CN108993516B - Composite oxide catalyst with nickel-titanium hydrotalcite as precursor and preparation method and application thereof - Google Patents
Composite oxide catalyst with nickel-titanium hydrotalcite as precursor and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 239000002243 precursor Substances 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- HZEWFHLRYVTOIW-UHFFFAOYSA-N [Ti].[Ni] Chemical compound [Ti].[Ni] HZEWFHLRYVTOIW-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910001000 nickel titanium Inorganic materials 0.000 title claims abstract description 19
- 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 16
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 16
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004202 carbamide Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000000967 suction filtration Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 12
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000009833 condensation Methods 0.000 claims abstract description 9
- 230000005494 condensation Effects 0.000 claims abstract description 9
- 238000010992 reflux Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 3
- 239000003599 detergent Substances 0.000 claims abstract description 3
- 239000012716 precipitator Substances 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 12
- 229910001868 water Inorganic materials 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 6
- 239000012495 reaction gas Substances 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 8
- 239000011593 sulfur Substances 0.000 abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 5
- 229910021529 ammonia Inorganic materials 0.000 abstract description 2
- 231100000572 poisoning Toxicity 0.000 abstract description 2
- 230000000607 poisoning effect Effects 0.000 abstract description 2
- 239000012153 distilled water Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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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- B01D53/34—Chemical or biological purification of waste gases
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/64—Pore diameter
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Abstract
The invention discloses a composite oxide catalyst taking nickel-titanium hydrotalcite (NiTi-LDH) as a precursor, and a preparation method and application thereof, belonging to the field of pollution control and technology. The method takes nickel nitrate hexahydrate and butyl titanate as raw materials, urea as a precipitator, deionized water as a solvent and a detergent, and prepares a NiTi-LDH precursor through the steps of solution preparation, oil bath condensation reflux, suction filtration washing, drying and the like; the precursor is roasted and pressed into sheets to prepare the nickel-titanium composite oxide (NiTi-LDO) denitration catalyst. The invention also provides the selective catalytic reduction (NH) of the catalyst in ammonia gas3-SCR) denitration reaction. The NiTi-LDO denitration catalyst prepared by the method has NO in the range of 240-360 DEG CxConversion rate over 90%, N2The selectivity is close to 95 percent, and the sulfur poisoning resistance is better.
Description
Technical Field
The invention relates to a composite oxide catalyst taking nickel-titanium hydrotalcite as a precursor, and a preparation method and application thereof, and belongs to the technical field of preparation of denitration catalysts.
Background
With the development of the coal burning industry and the rapid increase in the holding capacity of motor vehicles, a large amount of fossil fuels are consumed, resulting in Nitrogen Oxides (NO)x) Excessive discharge causes serious harm to human health and living environment. With the enhancement of environmental awareness and the stricter of laws and regulations, research and governance of NOxHas become an important content in the international environmental protection field. NH (NH)3The SCR technology becomes a mainstream denitration technology at home and abroad due to the mature and efficient characteristics of the SCR technology, and the key for the performance of the SCR technology is the preparation of a suitable catalyst under the operating condition. At present, vanadium-titanium catalysts are widely used, but the negative effects caused by component toxicity in the post-treatment process cannot be ignored. Therefore, the development of a novel, environment-friendly and efficient catalyst system is still a key topic in the research field of denitration.
Disclosure of Invention
The invention aims to provide a composite oxide catalyst taking nickel-titanium hydrotalcite as a precursor and a preparation method and application thereof, and particularly takes the advantages of Ni and Ti as entry points to be synergistically exerted, NiTi-LDH is prepared in situ to effectively assemble Ni and Ti, and the redox property and the acid-base property of the obtained composite metal oxide catalyst are optimized by adjusting the roasting temperature and the proportion of Ni and Ti, so that the composite oxide catalyst with good activity and N-nickel hydrotalcite is prepared2NH with high selectivity and strong water and sulfur resistance3-an SCR catalyst.
The reason for selecting Ni and Ti metal in the invention is that: the Ni-based oxide catalyst has the characteristics of rich acid sites, strong oxidation-reduction capability and environmental friendliness, and is applied to NH3SCR denitration reaction, N thereof2The selectivity is close to 100 percentCan effectively avoid N2And secondary generation of harmful gases such as O and the like. TiO 22The catalyst is an excellent catalyst carrier, has the characteristics of large specific surface area, low price and no toxicity, and simultaneously has good sulfur resistance. Hydrotalcite-like compounds (LDHs) are excellent precursors for preparing composite metal oxide (LDO) catalysts, and the prepared composite oxides usually have high specific surface area and regular ordered mesoporous structure, and the lattice confinement effect of the composite oxides can effectively promote the dispersion of active components and is beneficial to the electron transfer among metal ions. The invention prepares the NH with excellent catalytic performance and environmental friendliness by effectively assembling Ni and Ti by means of the hydrotalcite-like precursor and cooperatively playing the roles of the Ni and the Ti3-an SCR denitration catalyst.
The invention provides a composite oxide catalyst taking nickel-titanium hydrotalcite as a precursor, which takes nickel nitrate hexahydrate and butyl titanate as raw materials, urea as a precipitator, deionized water as a solvent and a detergent, and prepares a NiTi-LDH precursor through the steps of solution preparation, oil bath condensation reflux reaction, suction filtration washing and drying; the precursor is roasted and pressed into sheets to prepare the nickel-titanium composite oxide (NiTi-LDO) catalyst.
The invention provides a preparation method of the composite oxide catalyst taking nickel-titanium hydrotalcite as a precursor, which comprises the following steps:
(1) preparing a mixed solution: weighing nickel nitrate hexahydrate and urea in a round-bottom flask according to a proportion, weighing butyl titanate, adding deionized water, and magnetically stirring until the nickel nitrate hexahydrate and the urea are fully dissolved;
in the step, 2-3 mL of ethanol is dripped to promote the dissolution of the raw materials;
(2) preparation of NiTi-LDH: placing the mixed solution prepared in the step (1) into a magnetic stirring pot, carrying out oil bath condensation reflux, dissolving at 80-90 ℃ for 3-12 h, adjusting the oil bath temperature to 100-110 ℃, reacting for 12-48 h to obtain a NiTi-LDH turbid solution, and measuring the pH value of the obtained turbid solution;
(3) and (3) suction filtration and washing: carrying out suction filtration and water washing on the turbid liquid obtained in the step (2) to be neutral, and drying at the temperature of 60-80 ℃ overnight to obtain a NiTi-LDH precursor;
(4) roasting: and (3) roasting the prepared NiTi-LDH precursor in a muffle furnace to obtain the nickel-titanium composite oxide NiTi-LDO catalyst.
In the preparation method, in the step (1), the total concentration of the metal cations in the mixed solution is 0.0065 mol L-1And is andc(Ni2+): c(Ti4+) Controlling the ratio to be 2:1-6: 1; whereinc(Ni2+) Refers to the quantity concentration of nickel ion substances in the mixed solution,c(Ti4+) The quantity concentration of the titanium ion substances in the mixed solution is referred to; n (NO)3 -) N (urea) =1:1-2:1, wherein N (NO)3 -) Refers to NO in the mixed solution3 -N (urea) means the amount of urea in the mixed solution.
In the preparation method, in the step (2), the pH value of the turbid liquid is controlled to be 7.0-10.0.
In the preparation method, in the step (4), the obtained NiTi-LDH precursor is roasted in the air atmosphere, the roasting temperature is 400-.
The invention provides the selective catalytic reduction (NH) of the composite oxide catalyst taking the nickel-titanium hydrotalcite as the precursor in ammonia gas3-SCR) denitration reaction.
When in use, the catalyst is firstly tabletted: placing a NiTi-LDO catalyst sample in a tablet press, keeping the NiTi-LDO catalyst sample for 5-10 min under 20 MPa, grinding the NiTi-LDO catalyst sample by using a pestle, and screening the NiTi-LDO catalyst sample into particles of 40-60 meshes, wherein the particles can be directly applied to catalytic reaction;
the catalytic reaction tests were carried out in a fixed bed continuous flow quartz reactor. The granularity of the catalyst is 40-60 meshes, and the dosage is 0.29-0.35 g; the reaction gas composition is: [ NO ]]=600 ppm，[NH3]=600 ppm，[O2]=5.0 vol%，[SO2]=0 or 100 ppm, [ H ]2O]=0 or 10.0 vol%, N2As balance gas, the space velocity of the reaction gas is 45000 h-1(ii) a The catalytic reaction was carried out at 90-450 ℃ and activity data were collected after the reaction reached equilibrium. The product was analyzed by Thermofisiher IS10 FTIR detection, NO conversion and N2The selectivity is calculated by the following formula:
wherein [ NO ]]in、[NH3]inRespectively NO and NH at the inlet of the reactor3The concentration of the gas; [ NO ]]out、[NO2]out、[N2O]outRespectively indicating reactor outlet NO, NO2And N2The concentration of O.
The invention uses X-ray diffractometer to characterize and analyze the crystal structures of hydrotalcite-like precursor and roasted product.
The invention utilizes an automatic adsorption instrument to carry out sample determination on the calcined product of the hydrotalcite-like compound. The specific surface area was analyzed by the BET method, and the pore size and pore size distribution were analyzed by the BJH method.
The invention has the beneficial effects that:
(1) the invention prepares the NiTi-LDH precursor by means of urea uniform coprecipitation method in an oil bath condensation reflux mode, and prepares the NiTi-LDO catalyst by roasting, wherein the NiTi-LDO catalyst has larger specific surface area, regular and ordered mesoporous structure and uniformly dispersed active centers.
(2) The NiTi-LDO catalyst prepared by the invention is applied to NH3SCR reaction with over 90% catalytic activity in the temperature range of 240 ℃ and 360 ℃, N close to 95%2Selectivity and good sulfur poisoning resistance.
(3) The catalyst provided by the invention has the advantages of simple preparation method, low cost and environmental friendliness.
Drawings
FIG. 1 is the XRD patterns of NiTi-LDH and NiTi-LDO in example 1.
FIG. 2 shows the NOx conversion and N of the NiTi-LDO catalyst in example 22Selectivity curve: a represents NOx conversion and b represents N2Selectivity profile.
FIG. 3 is a graph showing the water and sulfur resistance of the NiTi-LDO catalyst of example 2.
FIG. 4 is the nitrogen adsorption/desorption curve and the pore size distribution diagram of NiTi-LDO in example 3.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
Example 1: (Ni: Ti =2:1, firing temperature 600 ℃ C.)
(1) Preparing a mixed solution: weighing 1.3 g of nickel nitrate hexahydrate and 1.1 g of urea by using an analytical balance, weighing 0.8 mL of butyl titanate and 100 mL of distilled water by using a measuring cylinder, respectively adding the butyl titanate and the distilled water into a 250 mL round-bottom flask, dropwise adding 3 mL of absolute ethyl alcohol by using a rubber head dropper, and magnetically stirring until the mixture is fully and uniformly mixed.
(2) Preparation of NiTi-LDH: and (3) placing the prepared mixed solution into a magnetic stirring pot, carrying out oil bath condensation reflux, dissolving at 90 ℃ for 12 hours, adjusting the oil bath temperature to 100 ℃, and reacting for 48 hours to obtain the NiTi-LDH turbid solution.
(3) And (3) suction filtration and washing: and (3) carrying out suction filtration and water washing on the turbid solution obtained in the step (2) to neutrality, and drying at the temperature of 60 ℃ overnight to obtain a NiTi-LDH precursor.
(4) Preparation of NiTi-LDO: and placing the NiTi-LDH powder in a crucible, placing the crucible in a muffle furnace, and roasting for 3 h at 600 ℃ to finally obtain the NiTi-LDO catalyst.
Performing X-ray diffraction analysis on the crystal fine powder products obtained in the steps (3) and (4), wherein the diffraction spectrogram is shown as an attached figure 1, and the NiTi-LDH spectrogram shows a special hydrotalcite diffraction peak and has a single crystal phase; the spectrogram of NiTi-LDO shows that the oxide of the NiTi-LDO mainly consists of NiO and TiO2And NiTiO3The composition and the crystallinity are higher.
Example 2: (Ni: Ti =4:1, firing temperature 500 ℃ C.)
(1) Preparing a mixed solution: weighing 1.5 g of nickel nitrate hexahydrate and 1.1 g of urea by using an analytical balance, weighing 0.5 mL of butyl titanate and 100 mL of distilled water by using a measuring cylinder, respectively adding the butyl titanate and the distilled water into a 250 mL round-bottom flask, dropwise adding 3 mL of absolute ethyl alcohol by using a rubber head dropper, and magnetically stirring until the mixture is fully and uniformly mixed.
(2) Preparation of NiTi-LDH: and (3) placing the prepared mixed solution into a magnetic stirring pot, carrying out oil bath condensation reflux, dissolving at 90 ℃ for 12 hours, adjusting the oil bath temperature to 100 ℃, and reacting for 48 hours to obtain the NiTi-LDH turbid solution.
(3) And (3) suction filtration and washing: and (3) carrying out suction filtration and water washing on the turbid solution obtained in the step (2) to neutrality, and drying at the temperature of 60 ℃ overnight to obtain a NiTi-LDH precursor.
(4) Preparation of NiTi-LDO: and placing the NiTi-LDH powder in a crucible, placing the crucible in a muffle furnace, and roasting for 3 hours at 500 ℃ to finally obtain the NiTi-LDO catalyst.
The product is used for denitration reaction, and is prepared into 40-60 mesh granules through tabletting.
(5) 0.38 g of the particles obtained in step (4) were weighed and the catalytic reaction test was carried out in a fixed bed continuous flow quartz reactor. The reaction gas composition is: [ NO ]]=600 ppm，[NH3]=600 ppm，[O2]=5.0 vol%, N2As balance gas, the space velocity of the reaction gas is 45000 h-1. The catalytic reaction was carried out at 90-450 ℃ and activity data were collected after the reaction reached equilibrium. The product was analyzed by Thermofisiher IS10 FTIR detection, NO conversion and N2The selectivity is calculated by the following formula:
wherein [ NO ]]in，[NH3]inRespectively NO and NH at the inlet of the reactor3The concentration of the gas; [ NO ]]out，[NO2]out，[N2O]outRespectively meaning reactor outlet NO, NO2And N2The concentration of O.
The catalytic activity results are shown in FIG. 2, where FIG. 2 shows the NOx conversion and N for the NiTi-LDO catalyst of this example2Selectivity curve: a represents NOx conversion and b represents N2Selectivity profile. The figure shows that: the catalyst has good catalytic performance, and has more than 90% of catalytic activity and N close to 95% under the window of 240-plus-360 DEG C2And (4) selectivity.
(6) And (3) weighing 0.38 g of the particles obtained in the step (4), filling the particles into a quartz tube, and evaluating the sulfur resistance and the water resistance of the catalyst. The conditions are as follows: test temperature 240 ℃; n is a radical of2For balance gas, [ NO ]]=600 ppm，[NH3]=600 ppm，[O2]=5.0 vol%，[SO2]=100 ppm，[H2O]=10 vol%; the space velocity of the mixed gas is 45000 h-1. The curve of the sulfur resistance and the water resistance is shown in the attached figure 3. First, 100 ppm SO was introduced2The catalyst NOx conversion decreased from 92.5% to 89.8%, followed by 10 vol% H2The conversion rate of O and NOx is reduced from 89.8 percent to 85.1 percent and is only reduced by about 4 percent, and when SO is removed2And H2After O, the catalyst NOx conversion gradually returns to the initial value. The test result shows that the NiTi-LDO catalyst has good water resistance and sulfur resistance.
Example 3: (Ni: Ti =6:1, firing temperature 400 ℃ C.)
(1) Preparing a mixed solution: weighing 1.6 g of nickel nitrate hexahydrate and 1.1 g of urea by using an analytical balance, weighing 0.3 mL of butyl titanate and 100 mL of distilled water by using a measuring cylinder, respectively adding the butyl titanate and the distilled water into a 250 mL round-bottom flask, dropwise adding 3 mL of absolute ethyl alcohol by using a rubber head dropper, and magnetically stirring until the mixture is fully and uniformly mixed.
(2) Preparation of NiTi-LDH: and (3) placing the prepared mixed solution into a magnetic stirring pot, carrying out oil bath condensation reflux, dissolving at 90 ℃ for 12 hours, adjusting the oil bath temperature to 100 ℃, and reacting for 48 hours to obtain the NiTi-LDH turbid solution.
(3) And (3) suction filtration and washing: and (3) carrying out suction filtration and water washing on the turbid solution obtained in the step (2) to neutrality, and drying at the temperature of 60 ℃ overnight to obtain a NiTi-LDH precursor.
(4) Preparation of NiTi-LDO: and placing the NiTi-LDH powder in a crucible, placing the crucible in a muffle furnace, and roasting for 3 h at 400 ℃ to finally obtain the NiTi-LDO catalyst.
(5) The particles obtained in step (4) were subjected to specific surface analysis, specific surface area analysis by the BET method, and pore size distribution analysis by the BJH method, and the results are shown in FIG. 4. As can be seen, the NiTi-LDO catalyst has a large specific surface area (225 m)2 g-1) Has obvious mesoporous structure and uniform pore size distribution (1-4 nm).
Claims (8)
1. A method for preparing a composite oxide catalyst by taking nickel-titanium hydrotalcite as a precursor is characterized by comprising the following steps: preparing a NiTi-LDH precursor by using nickel nitrate hexahydrate and butyl titanate as raw materials, urea as a precipitator, deionized water as a solvent and a detergent through the steps of solution preparation, oil bath condensation reflux reaction, suction filtration washing and drying; roasting and tabletting the precursor to prepare the nickel-titanium composite oxide catalyst;
the preparation method comprises the following steps:
(1) preparing a mixed solution: weighing nickel nitrate hexahydrate and urea in a round-bottom flask according to a proportion, weighing butyl titanate, adding deionized water, and magnetically stirring until the nickel nitrate hexahydrate and the urea are fully dissolved;
(2) preparation of NiTi-LDH: placing the mixed solution prepared in the step (1) into a magnetic stirring pot, carrying out oil bath condensation reflux, dissolving at 80-90 ℃ for 3-12 h, adjusting the oil bath temperature to 100-110 ℃, reacting for 12-48 h to obtain a NiTi-LDH turbid solution, and measuring the pH value of the obtained turbid solution;
(3) and (3) suction filtration and washing: carrying out suction filtration and water washing on the turbid liquid obtained in the step (2) to be neutral, and drying at the temperature of 60-80 ℃ overnight to obtain a NiTi-LDH precursor;
(4) roasting: and (3) roasting the prepared NiTi-LDH precursor in a muffle furnace to obtain the nickel-titanium composite oxide NiTi-LDO catalyst.
2. The method for preparing the composite oxide catalyst using the nickel titanium hydrotalcite as the precursor according to claim 1, wherein the method comprises the following steps: in the step (1), the total concentration of metal cations in the mixed solution is 0.0065 mol L-1And is andc(Ni2+): c(Ti4+) Controlling the ratio to be 2:1-6: 1; whereinc(Ni2+) Refers to the quantity concentration of nickel ion substances in the mixed solution,c(Ti4+) The quantity concentration of the titanium ion substances in the mixed solution is referred to; n (NO)3 -) N (urea) =1:1-2:1, wherein N (NO)3 -) Refers to NO in the mixed solution3 -N (urea) means the amount of urea in the mixed solution.
3. The method for preparing the composite oxide catalyst using the nickel titanium hydrotalcite as the precursor according to claim 1, wherein the method comprises the following steps: in the step (1), 2-3 mL of ethanol is added dropwise to promote the dissolution of the raw materials.
4. The method for preparing the composite oxide catalyst using the nickel titanium hydrotalcite as the precursor according to claim 1, wherein the method comprises the following steps: in the step (2), the pH value of the turbid liquid is controlled to be 7.0-10.0.
5. The method for preparing the composite oxide catalyst using the nickel titanium hydrotalcite as the precursor according to claim 1, wherein the method comprises the following steps: in the step (4), the obtained NiTi-LDH precursor is roasted in the air atmosphere, the roasting temperature is 400-700 ℃, and the roasting time is 2-5 h.
6. The application of the composite oxide catalyst prepared by the method of claim 1 and taking the nickel-titanium hydrotalcite as the precursor in the selective catalytic reduction denitration reaction of ammonia gas.
7. Use according to claim 6, characterized in that: when in use, the catalyst is firstly tabletted: placing a NiTi-LDO catalyst sample in a tablet press, keeping the NiTi-LDO catalyst sample for 5-10 min under 20 MPa, grinding the NiTi-LDO catalyst sample by using a pestle, and screening the NiTi-LDO catalyst sample into particles of 40-60 meshes, wherein the particles can be directly applied to catalytic reaction;
the catalytic reaction test is carried out in a fixed bed continuous flow quartz reactor; the granularity of the catalyst is 40-60 meshes, and the dosage is 0.29-0.35 g; the reaction gas composition is: [ NO ]]=600 ppm，[NH3]=600 ppm，[O2]=5.0 vol%，[SO2]=0 or 100 ppm, [ H ]2O]=0 or 10 vol%, N2As balance gas, the space velocity of the reaction gas is 45000 h-1(ii) a The catalytic reaction was carried out at 90-450 ℃ and activity data were collected after the reaction reached equilibrium.
8. Use according to claim 7, characterized in that: the resulting product was analyzed by Thermofisiher IS10 FTIR detection, NO conversion and N2The selectivity is calculated by the following formula:
wherein [ NO ]]in、[NH3]inRespectively NO and NH at the inlet of the reactor3The concentration of the gas; [ NO ]]out、[NO2]out、[N2O]outRespectively indicating reactor outlet NO, NO2And N2The concentration of O.
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