CN113351152A - Nitrogen oxide absorption composite material - Google Patents
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- CN113351152A CN113351152A CN202110445133.XA CN202110445133A CN113351152A CN 113351152 A CN113351152 A CN 113351152A CN 202110445133 A CN202110445133 A CN 202110445133A CN 113351152 A CN113351152 A CN 113351152A
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 238000010521 absorption reaction Methods 0.000 title claims description 30
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000000654 additive Substances 0.000 claims abstract description 10
- 239000002250 absorbent Substances 0.000 claims abstract description 9
- 230000002745 absorbent Effects 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims description 12
- 150000001340 alkali metals Chemical class 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 8
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 6
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 6
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 150000002910 rare earth metals Chemical class 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052582 BN Inorganic materials 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000012621 metal-organic framework Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000006104 solid solution Substances 0.000 claims description 2
- 239000006096 absorbing agent Substances 0.000 claims 9
- 238000010438 heat treatment Methods 0.000 abstract description 13
- 238000009472 formulation Methods 0.000 abstract 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 20
- 239000004317 sodium nitrate Substances 0.000 description 10
- 235000010344 sodium nitrate Nutrition 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000007873 sieving Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical group [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000011358 absorbing material Substances 0.000 description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium nitrate Inorganic materials [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 150000002697 manganese compounds Chemical class 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical class [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01D53/02—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 by adsorption, e.g. preparative gas chromatography
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
Abstract
The invention relates to a formulation for a nitrogen oxide absorbing composite material, which comprises a main absorbing composite material, a carrier composed of a large specific surface material and related additives. The nitrogen oxide absorbent material can absorb a large amount of NOx within the oxygen concentration range of 0-21% and the temperature range from room temperature to 400 ℃, and can completely and reversibly release the absorbed nitrogen oxide under the heating condition.
Description
Technical Field
The invention relates to a nitrogen oxide absorption composite material which is suitable for efficiently absorbing and storing low-concentration nitrogen oxide under the conditions of wider oxygen concentration and temperature and can completely and reversibly release nitrogen oxide under the heating condition.
Background
Nitrogen oxides (mainly nitrogen monoxide and nitrogen dioxide) are one of the main pollutants in the atmosphere at present, and the main sources of the nitrogen oxides are automobile exhaust and exhaust emissions of various chemical enterprises. It has great harm to human health, and also can destroy the ozone layer, cause acid rain and the like, destroy the ecological environment, so it must be eliminated from various emission sources. Considering that in some cases the composition or temperature of the emitted exhaust gas components are not suitable for direct catalytic reduction of nitrogen oxides therein, it may be considered to absorb and store them from the exhaust gas and then subsequently utilize or convert them to non-polluting substances.
The nitrogen oxide absorbing materials reported at present mainly focus on various noble metal-based materials, such as Pt, Pd, Rh, etc., and the main principle is that these noble metals have strong chemical adsorption effect on nitrogen oxide, and can stably adsorb a certain amount of nitrogen oxide molecules at low temperature (Applied Catalysis A: General, Volume 570, Pages 1-14). However, the adsorption amount of nitrogen oxides is in one-to-one correspondence to the number of adsorption positions of the precious metals, and if the adsorption amount is increased, the loading amount of the precious metals can be increased, the dispersion degree of the precious metals is reduced, the cost is high, and the challenge is large; meanwhile, in practical application, the emission of tail gas is usually accompanied with the emission of carbon monoxide and higher water vapor, and these substances and nitrogen oxides generate competitive adsorption on the surface of noble metals, so that the absorption amount of the materials to the nitrogen oxides is further reduced. Therefore, there is a need for an absorbent having a wide application range, a large absorption capacity and a low cost.
The invention relates to a non-noble metal-based nitrogen oxide absorbing material, which can absorb a large amount of nitrogen oxide in the environment with wider oxygen concentration, wider temperature range, high CO concentration and high water vapor concentration and has very good application prospect.
Disclosure of Invention
The nitride absorption material provided by the invention consists of a main body and an additive; the composite material consists of a main absorption composite material and an additive; the main absorption composite material consists of alkali metal-containing alkaline earth metal, various or different valence manganese compounds and rare earth element compounds; the mass ratio of the material main body to the additive is in the range of 200:1 to 1: 100.
The main absorption composite material mainly comprises a certain amount of alkali metal or alkali metal-containing compound or alkaline earth metal compound, manganese element compounds with different valence states and rare earth element compounds. Wherein the alkali metal or alkali metal-containing compound or alkaline earth metal compound is hydroxide, nitrate, nitrite and other compounds of the metals, and the mass ratio of the alkali metal or alkali metal-containing compound or alkaline earth metal compound in the main absorption composite material is 0-50%.
The manganese compound containing different valence states can be manganese oxide and can be obtained by pretreating a main composite material. The precursor can be permanganate, manganate, nitrate, manganese oxides (MnO2, Mn3O4, Mn2O3, MnO and the like) and hydroxides and the like with different valence states, and the mass ratio range of the precursor in the main absorption composite material is 0-99%.
The rare earth element compound is one or more rare earth element oxides, and the oxides can be directly used as commercial products, wherein the commercial products comprise single rare earth metals such as CeO2, ZrO2, ZrxPr1-xO2(0< x <1), ZrxCe1-xO2(0< x <1) and oxides of more than two rare earth metals; it can also be obtained by the pretreatment of the main composite material, and the precursor can be various compounds or mixtures containing rare earth elements. The mass ratio of the main absorbent composite material is 0-99%.
After the main composite material is pretreated (the pretreatment is a common pretreatment method at present), a certain composite structure can be formed, including but not limited to forming a mixed oxide or solid solution structure; may also form M2O/AMO-MnOx-REMOxA quaternary and higher poly oxide of (wherein M)2O is an alkali metal oxide, AMO is an alkaline earth metal oxide, REMOxIs a mixture of one or more than two rare earth metal oxides or the oxides of a plurality of rare earth metals.
The additive is a carrier and/or auxiliary material that can enhance the performance of the primary absorbent composite. In general, the carrier with a large specific surface can increase the effective use area of the main composite material and enhance the stability of the main composite material; and the performance of the material can be obviously improved by adding a small amount of auxiliary agent. The carrier is one or the combination of more than two of materials with large specific surface area, such as carbon materials, molecular sieves, metal organic framework materials, boron nitride, magnesium oxide, aluminum oxide and the like. The auxiliary agent is a mixture of one or more compounds consisting of alkali metal and/or alkaline earth metal. The mass ratio of the main absorbent composite to the above-mentioned additives preferably ranges from 200:1 to 1: 100.
The nitrogen oxide absorption composite material can absorb low-concentration nitrogen oxide from various environments, and the absorption reaction conditions can be as follows: the reaction pressure is between 0bar and 10bar, the absorption temperature is between room temperature and 400 ℃, the oxygen concentration required by the reaction is between 0 and 21 percent, the water vapor concentration is between 0 percent and 15 percent, and the reaction space velocity is between 500 h and 500000h-1。
Description of the attached tables
Attached table 1: the composite absorbing material prepared by different methods has the capability of absorbing and releasing nitrogen oxides under different temperature conditions. The absorption capacity at each temperature is the NO of the material under the constant temperature conditionxMaximum absorption amount of (c); the desorption amount is that NO in the material is heated to 500 ℃ after the material fully absorbs the nitrogen oxide at 300 DEG CxThe amount of (a) released.
Detailed Description
The following specific examples are presented to further illustrate the invention and are not intended to limit the scope of the invention as defined by the appended claims.
The first embodiment is as follows:
adding Mn (NO)3)2,Ce(NO3)3Mixing according to a certain proportion, dissolving with deionized water, adding a certain amount of citric acid, stirring for 2h, heating to volatilize water under the stirring action, transferring to a muffle furnace, heating from room temperature to 600 ℃ at the heating rate of 10 ℃/min, and keeping at the temperature of more than 600 ℃ for 5h to finally obtain the MnOx-CeO2 mixed oxide. After pulverizing, the solution impregnation method is to load sodium nitrate on the solid by using sodium nitrate solution, after the solution is volatilized, the solution is transferred to a muffle furnace, and the temperature is raised from room temperature to 600 ℃ at the temperature raising rate of 10 ℃/min and is kept for 5 hours above 600 ℃. This material is labeled composite 1. Grinding, tabletting again, sieving and granulating, and testing the absorption capacity and the release capacity of the powder on a fixed bed activity evaluation device for nitrogen oxides at different temperatures. The reaction conditions and associated results are listed in table 1.
Example two:
following the procedure of example one, the sodium nitrate solution was replaced with potassium nitrate and the resulting material was labeled composite 2. Grinding, tabletting again, sieving and granulating, and testing the absorption capacity and the release capacity of the powder on a fixed bed activity evaluation device for nitrogen oxides at different temperatures. The reaction conditions and associated results are listed in table 1.
Example three:
according to the procedure of example oneNaNO3,Mn(NO3)2,Ce(NO3)3Mixing according to a certain proportion, dissolving with deionized water, adding a certain amount of citric acid, stirring for 2h, heating under stirring to volatilize water, transferring to muffle furnace, heating from room temperature to 600 deg.C at a heating rate of 10 deg.C/min, and maintaining at 600 deg.C for 5h to obtain Na2O-MnOx-CeO2This material is denoted composite material 3. Grinding, tabletting again, sieving and granulating, and testing the absorption capacity and the release capacity of the powder on a fixed bed activity evaluation device for nitrogen oxides at different temperatures. The reaction conditions and associated results are listed in table 1.
Example four:
following the procedure of example three, the sodium nitrate solution was replaced with potassium nitrate and the resulting material was labeled composite 4. Grinding, tabletting again, sieving and granulating, and testing the absorption capacity and the release capacity of the powder on a fixed bed activity evaluation device for nitrogen oxides at different temperatures. The reaction conditions and associated results are listed in table 1.
Example five:
adding Mn (NO)3)2Dissolving with deionized water, and adding a certain amount of commercial CeO2(Sigma-Aldrich,nanopowder,<25nm particle size (BET)) and stirred well, was slowly added dropwise to the above mixture with excess NaOH solution, then stirred for 2h, the precipitate was filtered and washed, dried and treated in a muffle furnace at 600 ℃ for 5 h.
Then, the solution impregnation method is used for loading sodium nitrate on the solid by using a sodium nitrate solution, and after the solution is volatilized, the solution is transferred to a muffle furnace, is heated to 600 ℃ from room temperature at a heating rate of 10 ℃/min, and is kept for 5 hours at the temperature of more than 600 ℃. This material is labeled composite 5. Grinding, tabletting again, sieving and granulating, and testing the absorption capacity and the release capacity of the powder on a fixed bed activity evaluation device for nitrogen oxides at different temperatures. The reaction conditions and associated results are listed in table 1.
Example six:
adding Mn (NO)3)2Dissolving with deionized water, and adding certain amount of commercialized Ce0.8Pr0.2O2(Sigma-Aldrich,nanopowder,<100nm particle size) and stirred well, slowly added dropwise to the above mixture with excess NaOH solution, then stirred for 2h, the precipitate filtered and washed, dried and treated in a muffle furnace at 600 ℃ for 5 h. Then, the solution impregnation method is used for loading sodium nitrate on the solid by using a sodium nitrate solution, and after the solution is volatilized, the solution is transferred to a muffle furnace, is heated to 600 ℃ from room temperature at a heating rate of 10 ℃/min, and is kept for 5 hours at the temperature of more than 600 ℃. This material is labeled composite 6. Grinding, tabletting again, sieving and granulating, and testing the absorption capacity and the release capacity of the powder on a fixed bed activity evaluation device for nitrogen oxides at different temperatures. The reaction conditions and associated results are listed in table 1.
Example seven:
adding NaNO3,Mn(NO3)2,Ce(NO3)3Mixing according to a certain proportion, dissolving with deionized water, adding a small amount of ZSM-5 molecular sieve, performing ultrasonic treatment for 10min, adding a certain amount of citric acid, stirring for 2h, heating under stirring to volatilize water, transferring to a muffle furnace, heating from room temperature to 600 ℃ at a heating rate of 10 ℃/min, and keeping at the temperature of above 600 ℃ for 5h to finally obtain MnOx-CeO2Mixed oxides. After pulverizing, the solution impregnation method is to load sodium nitrate on the solid by using sodium nitrate solution, after the solution is volatilized, the solution is transferred to a muffle furnace, and the temperature is raised from room temperature to 600 ℃ at the temperature raising rate of 10 ℃/min and is kept for 5 hours above 600 ℃. This material is labeled composite 7. Grinding, tabletting again, sieving and granulating, and testing the absorption capacity and the release capacity of the powder on a fixed bed activity evaluation device for nitrogen oxides at different temperatures. The reaction conditions and associated results are listed in table 1.
Attached table of the specification
Attached table 1:
Claims (10)
1. a nitrogen oxide absorbent composite characterized by: the composite material consists of a main absorption composite material and an additive; the main absorption composite material consists of an alkali metal or alkaline earth metal compound, manganese oxides with different valence states and rare earth element oxides; the mass ratio of the main absorbent composite to the additive ranges from 200:1 to 1: 100.
2. A nitrogen oxide absorber composite as claimed in claim 1 wherein: the alkali metal or alkaline earth metal compound is hydroxide, nitrate or nitrite of the metal, and the mass ratio of the alkali metal or alkaline earth metal compound in the main absorption composite material is 0-50%.
3. A nitrogen oxide absorber composite as claimed in claim 1 wherein: the manganese oxides with different valence states can be obtained by pretreating the main composite material, precursors of the manganese oxides can be permanganate, manganate, nitrate, manganese oxides or hydroxides with different valence states and the like, and the mass ratio range of the manganese oxides in the main absorption composite material is 0-99%.
4. A nitrogen oxide absorber composite as claimed in claim 1 wherein: the rare earth element compound is one or more rare earth element oxides, and the oxides can be directly used in commercial products, wherein the commercial products comprise CeO2,ZrO2,ZrxPr1-xO2(0<x<1)，ZrxCe1-xO2(0<x<1) Oxides of single rare earth metal and more than two rare earth metals; the composite material can also be obtained by pretreating a main composite material, and the precursor of the composite material can be various compounds or mixtures containing rare earth elements, and the mass ratio of the precursor in the main absorption composite material ranges from 0% to 99%.
5. A nitrogen oxide absorber composite as claimed in claim 1 wherein: the primary absorbent composite material, after being mixed and pretreated, forms a composite structure including, but not limited to, forming a mixed oxide or solid solution structure.
6. The nitrogen oxide absorber composite of claim 1, wherein: the additive is a carrier and/or an auxiliary material which can enhance the performance of the main absorption composite material.
7. The nitrogen oxide absorber composite of claim 6, wherein: the carrier is a material with large specific surface area, such as one or a combination of more than two of carbon materials, molecular sieves, metal organic framework materials, boron nitride, magnesium oxide, aluminum oxide and the like.
8. The nitrogen oxide absorber composite of claim 6, wherein: the auxiliary agent is a mixture of one or more compounds consisting of alkali metals and/or alkaline earth metals.
9. The nitrogen oxide absorber composite of claim 1, wherein: the preferred range of mass ratio of the primary absorbent composite to the additive is 200:1 to 1: 100.
10. The use of a nitrogen oxide absorber composite as claimed in claim 1 wherein: the absorption reaction conditions are as follows: the reaction pressure is between 0bar and 10bar, the reaction temperature is between room temperature and 450 ℃, the concentration of oxygen required by the reaction is between 0 and 30 percent, the concentration of water vapor is between 0 percent and 15 percent, and the reaction space velocity is between 1000 and 500000h-1。
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| CN202110445133.XA CN113351152A (en) | 2021-04-24 | 2021-04-24 | Nitrogen oxide absorption composite material |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1556730A (en) * | 2001-09-19 | 2004-12-22 | 约翰逊马西有限公司 | Lean NOx trap/conversion catalyst |
| CN101610844A (en) * | 2006-11-29 | 2009-12-23 | 巴斯福催化剂公司 | The NO of resistant to thermal aging xStorage material and trap |
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