CN113976172A - Preparation and application of assistant doped Cu-SSZ-39 catalyst with high hydrothermal stability - Google Patents
Preparation and application of assistant doped Cu-SSZ-39 catalyst with high hydrothermal stability Download PDFInfo
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- CN113976172A CN113976172A CN202111184738.4A CN202111184738A CN113976172A CN 113976172 A CN113976172 A CN 113976172A CN 202111184738 A CN202111184738 A CN 202111184738A CN 113976172 A CN113976172 A CN 113976172A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010949 copper Substances 0.000 claims description 44
- 229910052700 potassium Inorganic materials 0.000 claims description 34
- 229910052708 sodium Inorganic materials 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 31
- 229910052791 calcium Inorganic materials 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
- 239000012266 salt solution Substances 0.000 claims description 22
- 239000002808 molecular sieve Substances 0.000 claims description 21
- 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 21
- 238000005342 ion exchange Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 229910001424 calcium ion Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 150000003863 ammonium salts Chemical class 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 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 5
- 238000003379 elimination reaction Methods 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 230000008030 elimination Effects 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-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
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 18
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 230000009466 transformation Effects 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000011734 sodium Substances 0.000 description 40
- 238000010335 hydrothermal treatment Methods 0.000 description 35
- 239000011575 calcium Substances 0.000 description 34
- 238000012360 testing method Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004846 x-ray emission Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- -1 Cu-ZSM-5 Chemical compound 0.000 description 1
- 229910016553 CuOx Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
-
- 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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
- F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
-
- 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
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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- General Engineering & Computer Science (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
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Abstract
The invention belongs to the technical field of catalytic materials, and particularly relates to preparation and application of an assistant-doped Cu-SSZ-39 catalyst with high hydrothermal stability3By selective catalytic reduction of NOxCan reach 250 ℃ to>90% NOxThe transformation can be achieved within the range of 250-550 DEG C>80% NOxConverted and still has better NO after high-temperature treatment at 750 ℃ or 800 DEG CxHigh conversion rate and hydrothermal stability and excellent performanceLow temperature NH3SCR activity and high-temperature hydrothermal stability, and can be used as a denitration catalyst for eliminating nitrogen oxides in diesel engine exhaust.
Description
Technical Field
The invention belongs to the technical field of catalytic materials, and particularly relates to preparation and application of an auxiliary agent doped Cu-SSZ-39 catalyst with high hydrothermal stability.
Background
Nitrogen oxides [ NO ] discharged from exhaust gas of power plant and motor vehiclex(NO、NO2And N2O) is a major class of atmospheric pollutants.The substances not only can generate the phenomena of greenhouse effect, acid rain, chemical light fog and the like, but also can cause great damage to the respiratory system of human beings, thereby seriously influencing the ecological environment and the physical health of the human beings depending on the survival. Thus, eliminating NOxIs particularly important.
Ammonia-selective catalysis of NOxReduction (NH)3SCR) is NO eliminationxIs one of the most efficient approaches. Currently, for the selective catalysis of NOxReduced NH3The SCR catalyst mainly comprises commercial catalysts V-W-Ti and Cu ion exchanged molecular sieve catalysts (such as Cu-ZSM-5, Cu-Beta and the like). However, these catalysts all have a narrow activity window and a high temperature N2Poor selectivity, poor hydrothermal stability and the like, which results in poor application effect in certain application fields. For example, in a Diesel Particulate Filter (DPF) in a tail gas treatment system of a national six-Diesel engine at present, since the regeneration process of the DPF usually requires a temperature of more than 800 ℃, an SCR bed layer will be in a high-temperature and high-humidity environment in the process, and thus the requirement on the hydrothermal stability of an SCR catalyst is high. Therefore, the development of SCR catalysts with good catalytic activity and high hydrothermal stability is the focus and focus of current research.
In recent years, small pore molecular sieves represented by SSZ-13 (CHA-type framework structure) have been proposed because of their wide NO contentxWindow of conversion, higher N2Selectivity and higher hydrothermal stability, and is widely researched and applied. Among them, the most widely used contemporary Cu-SSZ-13 molecular sieve. However, although Cu-SSZ-13 has better hydrothermal stability, its skeleton is severely collapsed after hydrothermal treatment at 850 ℃. Research shows that Al atoms on a Cu-SSZ-13 framework are detached and active Cu is removed in the high-temperature hydrothermal treatment process2+Conversion of ions to CuOxIs caused to be Cu-SSZ-13 in NH3The main cause of deactivation during the SCR reaction. Therefore, in order to improve the hydrothermal stability of Cu-SSZ-13, it is necessary to improve the stability of Al as a skeleton and to reduce the aggregation of Cu.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention adopts SSZ-3The zeolite molecular sieve 9(AEI framework structure) is used as a carrier, the Cu species is used as an active component, Na, K and Ca ions are used as auxiliaries, the Cu-SSZ-39 catalyst is a pure-phase AEI type molecular sieve, and the Cu species mainly comprises Cu2+And [ Cu (OH) ]]+Mainly ions, these Cu ions are located in the plane of one of the 6-membered rings of d6 r. After Na, K and Ca ion modification, the obtained catalyst has excellent low-temperature NH3SCR activity and high temperature hydrothermal stability.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a preparation method of an assistant doped Cu-SSZ-39 catalyst with high hydrothermal stability, which is prepared by calcining an SSZ-39(AEI framework) molecular sieve serving as a catalyst, Cu serving as a main active component and Na, K or Ca serving as a catalyst assistant.
As a preferred embodiment of the invention, the preparation method of the assistant doped Cu-SSZ-39 catalyst with high hydrothermal stability comprises the following steps:
s1, exchange copper: carrying out ion exchange on Na-SSZ-39 or K-SSZ-39 or Ca-SSZ-39 and a Cu salt solution, and washing and drying to prepare the auxiliary agent doped Cu-SSZ-39;
s2, calcining: and (3) placing the assistant-doped Cu-SSZ-39 obtained in the step (S1) at 250-300 ℃ and 550-600 ℃ for segmented heat treatment, cooling to room temperature at a cooling speed of 1-2 ℃/min, and finally grinding, tabletting and granulating to obtain the assistant-doped Cu-SSZ-39 catalyst.
Preferably, the Cu salt solution in step S1 includes a copper nitrate solution, a copper acetate solution, a copper chloride solution, and a copper sulfate solution, and the concentration of the Cu salt solution is 0.001mol/L to 1 mol/L. Further, the concentration of the Cu salt solution is 0.025 mol/L.
Preferably, the feed-liquid ratio of the Na-SSZ-39 or K-SSZ-39 or Ca-SSZ-39 to the Cu salt solution in the step S1 is 2g/200 mL.
Preferably, the ion exchange in the step S1 is carried out for 12-36 h at 20-40 ℃.
Preferably, the step S1 includes heating to 250-300 deg.C at a heating rate of 2 deg.C/min for 4h, and then heating to 550-600 deg.C at a heating rate of 2 deg.C/min for 6 h.
Preferably, the preparation method of Na-SSZ-39, K-SSZ-39 and Ca-SSZ-39 comprises the following steps:
s11, Na-SSZ-39: uniformly mixing an inorganic alkali solution, a template agent solution and a silicon source and aluminum source to prepare sol, then crystallizing at 135-145 ℃ for 72-168 h to obtain a crystallized product, washing and drying the crystallized product, and then carrying out segmented heat treatment at 250-300 ℃ and 550-600 ℃ to obtain Na-SSZ-39;
s12 preparation of NH4-SSZ-39: carrying out ion exchange on the Na-SSZ-39 obtained in the step S11 and an ammonium salt solution, and washing and drying to obtain NH4-SSZ-39；
S13, exchange K ion or Ca ion: NH of step S124And (3) carrying out ion exchange on the SSZ-39 and a K salt solution or a Ca salt solution, and washing and drying to obtain the K-SSZ-39 or Ca-SSZ-39.
Compared with the mesoporous and macroporous molecular sieves such as Cu-ZSM-5, Cu-beta and the like, the SSZ-39(AEI type) microporous structure can inhibit framework dealumination to form copper-aluminate, thereby being beneficial to improving the activity of the catalyst. The structure of SSZ-39(AEI type) contains six-membered ring, and has large cage connected by three small eight-membered rings (8-R), the copper element is preferentially located under the plane coordinated with three oxygen atoms in the double six-membered ring framework unit, and the thermal stability of the catalyst can be obviously improved. In addition, Cu-SSZ-39 has more excellent hydrothermal stability than Cu-SSZ-13, and further introduction of Na, K or Ca element contributes to improvement of low-temperature activity of the catalyst, and the catalyst has NH resistance3The SCR performance is also improved.
The Cu exchanged molecular sieve catalyst prepared by the invention is used for NH after being modified by Na, K and Ca ions3By selective catalytic reduction of NOxIt was found that the CuM-SSZ-39 catalyst (M ═ Na, K and Ca) obtained by the synthesis method of the present invention has excellent NOxAn elimination property which can be achieved at 250 DEG C>90% NOxThe transformation can reach 250-550 DEG C>80% NOxConverted and still has better NO after high-temperature treatment at 750 ℃ or 800 DEG CxThe conversion rate and the hydrothermal stability are good.
Further, the step S11 includes heating to 250-300 ℃ at a heating rate of 1-5 ℃/min for 2-6 h, and then heating to 550-600 ℃ at a heating rate of 1-3 ℃/min for 4-9 h.
Further, in steps S12 and S13, the ion exchange is performed for 2 to 10 hours at a temperature of 70 to 90 ℃, and the ion exchange of step S12 is repeated 2 to 3 times.
Further, the inorganic base comprises sodium hydroxide. The template agent comprises N, N-dimethyl-3, 5-dimethylpiperidine hydroxide.
Further, the silicon source and the aluminum source are CBV 720.
Further, the ammonium salt solution comprises an ammonium acetate solution, an ammonium nitrate solution and an ammonium chloride solution, and the concentration of the ammonium salt solution is 0.5-2 mol/L.
Further, the feed-liquid ratio of the Na-SSZ-39 to the ammonium salt solution is 1 g: 50mL to 200 mL. Specifically, the feed-liquid ratio of the Na-SSZ-39 to the ammonium salt solution is 1 g: 200 mL.
Further, the molar ratio of the aluminum source to the silicon source is 0.067: 1.
Further, the molar ratio of the template agent to the silicon source is 0.1-0.3: 1.
Further, the molar ratio of the inorganic base to the silicon source is 0.15-0.3: 1.
Further, the concentration of the inorganic alkali solution is 1 g/(25-30) g.
Further, in step S11, the step-by-step heat treatment is to heat up to 290 ℃ at a heating rate of 2 ℃/min for 4 hours, and then to 550 ℃ for 5 hours.
Further, the K salt solution comprises a potassium nitrate solution, the Ca salt solution comprises a calcium nitrate solution, and the concentration of the Ca salt solution or the K salt solution is 0.5-2 mol/L.
The invention also provides the assistant doped Cu-SSZ-39 catalyst with high hydrothermal stability, which is prepared by the preparation method.
The invention also provides application of the assistant doped Cu-SSZ-39 catalyst with high hydrothermal stability in eliminating nitrogen oxides in diesel engine tail gas.
The preparation method of the assistant-doped Cu-SSZ-39 catalyst with high hydrothermal stability provided by the invention has the advantage that the prepared assistant-doped Cu-SSZ-39 catalyst has excellent low-temperature NH3SCR activity and high-temperature hydrothermal stability, and can be applied to elimination of nitrogen oxides in diesel engine exhaust.
Compared with the prior art, the invention has the beneficial effects that:
the invention prepares an assistant-doped Cu-SSZ-39 catalyst for NH by using an SSZ-39(AEI framework) molecular sieve as a catalyst, using Cu as a main active component and using Na, K or Ca as a catalyst assistant3By selective catalytic reduction of NOxCan reach 250 ℃ to>90% NOxThe transformation can be achieved within the range of 250-550 DEG C>80% NOxConverted and still has better NO after high-temperature treatment at 750 ℃ or 800 DEG CxThe conversion rate and the hydrothermal stability are good. Therefore, the auxiliary agent doped Cu-SSZ-39 catalyst prepared by the invention has more excellent low-temperature NH3SCR activity and high-temperature hydrothermal stability, and can be used as a denitration catalyst for eliminating nitrogen oxides in diesel engine exhaust.
Drawings
Fig. 1 is an X-ray diffraction pattern of a CuM-SSZ-39 catalyst (M ═ Na, K, Ca);
fig. 2 is an SEM image of the CuM-SSZ-39 catalyst (M ═ Na, K, Ca);
FIG. 3 shows CuM-SSZ-39 catalyst (M ═ Na, K, Ca)27An Al solid nuclear magnetic spectrum;
FIG. 4 shows NH of CuM-SSZ-39 catalyst (M ═ Na, K, Ca)3-SCR activity evaluation;
FIG. 5 is the N of CuM-SSZ-39 catalyst (M ═ Na, K, Ca)2A selectivity curve;
FIG. 6 is an X-ray diffraction pattern of CuM-SSZ-39 catalyst (M ═ Na, K, Ca) after hydrothermal treatment at 750 ℃;
FIG. 7 shows CuM-SSZ-39 catalyst (M ═ Na, K, Ca) after hydrothermal treatment at 750 ℃ in the presence of water27An Al solid nuclear magnetic spectrum;
FIG. 8 shows NH of CuM-SSZ-39 catalyst (M ═ Na, K, Ca) after hydrothermal treatment at 750 ℃3-SCR activity evaluation;
FIG. 9 shows N of CuM-SSZ-39 catalyst (M ═ Na, K, Ca) after hydrothermal treatment at 750 ℃ in the presence of water2A selectivity curve;
fig. 10 is an X-ray diffraction pattern of a CuM-SSZ-39 catalyst (M ═ Na, K, Ca) after hydrothermal treatment at 800 ℃;
FIG. 11 shows CuM-SSZ-39(M ═ Na, K, Ca) after hydrothermal treatment at 800 deg.C27An Al solid nuclear magnetic spectrum;
FIG. 12 shows NH of CuM-SSZ-39 catalyst (M ═ Na, K, Ca) after hydrothermal treatment at 800 deg.C3-SCR activity evaluation;
FIG. 13 shows N of CuM-SSZ-39 catalyst (M ═ Na, K, Ca) after hydrothermal treatment at 800 deg.C2Selectivity profile.
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The experimental procedures in the following examples were carried out by conventional methods unless otherwise specified, and the test materials used in the following examples were commercially available by conventional methods unless otherwise specified.
Example 1 preparation of denitration catalyst CuNa-SSZ-39
The preparation method comprises the following steps:
(1) preparation of Na-SSZ-39
Adding 2g of sodium hydroxide into 51g of water, adding a template agent of N, N-dimethyl-3, 5-dimethylpiperidine hydroxide (the concentration is 0.280mol/kg), stirring for 2h, adding 22g of molecular sieve CBV720 (the molar ratio of an aluminum source to a silicon source is 0.067:1, purchased from Zeolyst company) serving as a silicon source and an aluminum source at the same time, continuously stirring for 6h to obtain sol, transferring the sol to a 300mL reaction kettle, crystallizing for 144h in a 140 ℃ oven to obtain a crystalline product, washing for 5 times with water, washing for 3 times with absolute ethyl alcohol, drying for 24h at the temperature of 110 ℃, then heating to 290 ℃ at the heating rate of 2 ℃/min for processing for 4h, then heating to 550 ℃ and processing for 5h at the temperature of 550 ℃ to obtain Na-SSZ-39.
(2) Exchange of Cu ions
2g of Na-SSZ-39 was mixed with 200mL of a 0.025mol/L copper nitrate solution and ion-exchanged at 30 ℃ for 24 hours, followed by dispersion-washing with stirring in hot water at 80 ℃ for 3 times and finally drying in an oven at 110 ℃ for 6 hours to obtain CuNa-SSZ-39.
(3) Calcination of
Placing the CuNa-SSZ-39 molecular sieve catalyst after copper exchange in a muffle furnace, heating to 300 ℃ at the heating rate of 2 ℃/min, maintaining for 4h, subsequently heating to 550 ℃ at the heating rate of 2 ℃/min, maintaining for 6h, and then cooling to room temperature at the cooling rate of 2 ℃/min. Finally grinding, tabletting and granulating (the grain diameter is 60-100 meshes) to obtain the Cu-SSZ-39 molecular sieve catalyst.
The Cu-SSZ-39 series catalyst obtained in example 1 had a Cu content of 2.1% by mass and a Na content of 1.8% by XRF (X-ray fluorescence spectroscopy) detection. Hence, also called Cu0.21Na0.18-SSZ-39. The XRD spectrogram intensity is shown in Table 1, which shows that the sample is SSZ-39 molecular sieve with better crystallinity and has higher stability.
TABLE 1 table of intensities of the XRD ray patterns of the CuNa-SSZ-39 catalyst
Note: the strongest line in the X-ray map is assigned a value of 100, where W is weak (>0 to ≦ 20); m-medium (>20 to ≦ 40); s-strong (>40 to ≦ 60); VS is very strong (>60 to ≦ 100).
Example 2 preparation of denitration catalyst CuK-SSZ-39
The preparation method comprises the following steps:
(1) preparation of Na-SSZ-39: the procedure is as in example 1.
(2) Preparation of NH4-SSZ-39
Adding 1g of Na-SSZ-39 into 100mL of ammonium acetate solution with the concentration of 1mol/L, and carrying out ion exchange at 85 ℃ for 6 h; repeating the ion exchange process for 2 times, washing with water for 3 times, and drying in an oven at 110 deg.C for 24 hr to obtain NH4-SSZ-39；
(3) Exchange of K ions
Adding 1g of NH4the-SSZ-39 powder was mixed with 200mL of a 1mol/L potassium nitrate solution and ion-exchanged at 80 ℃ for 6h, washed 3 times with water and dried in an oven at 120 ℃ for 20h to give K-SSZ-39.
(4) Exchange of Cu ions
2g K-SSZ-39 was mixed with 200mL of 0.025mol/L copper nitrate solution and ion-exchanged at 80 ℃ for 2 hours, followed by dispersion washing with stirring in hot water at 80 ℃ for 3 times, and then dried in an oven at 110 ℃ for 6 hours to give CuK-SSZ-39.
(5) And (3) calcining: the procedure is as in example 1 to obtain a CuK-SSZ-39 molecular sieve catalyst.
The weight fraction of Cu in the CuK-SSZ-39 catalyst obtained in example 2 was 1.9% and the K content was 2.0% by XRF detection. Hence, also called Cu0.19K0.20-SSZ-39. The XRD spectrogram intensity is shown in Table 2, which shows that the sample is SSZ-39 molecular sieve with better crystallinity and has higher stability.
TABLE 2 XRD ray pattern intensity chart of CuK-SSZ-39 catalyst
Note: the strongest line in the X-ray map is assigned a value of 100, where W is weak (>0 to ≦ 20); m-medium (>20 to ≦ 40); s-strong (>40 to ≦ 60); VS is very strong (>60 to ≦ 100).
Example 3 preparation of denitration catalyst CuCa-SSZ-39
The preparation method comprises the following steps:
(1) preparation of Na-SSZ-39: the procedure is as in example 1.
(2) Preparation of NH4-SSZ-39: the procedure is as in example 2.
(3) Exchange of Ca ions
Adding 1g of NH4-SSZ-39 powder was mixed with 200mL of 1mol/L calcium nitrate solution and ion-exchanged at 80 ℃ for 6h, washed 3 times with water and dried in an oven at 120 ℃ for 20h to give Ca-SSZ-39.
(4) Exchange of Cu ions
2g of Ca-SSZ-39 was mixed with 200mL of 0.025mol/L copper nitrate solution, ion-exchanged at 80 ℃ for 2 hours, then dispersedly washed in hot water at 80 ℃ with stirring for 3 times, and then dried in an oven at 110 ℃ for 6 hours to obtain CuCa-SSZ-39.
(5) And (3) calcining: the procedure is as in example 1 to obtain a CuCa-SSZ-39 molecular sieve catalyst.
The weight fraction of Cu in the CuCa-SSZ-39 catalyst obtained in example 3 was 1.8% and the content of Ca was 2.2% by XRF detection. Hence, also called Cu0.18Ca0.22-SSZ-39. The XRD spectrogram intensity is shown in Table 3, which shows that the sample is SSZ-39 molecular sieve with better crystallinity and has higher stability.
TABLE 3 XRD ray pattern intensity chart of CuCa-SSZ-39 catalyst
Note: the strongest line in the X-ray map is assigned a value of 100, where W is weak (>0 to ≦ 20); m-medium (>20 to ≦ 40); s-strong (>40 to ≦ 60); VS is very strong (>60 to ≦ 100).
Experimental example 1 Performance test
(1) XRD test
XRD testing was performed on the Na, K and Ca ion modified Cu exchanged Cu-SSZ-39 series catalyst, CuM-SSZ-39(M ═ Na, K or Ca), using a STOE STADI P ESSENTIAL X-ray diffractometer.
As shown in FIG. 1, there was no significant decrease in crystallinity for the Na, K and Ca ion modified Cu exchanged Cu-SSZ-39 series of catalysts. Meanwhile, the diffraction peaks (35.6 ° and 38.8 ° in 2 θ) of CuO were not detected by the Cu-SSZ-39 series catalyst, which is probably due to the high dispersion of Cu species on the SSZ-39 catalyst without aggregation into CuO species.
(1) SEM test
A Scanning Electron Microscope (SEM) test was performed on CuM-SSZ-39(M ═ Na, K, or Ca) using ultra-high resolution FE-SEM SU 8010.
As shown in figure 2, the CuM-SSZ-39 zeolite molecular sieve has an orthogonal cuboid block shape, the length and width of the molecular sieve are 2-3 um, and the height dimension of the molecular sieve is 0.5-1 um.
(3) Method for preparing CuM-SSZ-39 modified by Na, K and Ca ions27Al solid nuclear magnetic spectrum (Bruker AVANCE III 600 nuclear magnetic spectrometer)
As shown in FIG. 3, the peak having a chemical shift of 60ppm is ascribed to the peak of skeleton Al atom, and the peak of non-skeleton Al atom (the peak having a chemical shift of 0ppm or 30 ppm) does not appear in all the samples (CuM-SSZ-39, abbreviated as CuCaZ, CuKZ, CuNaZ), indicating that all the samples have a high degree of crystallization.
(4) NH of Na, K and Ca ion modified CuM-SSZ-393SCR activity and N2Selectivity is
Using Cu obtained in example 10.21Na0.18Catalyst SSZ-39, Cu obtained in example 20.19K0.20Catalyst SSZ-39, Cu obtained in example 30.18Ca0.22Catalyst of the-SSZ-39 series at a NO concentration of 500ppm, NH3The concentration is 500ppm, O2Volume concentration of 5% N2For balancing gas, the space velocity is 80000h-1The denitration temperature is 150 ℃, 175 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃ and 550 ℃ in sequence. NH (NH)3SCR reaction tests were carried out on a fixed bed quartz flow reactor, and the detection was carried out by Thermo Scientific Nicolet Antaris IGS equipped with a TCD probe cooled with liquid nitrogen: (77K)。
As shown in Table 4 and FIG. 4, the CuM-SSZ-39 catalyst has excellent NOxAn elimination performance which can be reached at 250 DEG C>90% NOxAnd (4) transformation. The CuM-SSZ-39 catalyst can reach the temperature of 250 ℃ and 550 DEG C>80% NOxAnd (4) transformation.
As shown in Table 5 and FIG. 5, N of Cu-SSZ-39 modified with Na, K and Ca ions2The selectivity is more than 90% in the range of 200 ℃ and 550 ℃ and more than 97% in the range of 250 ℃ and 550 ℃.
TABLE 4 NO at different temperatures for CuM-SSZ-39xConversion rate
TABLE 5N of CuM-SSZ-39 at different temperatures2Selectivity is
(5) Hydrothermal stability testing of Na, K and Ca ion modified CuM-SSZ-39
1) Hydrothermal treatment at 750 deg.C
Placing the prepared CuM-SSZ-39 catalyst in wet air for high-temperature hydrothermal treatment, wherein the air flow rate is 100mL/min, and H is2The volume percentage of O is 20%, the temperature is increased to 750 ℃ at the heating rate of 10 ℃/min, and the temperature is maintained for 12 h. After the high-temperature hydrothermal treatment is finished, the temperature is reduced to the room temperature at the cooling rate of 10 ℃/min.
XRD testing was performed on the hydrothermally treated CuM-SSZ-39. As shown in fig. 6, all samples maintained good crystallinity after the 750 ℃ hydrothermal treatment. The Na, K and Ca ion modified Cu-SSZ-39 has higher hydrothermal stability.
The CuM-SSZ-39 after the hydrothermal treatment is carried out27And (5) carrying out Al solid nuclear magnetic spectrum test. As shown in FIG. 7, the solid aluminum nuclear magnetic material shows that the amount of skeleton Al remains substantially unchanged and the amount of non-skeleton aluminum is very small in all samples after the hydrothermal treatment at 750 ℃, which indicates that the samples haveHas good hydrothermal stability.
NH is carried out on the CuM-SSZ-39 after the hydrothermal treatment3-SCR activity measurement. As shown in Table 6 and FIG. 8, when Na was used as a modification, Cu was formed after hydrothermal treatment0.21Na0.18NO on SSZ-39-750 samplexA slight decrease in conversion occurred and reached 93% at 250 ℃ and a slight decrease after 400 ℃ of 89% at 550 ℃. When K is used as a modifier, Cu0.19K0.20SSZ-39, the activity decreases at low temperature, reaching 70% at 200 ℃ and 95% at 250 ℃ and slightly after 400 ℃ and 87% at 550 ℃. When Ca is used as a modifier, Cu0.18Ca0.22The low temperature activity of SSZ-39 decreases, reaching 69% at 200 ℃ and 95% at 250 ℃ and slightly after 400 ℃ and 84% at 550 ℃.
TABLE 6 NO at different temperatures after hydrothermal treatment of CuM-SSZ-39 at 750 deg.CxConversion rate
Performing N on the CuM-SSZ-39 after the hydrothermal treatment2And (4) selective measurement. As shown in Table 7 and FIG. 9, N of Cu-SSZ-39 modified with Na, K and Ca ions2The selectivity is more than 90% in the range of 200 ℃ and 550 ℃ and more than 97% in the range of 250 ℃ and 550 ℃.
TABLE 7N at different temperatures of CuM-SSZ-39 after hydrothermal treatment at 750 deg.C2Selectivity is
1) Hydrothermal treatment at 800 deg.C
Placing the prepared CuM-SSZ-39 catalyst in wet air for high-temperature hydrothermal treatment, wherein the air flow rate is 100mL/min, and H is2The volume percentage of O is 20 percent, the temperature is increased to 800 ℃ at the heating rate of 10 ℃/min and the temperature is maintained for 12 hours. After the high-temperature hydrothermal treatment is finished, the temperature is reduced to the room temperature at the cooling rate of 10 ℃/min.
XRD testing was performed on the hydrothermally treated CuM-SSZ-39. As shown in fig. 10, all samples maintained good crystallinity after the 800 ℃ hydrothermal treatment. The Na, K and Ca ion modified Cu-SSZ-39 has higher hydrothermal stability.
And carrying out 27Al solid nuclear magnetic spectrum test on the CuM-SSZ-39 after the hydrothermal treatment. As shown in fig. 11, the nuclear magnetic property of solid aluminum was found to keep the amount of framework Al substantially unchanged and the amount of non-framework aluminum very small in all samples after hydrothermal treatment at 800 ℃, indicating that the samples had good hydrothermal stability.
NH is carried out on the CuM-SSZ-39 after the hydrothermal treatment3-SCR activity measurement. As shown in Table 8 and FIG. 12, in the case of Na as a modification, Cu was formed after hydrothermal treatment at 800 ℃ C0.21Na0.18NO on SSZ-39 samplesxA slight decrease in conversion occurred and reached 93% at 250 ℃ and a slight decrease after 400 ℃ of 89% at 550 ℃. When K is used as a modification, Cu is subjected to hydrothermal treatment at 800 DEG C0.19K0.20SCR low temperature NO of SSZ-39 samplexThe conversion rate decreased, reaching 70% at 200 ℃ and 95% at 250 ℃ and decreased slightly after 400 ℃ and 87% at 550 ℃. When Ca is used as modification, Cu is treated by hydrothermal treatment at 800 DEG C0.18Ca0.22-SSZ-39 Low temperature NOxThe conversion rate decreased to 69% at 200 ℃ and 95% at 250 ℃ and slightly decreased after 400 ℃ to 84% at 550 ℃.
TABLE 8 NO at different temperatures after hydrothermal treatment of CuM-SSZ-39 at 800 deg.CxConversion rate
Performing N on the CuM-SSZ-39 after the hydrothermal treatment2And (4) selective measurement. As shown in Table 9 and FIG. 13, N of Na, K and Ca ion-modified Cu-SSZ-39 after hydrothermal treatment at 800 deg.C2The selectivity is more than 90% in the range of 200 ℃ and 550 ℃ and more than 97% in the range of 250 ℃ and 550 ℃.
TABLE 9 CuM-SSZ-39N at different temperatures after hydrothermal treatment at 800 DEG C2Selectivity is
Thus, the CuM-SSZ-39(M ═ Na, K or Ca) catalyst prepared by the invention is treated at high temperature of 750 ℃ or 800 ℃, and NH is added3SCR activity and N2The selectivity is only slightly reduced, and better NO is still obtainedxThe conversion rate and the hydrothermal stability are good.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.
Claims (10)
1. A preparation method of an assistant doped Cu-SSZ-39 catalyst with high hydrothermal stability is characterized in that an SSZ-39 molecular sieve is used as a catalyst, Cu is used as a main active component, Na, K or Ca is used as a catalyst assistant, and the catalyst is prepared by calcining.
2. The preparation method of the additive doped Cu-SSZ-39 catalyst with high hydrothermal stability as claimed in claim 1, characterized by comprising the following steps:
s1, exchange copper: carrying out ion exchange on Na-SSZ-39 or K-SSZ-39 or Ca-SSZ-39 and a Cu salt solution, and washing and drying to prepare the auxiliary agent doped Cu-SSZ-39;
s2, calcining: and (3) placing the assistant-doped Cu-SSZ-39 obtained in the step (S1) at 250-300 ℃ and 550-600 ℃ for segmented heat treatment, cooling to room temperature at a cooling speed of 1-2 ℃/min, and finally grinding, tabletting and granulating to obtain the assistant-doped Cu-SSZ-39 catalyst.
3. The method as claimed in claim 2, wherein the Cu salt solution in step S1 comprises a copper nitrate solution, a copper acetate solution, a copper chloride solution, and a copper sulfate solution, and the concentration of the Cu salt solution is 0.001mol/L to 1 mol/L.
4. The method for preparing the assistant-doped Cu-SSZ-39 catalyst with high hydrothermal stability according to claim 2, wherein the ion exchange in step S1 is performed at 20-40 ℃ for 12-36 h.
5. The method for preparing the assistant-doped Cu-SSZ-39 catalyst with high hydrothermal stability as claimed in claim 2, wherein the step S1 comprises heating to 250-300 ℃ at a heating rate of 2 ℃/min for 4h, and then heating to 550-600 ℃ at a heating rate of 2 ℃/min for 6 h.
6. The preparation method of the high hydrothermal stability assistant doped Cu-SSZ-39 catalyst as claimed in claim 2, wherein the preparation method of the Na-SSZ-39, K-SSZ-39 and Ca-SSZ-39 comprises the following steps:
s11, Na-SSZ-39: uniformly mixing an inorganic alkali solution, a template agent solution and a silicon source and aluminum source to prepare sol, then crystallizing at 135-145 ℃ for 72-168 h to obtain a crystallized product, washing and drying the crystallized product, and then carrying out segmented heat treatment at 250-300 ℃ and 550-600 ℃ to obtain Na-SSZ-39;
s12 preparation of NH4-SSZ-39: carrying out ion exchange on the Na-SSZ-39 obtained in the step S11 and an ammonium salt solution, and washing and drying to obtain NH4-SSZ-39；
S13, exchange K ion or Ca ion: NH of step S124And (3) carrying out ion exchange on the SSZ-39 and a K salt solution or a Ca salt solution, and washing and drying to obtain the K-SSZ-39 or Ca-SSZ-39.
7. The preparation method of the assistant-doped Cu-SSZ-39 catalyst with high hydrothermal stability according to claim 6, wherein the step S11 comprises heating to 250-300 ℃ at a heating rate of 1-5 ℃/min for 2-6 h, and then heating to 550-600 ℃ at a heating rate of 1-3 ℃/min for 4-9 h.
8. The method for preparing the assistant-doped Cu-SSZ-39 catalyst with high hydrothermal stability of claim 6, wherein the ion exchange is performed at a temperature of 70-90 ℃ for 2-10 h in steps S12 and S13, and the ion exchange in step S12 is repeated 2-3 times.
9. The auxiliary agent with high hydrothermal stability, prepared by the preparation method of any one of claims 1 to 8, is doped with the Cu-SSZ-39 catalyst.
10. The use of the high hydrothermal stability co-doped Cu-SSZ-39 catalyst of claim 9 for the elimination of nitrogen oxides from diesel exhaust.
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