CN108607602B - Denitration catalyst resistant to alkali metal poisoning and preparation method thereof - Google Patents
Denitration catalyst resistant to alkali metal poisoning and preparation method thereof Download PDFInfo
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- CN108607602B CN108607602B CN201810267732.5A CN201810267732A CN108607602B CN 108607602 B CN108607602 B CN 108607602B CN 201810267732 A CN201810267732 A CN 201810267732A CN 108607602 B CN108607602 B CN 108607602B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 229910052783 alkali metal Inorganic materials 0.000 title claims abstract description 32
- 150000001340 alkali metals Chemical class 0.000 title claims abstract description 32
- 206010027439 Metal poisoning Diseases 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000002808 molecular sieve Substances 0.000 claims abstract description 45
- 230000003197 catalytic effect Effects 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- WCMHZFHLWGFVCQ-UHFFFAOYSA-N [Ba].[Mn] Chemical compound [Ba].[Mn] WCMHZFHLWGFVCQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005342 ion exchange Methods 0.000 claims abstract description 8
- 239000011148 porous material Substances 0.000 claims abstract description 7
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 238000010306 acid treatment Methods 0.000 claims description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- ZZCNKSMCIZCVDR-UHFFFAOYSA-N barium(2+);dioxido(dioxo)manganese Chemical compound [Ba+2].[O-][Mn]([O-])(=O)=O ZZCNKSMCIZCVDR-UHFFFAOYSA-N 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229910001414 potassium ion Inorganic materials 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical group OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- 229910001431 copper ion Inorganic materials 0.000 claims 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 description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 101100008649 Caenorhabditis elegans daf-5 gene Proteins 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- IXZOTKANSDQAHZ-UHFFFAOYSA-N manganese(ii) titanate Chemical group [O-2].[O-2].[O-2].[Ti+4].[Mn+2] IXZOTKANSDQAHZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 30
- 230000000694 effects Effects 0.000 abstract description 7
- 230000007246 mechanism Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 description 3
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- UJZQBMQZMKFSRV-RGKBJLTCSA-N (2s,3s)-4-[(e)-3-[(1r)-1-carboxy-2-(3,4-dihydroxyphenyl)ethoxy]-3-oxoprop-1-enyl]-2-(3,4-dihydroxyphenyl)-7-hydroxy-2,3-dihydro-1-benzofuran-3-carboxylic acid Chemical compound C([C@H](C(=O)O)OC(=O)\C=C\C=1C=2[C@H](C(O)=O)[C@H](OC=2C(O)=CC=1)C=1C=C(O)C(O)=CC=1)C1=CC=C(O)C(O)=C1 UJZQBMQZMKFSRV-RGKBJLTCSA-N 0.000 description 1
- UJZQBMQZMKFSRV-PHQFMFTGSA-N Lithospermic acid Natural products O([C@@H](C(=O)O)Cc1cc(O)c(O)cc1)C(=O)/C=C/c1c2[C@@H](C(=O)O)[C@H](c3cc(O)c(O)cc3)Oc2c(O)cc1 UJZQBMQZMKFSRV-PHQFMFTGSA-N 0.000 description 1
- NFOCYHUCMXEHDG-UHFFFAOYSA-N Monomethyl lithospermate Natural products COC(=O)C1C(C=2C=C(O)C(O)=CC=2)OC(C(=CC=2)O)=C1C=2C=CC(=O)OC(C(O)=O)CC1=CC=C(O)C(O)=C1 NFOCYHUCMXEHDG-UHFFFAOYSA-N 0.000 description 1
- -1 SAPO-34 Chemical compound 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- CDTSJTCJCHLEDD-UHFFFAOYSA-N barium(2+);manganese(2+);oxygen(2-) Chemical compound [O-2].[O-2].[Mn+2].[Ba+2] CDTSJTCJCHLEDD-UHFFFAOYSA-N 0.000 description 1
- 229910052601 baryte Inorganic materials 0.000 description 1
- 239000010428 baryte Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002498 deadly effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 231100000584 environmental toxicity Toxicity 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009993 protective function Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- STCJJTBMWHMRCD-UHFFFAOYSA-N salvianolic acid B Natural products OC(=O)C(Cc1ccc(O)c(O)c1)OC(=O)C=Cc2cc(O)c(O)c3OC(C(C(=O)OC(Cc4ccc(O)c(O)c4)C(=O)O)c23)c5ccc(O)c(O)c5 STCJJTBMWHMRCD-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical compound [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention relates to an alkali metal poisoning resistant denitration catalyst and a preparation method thereof. The key points of the invention are as follows: the novel alkali metal ion capturing method is used for fixing alkali metal ions in the pore channels of the manganese barium ore oxide through an ion exchange mechanism, so that the catalytic activity of the molecular sieve is not influenced, and the alkali metal poisoning resistance is greatly improved. The catalyst uses the molecular sieve to provide SCR catalytic activity and has the advantages of high activity, good selectivity, wide temperature window and the like. The alkaline metal ions are captured by utilizing the manganite oxide, so that the alkaline metal poisoning resistance of the catalyst is effectively improved. The method has the advantages of environmental friendliness, simple production process, suitability for large-scale industrial production and the like, and can be used for removing the nitrogen oxides discharged by fixed sources and mobile sources.
Description
Technical Field
The invention relates to an alkali metal poisoning resistant denitration catalyst and a preparation method thereof, in particular to a MnBa ore MnTi oxide reinforced Cu-SAPO-34 molecular sieve denitration catalyst and a preparation method thereof.
Background
Nitrogen oxide is a common atmospheric pollutant, and is known to cause acid rain, photochemical smog and haze and cause direct damage to the respiratory system of a human body. Currently, various technical means have been used to control the reduction of nitrogen oxide emissions, and Selective Catalytic Reduction (SCR) technology is the most mature of the commonly used nitrogen oxide removal technologies, among which NH is used3Catalytic technology studies are the most common for reducing agents. Since 1986, transition metal ion exchanged molecular sieve series catalysts have attracted increasing attention for their excellent catalytic performance. Among them, there have been many reports on the study of the CHA-type Cu-SSZ-13 molecular sieve. In recent times, Cu-SAPO-34 catalyst was considered to be a very excellent catalyst due to its better SCR catalytic activity, nitrogen selectivity and hydrothermal stability. Therefore, it has passedTransition metal ion exchanged molecular sieve catalysts hold great potential.
In practical applications, the alkali metals and alkaline earth metals in the exhaust ash cause a drastic decrease in the catalyst activity. Many researchers have pointed out that alkali metals can cause the catalyst pore channel to be blocked and cover the surface of the catalyst, and even more deadly, the reduction of acid sites on the surface can affect the adsorption of ammonia, so that the normal SCR reaction can not occur. In fact, considerable research has been conducted on the mechanism of alkali metal poisoning and the design and preparation of highly effective alkali metal resistant catalysts. For example, Wu faithful et al (Wang, P.; Wang, H.; Chen, X.; Liu, Y.; Weng, X.; Wu, Z.J.Mater.chem.A 2015,3,680-690.) utilize ion-exchanged titanium nanotubes as supports for SCR catalysts, whose surface rich hydroxyl groups lead to an increase in the concentration and strength of the acidic sites, thereby increasing the alkali metal resistance. Li Junhua et al (Peng, Y.; Li, J.; Shi, W.; Xu, J.; Hao, J. environ. Sci. technol.2012,46, 12623-. In summary, the conventional methods for resisting alkali metal poisoning generally increase acid sites and active sites, but these measures have not been obvious and cannot completely meet the requirement of resisting alkali metal poisoning in the practical application of the SCR catalyst.
Disclosure of Invention
The invention aims to provide a denitration catalyst capable of resisting alkali metal poisoning, aiming at overcoming the defects of the existing denitration catalyst.
The second purpose of the invention is to provide a preparation method of the catalyst, which has the characteristics of good activity, good selectivity, strong alkali metal poisoning resistance and simple preparation process and is suitable for large-scale industrial production.
In order to achieve the purpose, the invention adopts the following technical scheme:
an alkali metal poisoning resistant denitration catalyst, characterized in that the catalyst has the structure: the molecular sieve providing catalytic activity is inside the material, and the barium manganese ore type oxide capturing alkali metal ions provides a protective function outside the material.
A preparation method for preparing the denitration catalyst resistant to alkali metal poisoning is characterized by comprising the following specific steps:
a. mixing titanium dioxide, manganese oxide and potassium carbonate according to a proportion of 24: 4: and 3, fully grinding the mixture, and calcining the mixture for 8 to 10 hours at the temperature of between 1000 and 1200 ℃ to obtain the barium-manganese ore type oxide.
b, washing out potassium ions in the pore channels of the manganesite-barium oxide by acid treatment for 3-8 hours to obtain the manganesite-barium oxide after the acid treatment;
c. and c, mixing the Cu-SAPO-34 molecular sieve with the acid-treated barium manganate type oxide obtained in the step b according to the weight ratio of 9: and (2) placing the mixture in deionized water according to the mass ratio of 1, fully mixing, removing water, and drying the residual solid to obtain the denitration catalyst resistant to alkali metal poisoning.
The preparation method of the Cu-SAPO-34 molecular sieve comprises the following steps:
a. adding a hydrogen type molecular sieve into an ammonium ion precursor salt solution, adjusting the pH value of the solution to 3.5, stirring at 80 ℃ for 2-4 h, filtering, and drying to obtain the ammonium type molecular sieve; the concentration of the ammonium radical exchange solution is 3.243mol/L, and the solid-to-liquid ratio of the hydrogen type molecular sieve to the solution is 1g/20 ml;
b. adding the ammonium type molecular sieve obtained in the step a into Cu2+Exchanging for 1-6 h at 80 ℃ in the ion precursor salt solution, filtering, washing, drying, and calcining for 5-7 h at 550 ℃ to obtain the Cu-SAPO-34 molecular sieve; the concentration of the copper ion exchange solution is 0.025mol/L, and the solid-to-liquid ratio of the ammonium molecular sieve to the solution is 1g/100 ml;
the hydrogen-type molecular sieve is a CHA-type molecular sieve such as SAPO-34, SSZ-13 or DAF-5, or an ERI-type molecular sieve such as AIPO-17 or LZ-220.
The ammonium ion precursor salt is ammonium nitrate, ammonium chloride or ammonium sulfate.
Cu as described above2+The precursor salt of the ion is copper chloride, copper acetate, copper nitrate or copper sulfate.
The above-mentioned manganite-type oxide is a manganese titanium oxide, a manganese oxide or a titanium oxide.
In the preparation process, the ion exchange time of the molecular sieve is different, the amount of copper ions successfully exchanged in the molecular sieve is also different, and the catalytic activity of the finally obtained catalyst is also greatly changed.
In the preparation process, different types of acids used for treating the lithospermic acid and different treatment temperatures and times can cause different contents of residual potassium ions in the lithospermic oxide pore canals, and finally the obtained catalyst has different alkali metal poisoning resistance.
The temperature in the dipping rotary evaporation process is not too high or too low and is kept between 45 and 55 ℃; the evaporation rate is kept at 3-5 h/70ml in a moderate manner; otherwise, the dispersibility of the active components of the catalyst is not ideal, and the catalytic activity is affected.
The calcination temperature rise rate is 1-5 ℃/min, the calcination time of the transition metal ion exchanged molecular sieve is 5-7 h, the calcination time of the barite manganese oxide is 8-10 h, and if the temperature rise rate and the time exceed the range, the sintering of the catalyst or the change of the crystal growth speed can be caused, so that the structure and the surface appearance of the catalyst are damaged, the specific surface area of the catalyst is rapidly reduced, and the catalytic activity of the calcined catalyst is not facilitated.
Compared with the prior art, the invention has the following advantages:
(1) the catalyst adopts a novel alkali metal ion capturing method, and alkali metal ions are fixed in the pore channels of the manganese barium ore oxide through an ion exchange mechanism, so that the catalytic activity of the molecular sieve is not influenced, and the alkali metal poisoning resistance is greatly improved.
(2) The catalyst uses the molecular sieve to provide SCR catalytic activity and has the advantages of high activity, good selectivity, wide temperature window and the like.
(3) Compared with the traditional vanadium tungsten titanium catalyst, the catalyst has the advantages of small environmental toxicity, high catalytic activity, strong alkali metal poisoning resistance and the like, is simple in preparation process, and can effectively control the production cost.
Detailed Description
In order to more clearly illustrate the present invention, the following examples are given, but the present invention is not limited to the scope of the examples.
The first embodiment is as follows:
the H-SAPO-34 molecular sieve is prepared by a hydrothermal method. 17.3468g ammonium chloride was dissolved in 100ml deionized water, 5g H-SAPO-34 was added, the pH was adjusted to 3.5 with hydrochloric acid, stirred at 80 ℃ for 2h, filtered, dried in an oven at 120 ℃ overnight to give NH4SAPO-34. 0.6242g of copper sulfate was dissolved in 100ml of deionized water, and 1g of NH was added4And (3) adding SAPO-34 into the solution, performing ion exchange at 80 ℃ for 3h, filtering, washing, drying at 120 ℃ overnight, and calcining at 550 ℃ for 5h to obtain the Cu-SAPO-34 molecular sieve. Then 0.2073g of potassium carbonate, 0.9584g of titanium dioxide and 0.3157g of manganese sesquioxide are mixed uniformly and fully ground, and the mixture is placed in a muffle furnace to be calcined for 8 hours in air at 1000 ℃. The resulting powder was treated with a mixed acid of sulfuric acid and nitric acid (volume ratio 3:1) at 80 ℃ for 3 hours, filtered and washed to neutrality. And then, fully mixing the obtained Cu-SAPO-34 and the barium manganese oxide subjected to acid treatment in deionized water, evaporating the water by using a rotary evaporator, and drying the residual solid in an oven at 120 ℃ overnight to obtain the efficient alkali metal poisoning resistant catalyst of the barium manganese oxide-reinforced Cu-SAPO-34 molecular sieve.
The catalysts described above were tested for catalytic activity and resistance to alkali metal poisoning: 0.3g of the prepared catalyst is put into a fixed bed quartz tube reactor for activity test, the reaction temperature is 90-360 ℃, and the space velocity is 40000h-1Under the condition of (1), the removal rate of nitrogen oxides can be kept above 90% at the temperature of 220-360 ℃. After 0.5 wt% of potassium poisoning, the highest nitrogen oxide removal rate is still kept around 90%. Simulating the smoke from N2、O2NO and NH3Composition of, wherein NO/NH31:1, 500 ppm by volume, O2The concentration is 3%, and the balance gas is nitrogen.
Example two:
the H-SAPO-34 molecular sieve is prepared by a hydrothermal method. 25.9581g of ammonium nitrate was dissolved in 100ml of deionized water, 5g H-SAPO-34 was added thereto, the pH was adjusted to 3.5 with nitric acid, stirred at 80 ℃ for 2h, filtered, and placed in an ovenDrying overnight at 120 ℃ to give NH4SAPO-34. 0.6242g of copper sulfate was dissolved in 100ml of deionized water, and 1g of NH was added4And (3) adding SAPO-34 into the solution, performing ion exchange at 80 ℃ for 3h, filtering, washing, drying at 120 ℃ overnight, and calcining at 550 ℃ for 5h to obtain the Cu-SAPO-34 molecular sieve. Then 0.2073g of potassium carbonate, 0.9584g of titanium dioxide and 0.3157g of manganese sesquioxide are mixed uniformly and fully ground, and the mixture is placed in a muffle furnace to be calcined for 8 hours in air at 1000 ℃. The resulting powder was treated with a mixed acid of sulfuric acid and nitric acid (volume ratio 3:1) at 80 ℃ for 3 hours twice, filtered and washed to neutrality. And then, fully mixing the obtained Cu-SAPO-34 and the barium manganite oxide after acid treatment in deionized water, evaporating water to dryness by using a rotary evaporator, and drying the residual solid in an oven at 120 ℃ overnight to obtain the high-efficiency alkali metal poisoning resistant catalyst.
The catalysts described above were tested for catalytic activity and resistance to alkali metal poisoning: 0.3g of the prepared catalyst is put into a fixed bed quartz tube reactor for activity test, the reaction temperature is 90-360 ℃, and the space velocity is 40000h-1Under the condition of (1), the removal rate of nitrogen oxides can be kept above 90% at the temperature of 230-360 ℃. After 0.5 wt% of potassium poisoning, the maximum nitrogen oxide removal rate is still kept around 92%. Simulating the smoke from N2、O2NO and NH3Composition of, wherein NO/NH31:1, 500 ppm by volume, O2The concentration is 3%, and the balance gas is nitrogen.
Example three:
the H-SAPO-34 molecular sieve is prepared by a hydrothermal method. 17.3468g ammonium chloride was dissolved in 100ml deionized water, 5g H-SAPO-34 was added, the pH was adjusted to 3.5 with hydrochloric acid, stirred at 80 ℃ for 2h, filtered, dried in an oven at 120 ℃ overnight to give NH4SAPO-34. 0.4689g of copper nitrate was dissolved in 100ml of deionized water, and 1g of NH was added4And (3) adding SAPO-34 into the solution, performing ion exchange at 80 ℃ for 4h, filtering, washing, drying at 120 ℃ overnight, and calcining at 550 ℃ for 5h to obtain the Cu-SAPO-34 molecular sieve. Then 0.2073g of potassium carbonate, 0.9584g of titanium dioxide and 0.3157g of manganese sesquioxide are mixed uniformly and fully ground, and the mixture is placed in a muffle furnace at 1000 DEG CAir calcination was carried out for 8 h. The resulting powder was treated with a mixed acid of sulfuric acid and nitric acid (volume ratio 3:1) at 80 ℃ for 3 hours twice, filtered and washed to neutrality. And then, fully mixing the obtained Cu-SAPO-34 and the acid-treated manganite oxide in deionized water, evaporating the water to dryness by using a rotary evaporator, and drying the residual solid in an oven at 120 ℃ overnight to obtain the efficient alkali metal poisoning resistant catalyst of the manganite-manganesium oxide reinforced Cu-SAPO-34 molecular sieve.
The catalysts described above were tested for catalytic activity and resistance to alkali metal poisoning: 0.3g of the prepared catalyst is put into a fixed bed quartz tube reactor for activity test, the reaction temperature is 90-360 ℃, and the space velocity is 40000h-1Under the condition of (2), the removal rate of nitrogen oxides can be kept above 90% at the temperature of 240 ℃ and 360 ℃. After 0.5 wt% of potassium poisoning, the highest nitrogen oxide removal rate is still maintained at about 91%. Simulating the smoke from N2、O2NO and NH3Composition of, wherein NO/NH31:1, 500 ppm by volume, O2The concentration is 3%, and the balance gas is nitrogen.
Claims (7)
1. An alkali metal poisoning resistant denitration catalyst, characterized in that the catalyst has the structure: the molecular sieve providing catalytic activity is arranged in the material, the barium manganese ore type oxide capturing alkali metal ions provides a protection function outside the material, and the denitration catalyst resisting alkali metal poisoning is prepared by the following method steps:
a. mixing titanium dioxide, manganese oxide and potassium carbonate according to a proportion of 24: 4: 3, fully grinding the mixture, and calcining the mixture for 8 to 10 hours at the temperature of between 1000 and 1200 ℃ to obtain a barium-manganese ore type oxide;
b. washing out potassium ions in the pore channels of the manganite-barium oxide by acid treatment, wherein the acid treatment time is 3-8 hours and the temperature is 80 ℃, and obtaining the manganite-barium oxide after the acid treatment;
c. and c, mixing the Cu-SAPO-34 molecular sieve with the acid-treated barium manganate type oxide obtained in the step b according to the weight ratio of 9: and (2) placing the mixture in deionized water according to the mass ratio of 1, fully mixing, removing water, and drying the residual solid to obtain the denitration catalyst resistant to alkali metal poisoning.
2. A method for preparing the denitration catalyst resistant to alkali metal poisoning according to claim 1, comprising the steps of:
a. mixing titanium dioxide, manganese oxide and potassium carbonate according to a proportion of 24: 4: 3, fully grinding the mixture, and calcining the mixture for 8 to 10 hours at the temperature of between 1000 and 1200 ℃ to obtain a barium-manganese ore type oxide;
b. washing out potassium ions in the pore channels of the manganite-barium oxide by acid treatment, wherein the acid treatment time is 3-8 hours and the temperature is 80 ℃, and obtaining the manganite-barium oxide after the acid treatment;
c. and c, mixing the Cu-SAPO-34 molecular sieve with the acid-treated barium manganate type oxide obtained in the step b according to the weight ratio of 9: and (2) placing the mixture in deionized water according to the mass ratio of 1, fully mixing, removing water, and drying the residual solid to obtain the denitration catalyst resistant to alkali metal poisoning.
3. The method for preparing a denitration catalyst resistant to alkali metal poisoning according to claim 2, wherein the Cu-SAPO-34 molecular sieve in the step c is prepared by:
c-1, adding a hydrogen type molecular sieve into an ammonium ion precursor salt solution, adjusting the pH value of the solution to 3.5, stirring for 2-4 h at 80 ℃, filtering, and drying to obtain the ammonium type molecular sieve; the concentration of the ammonium radical exchange solution is 3.243mol/L, and the solid-to-liquid ratio of the hydrogen type molecular sieve to the solution is 1g/20 ml;
c-2, adding the ammonium type molecular sieve obtained in the step c-1 into Cu2+Exchanging for 1-6 h at 80 ℃ in the ion precursor salt solution, filtering, washing, drying, and calcining for 5-7 h at 550 ℃ to obtain the Cu-SAPO-34 molecular sieve; the concentration of the copper ion exchange solution is 0.025mol/L, and the solid-to-liquid ratio of the ammonium molecular sieve to the solution is 1g/100 ml;
4. the method of claim 3, wherein the hydrogen-type molecular sieve is a CHA-type molecular sieve or an ERI-type molecular sieve, the hydrogen-type molecular sieve is SAPO-34, SSZ-13 or DAF-5, and the ERI-type molecular sieve is AIPO-17 or LZ-220.
5. The method of claim 3, wherein the ammonium ion precursor salt is ammonium nitrate, ammonium chloride or ammonium sulfate.
6. The method of claim 3, wherein said Cu is2+The precursor salt of the ion is copper chloride, copper acetate, copper nitrate or copper sulfate.
7. The method according to claim 2, wherein the manganite-type oxide is manganese titanium oxide, manganese oxide or titanium oxide.
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| CN106732755A (en) * | 2016-12-23 | 2017-05-31 | 中节能万润股份有限公司 | A kind of preparation method of the compound integral extruding type denitrating catalyst of molecular sieve multivariant oxide |
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| CN106732755A (en) * | 2016-12-23 | 2017-05-31 | 中节能万润股份有限公司 | A kind of preparation method of the compound integral extruding type denitrating catalyst of molecular sieve multivariant oxide |
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