, and performing hydrothermal crystallization, suction filtration, washing and drying to prepare an SDSO intercalated CuMgAl hydrotalcite-like precursor; roasting the mixture in nitrogen atmosphere and then roasting the mixture in 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 substance is 0.2-0.4 mol/L;
the preparation method of the hydrotalcite-based carbon doped copper-magnesium-aluminum composite oxide catalyst comprises the following steps:
(1) Preparing mixed salt solution
1.0 mol L of Bunge were prepared separately using a volumetric flask -1 0.5 mol L of copper nitrate trihydrate -1 0.5 mol L of magnesium nitrate hexahydrate -1 Aluminum nitrate nonahydrate aqueous solution; respectively weighing three prepared salt solutions, mixing into a beaker, stirring for 10-20 min to form a transparent solution, and transferring the transparent solution into a dropping funnel I for standby, wherein (Cu 2+ +Mg 2+ ) With Al 3+ The ratio of the amounts of the substances is 2:1-4:1; mg of 2+ With Cu 2+ The ratio of the amounts of the substances is 1:2-2:1;
(2) Preparing sodium hydroxide solution
Dissolving NaOH in deionized water to obtain solution with concentration of 1.0 mol -1 Transferring the aqueous solution of NaOH into a second dropping funnel for standby;
(3) Preparing sodium dodecyl sulfonate solution
Adding 6.5-13.0. 13.0 g sodium dodecyl sulfonate into deionized water containing 120-ml-240 ml to obtain sodium dodecyl sulfonate solution;
(4) Preparation of SDSO intercalated CuMgAl hydrotalcite-like precursor
Taking the sodium dodecyl sulfate solution prepared in the step (3) to N 2 In the four-neck round-bottom flask, the round-bottom flask is fixed in a magnetic water bath kettle, the solution in the first dropping funnel and the solution in the second dropping funnel are slowly dropped into the round-bottom flask under magnetic stirring, and the dropping speed of the mixed salt solution is controlled to be 2-3 ml min -1 The pH value of the solution is maintained to be 9-10 by adjusting the dropping speed of the sodium hydroxide solution; after the titration is finished, the temperature of the magnetic water bath kettle is increased to 65 ℃ for crystallization 12-48 h; filtering, washing and drying to obtain a SDSO intercalated CuMgAl hydrotalcite-like precursor CuMgAl-SDSO-LDH;
(5) Preparation of CuMgAl-SDSO-LDO denitration catalyst
And (3) roasting the precursor obtained in the step (4) under the nitrogen atmosphere for 4-6 h, and roasting in air for 3-5 h to obtain the CuMgAl-SDSO-LDO denitration catalyst.
2. Hydrotalcite-based carbon doped copper magnesium aluminum complex according to claim 1A mixed oxide catalyst characterized by: in the step (1), mg is added 2+ With Al 3+ The ratio of the amounts of the substances is 1:1-2:1.
3. The hydrotalcite-based carbon doped copper magnesium aluminum composite oxide catalyst according to claim 1, wherein: in the step (4), the volume ratio of the added SDSO solution to the mixed salt solution is 0.5-1: 1.
4. the hydrotalcite-based carbon doped copper magnesium aluminum composite oxide catalyst according to claim 1, wherein: in the step (4), the whole precursor preparation process is carried out in N 2 In an atmosphere.
5. The hydrotalcite-based carbon doped copper magnesium aluminum composite oxide catalyst according to claim 1, wherein: in the step (5), the flow rate of the introduced nitrogen is controlled to be 60 ml min -1 ～100 ml▪min -1 The method comprises the steps of carrying out a first treatment on the surface of the The temperature programming rate is 2-10 ℃ for min -1 The method comprises the steps of carrying out a first treatment on the surface of the The roasting temperature is 400-600 ℃ under the nitrogen atmosphere; the baking temperature is set to 350-500 ℃ in the air.
6. A hydrotalcite-based carbon doped copper magnesium aluminum composite oxide catalyst according to claim 1 in NH 3 -application in SCR.
7. The use according to claim 6, 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 composition of the reaction gas is as follows: 500 ppm NO,500 ppm NH 3 ，100 ppm SO 2 ，5% O 2 ，N 2 As balance gas, the space velocity of the reaction gas is 45000 h -1 The method comprises the steps of carrying out a first treatment on the surface of the The catalytic reaction is carried out at 150-270 ℃, and the activity data is collected after the reaction reaches equilibrium;
denitration activity test and sulfur resistance evaluation show that the CuMgAl-SDSO-LDO catalyst has high NH at 150-270 DEG C 3 SCR activitySex, good N 2 Selectivity and strong sulfur resistance.
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