CN108525701A - For low temperature NH3- SCR removes diesel engine NOxCopper-based molecular sieve catalyst and preparation method thereof - Google Patents
For low temperature NH3- SCR removes diesel engine NOxCopper-based molecular sieve catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- 239000002808 molecular sieve Substances 0.000 title claims abstract 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 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 26
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 26
- 239000010949 copper Substances 0.000 claims abstract description 22
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- SKEYZPJKRDZMJG-UHFFFAOYSA-N cerium copper Chemical compound [Cu].[Ce] SKEYZPJKRDZMJG-UHFFFAOYSA-N 0.000 claims abstract description 7
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 52
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 27
- 235000011007 phosphoric acid Nutrition 0.000 claims description 26
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 21
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 238000003760 magnetic stirring Methods 0.000 claims description 16
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical class [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 14
- 229910001593 boehmite Inorganic materials 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 9
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 229940000406 drug candidate Drugs 0.000 claims description 6
- 239000003777 experimental drug Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 150000002823 nitrates Chemical class 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000003828 vacuum filtration Methods 0.000 claims description 6
- 206010013786 Dry skin Diseases 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 3
- CQGVSILDZJUINE-UHFFFAOYSA-N cerium;hydrate Chemical compound O.[Ce] CQGVSILDZJUINE-UHFFFAOYSA-N 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 37
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 abstract description 5
- 239000011593 sulfur Substances 0.000 abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- 230000032683 aging Effects 0.000 abstract description 4
- 239000002283 diesel fuel Substances 0.000 abstract description 3
- 238000005580 one pot reaction Methods 0.000 abstract description 3
- 239000003426 co-catalyst Substances 0.000 abstract description 2
- 239000000470 constituent Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 229910052720 vanadium Inorganic materials 0.000 abstract description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 2
- 241000269350 Anura Species 0.000 abstract 2
- 229910052729 chemical element Inorganic materials 0.000 abstract 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 24
- 239000003085 diluting agent Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000003638 chemical reducing agent Substances 0.000 description 8
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- 229910052684 Cerium Inorganic materials 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 239000004575 stone Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000421 cerium(III) oxide Inorganic materials 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000002502 liposome Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 208000036142 Viral infection Diseases 0.000 description 1
- QFBSRHBPIJYSLI-UHFFFAOYSA-N [Ce].[Tm] Chemical compound [Ce].[Tm] QFBSRHBPIJYSLI-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 150000003681 vanadium Chemical class 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
- B01D53/92—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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Materials Engineering (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
One kind being used for low temperature NH3SCR removes diesel engine NOxCopper-based molecular sieve catalyst, belong to diesel engine vent gas exhaust pollutant control technical field.The present invention uses sial phosphorus oxygen tetrahedron (SAPO 34) for carrier, and with Cu for main active component, Ce is cocatalyst component.Synthesize the proportioning of each chemical element that uses for：1Al：1P：0.25Si：0.06Cu‑TEPA：(0.01/0.04/0.06/0.08)Ce：1.6PA：40H2O.Specifically catalyst preparation process includes：The synthesis of Cu TEPA；Copper is as load and the Ce determination and load as co-catalyst load capacity of main active constituent, 34 integrally-built one-pot synthesis of CuCe SAPO.The present invention replaces traditional catalytic component based on vanadium using copper cerium molecular sieve catalyst, reduces the environmental hazard of catalyst, to low temperature active and and height temperature selective have a more substantial increase, effectively reduce NO in 150~550 DEG C of wide temperature windowsx, which has stronger sulfur resistive and water resistant heat aging performance, suitable for the high-sulfur diesel oil in China and urban road traffic status.
Description
Technical field
The present invention relates to one kind being used for low temperature NH3- SCR (ammonia-selective catalytic reduction) removes diesel engine NOxCopper cerium
Based molecular sieve catalyst, especially a kind of low temperature active simultaneously containing copper and cerium have 150~550 DEG C of excellent low temperature
NH3- SCR removes diesel engine NOxCopper cerium based molecular sieve catalyst, belong to diesel engine vent gas exhaust pollutant control technical field.
Background technology
Burning optimization combination urea (Urea)-SCR is considered as diesel vehicle NO under current technical conditionsxDischarge reaches Europe VI
The preferred plan of even higher discharge standard.In recent years, automobile-used Urea-SCR technologies become domestic and international focus of attention. Urea-
SCR is substantially with NH3For the selective catalytic reduction reaction of reducing agent, because urea is not direct and NOxReaction, but first quilt
Evaporation is pyrolyzed into gaseous state NH3。
Commercial vanadium (V)-base catalyst (V2O5/WO3/TiO2) in 300-400 DEG C of temperature range to being marked shown in equation (1)
Quasi- SCR, which reacts, higher catalytic activity, but low temperature (<250 DEG C) it is active poor.
4NH3+4NO+O2→4N2+6H2O (1)
Diesel engine truck exhaust temperature changes very (possible range greatly with operating mode difference：100~550 DEG C), to improve low temperature NOxAlso
Former efficiency, foreign countries propose technical solution of the NO pre-oxidation in conjunction with SCR, i.e., accounting for NO in exhaustxThe parts NO of 90% or more total amount
It is oxidized to NO2, realize quickly SCR reactions shown in equation (2).
2NH3+NO+NO2→2N2+3H2O (2)
The study found that low temperature (<250 DEG C) under the conditions of, work as NO2With the molar ratio of NO close to 1:When 1, (2) rate is reacted
It is more order of magnitude greater than reaction (1) rate.Installing oxidation catalyzer (DOC) on diesel vehicle can the efficient oxidation NO.DOC is general
Catalyst is done using noble metal (Pt, Pd), but such catalyst is expensive and sulfur poisoning easily occurs, it is desirable that sulfur is not in diesel oil
It can exceed that 50ppm.The standard of fuel in China is also not up to EUROIII Emission Standard (sulfur content 350ppm), the mesh of distance 50ppm at present
Mark also wants significant period of time.
In addition, precious metal oxidation catalyst can increase SCR system complexity and cost, increase hardly possible to practical promote and apply
Therefore degree only has higher work in high temperature section (300-400 DEG C) for the catalyst of current diesel vehicle SCR system to SCR reactions
Property, it develops in wider temperature range especially (100-550 DEG C) of cryogenic temperature section with high activity and highly selective new
Type catalyst is more preferably scheme.
In recent years, copper-based molecular sieve catalyst is had received widespread attention due to its good characteristic, the wherein copper-based boiling of aperture
Stone (Cu-CHA) catalyst such as Cu-SAPO-34 and Cu-SSZ-13 have very excellent NH3-SCR activity and better water
Hot ageing stability.Wherein Cu-SAPO-34 has very excellent low temperature active, can be in diesel exhaust gas temperature range
Reach higher NOx removal efficiency, causes attention and the research interest of domestic and international researcher.
Generally, most traditional and using most Cu-SAPO-34 synthetic methods be ion-exchange (including solution from
Sub- exchange process and solid liposome nanoparticle method).Solion exchange process includes exchange process, filtering, washing and roasting, cumbersome conjunction
The practical application of this method is strongly limited at process.Solid liposome nanoparticle method needs synthesize under conditions of particularly severe
(800 DEG C of calcination temperature), may result in the pyrolysis of this structure.In recent years, a kind of entitled one kettle way of novel synthetic method
Successfully be used in the synthesis of Cu-SAPO-34, Raquel et al. by the study found that one pot process Cu-SAPO-34
NO removal efficiency reached 90% in 200 to 450 DEG C of temperature window, and old by 750 DEG C of 13 hours hydro-thermals
After change processing, NO conversion ratios only reduce 10%.Niu Can et al. has carried out the Cu-SAPO-34 of one pot process more harsh
The hydrothermal aging (800 DEG C of 16h) of condition finds that the catalyst after aging can still have big in 225-400 DEG C of temperature window
In 90% efficiency.Ce elements are innovatively added on the basis of existing present Research in the invention, to further increase catalysis
The low temperature active of agent widens low temperature active window, improves the selectivity of total temperature window.
Invention content
The technical problem to be solved by the present invention is to overcome previous NH3- SCR vanadium class catalyst low temperature (<250 DEG C) condition
Lower activity is relatively low, high temperature (>450 DEG C) under the conditions of selectivity poor, the defect of active temperature windows relatively narrow (250~450 DEG C),
The different temperatures characteristic that the activity and selectivity of later catalyst is loaded for copper and cerium, according to the principle of mutual supplement with each other's advantages, warp
Test of many times research, research and design are suitable for diesel vehicle NH3(100~550 DEG C) the wide reaction temperature window of low temperature of SCR system
The copper cerium based molecular sieve catalyst of mouthful high activity/highly selective.The catalyst, which has, to be adapted in reaction temperature be 100~550
Higher catalytic activity and the features such as preferable selectivity in DEG C.
The present invention is achieved through the following technical solutions, and in the present invention, catalyst support component is sial phosphorus oxygen
Tetrahedron (SAPO-34), main active component are Cu, Supplementary active compounds Ce.
Further, in the present invention, carrier component sial phosphorus oxygen tetrahedron (SAPO-34) and main active component are
Cu and Supplementary active compounds are Ce, the element ratio used in building-up process for：1Al：1P：0.25Si：0.06 Cu-TEPA：
(0.01/0.04/0.06/0.08)Ce：1.6PA：40H2O.
Further, in the present invention, it is Salzburg vitriol, auxiliary activity that main active component, which is the presoma of Cu elements,
The presoma that group is divided into Ce is six nitric hydrate ceriums, and the presoma of carrier component sial phosphorus oxygen tetrahedron (SAPO-34) is respectively
Boehmite, phosphoric acid solution, white carbon and propylamine.
Further, in the present invention, catalyst particle size obtained is ranging from：40~60 mesh.
Further, in the present invention, its specific surface area of finished catalyst obtained is in 400-480m2Between/g.
In the present invention, catalyst using sial phosphorus oxygen tetrahedron (SAPO-34) be used as carrier, main active component by
Cu elements collectively form, and use Ce elements for cocatalyst component；Wherein constitute carrier sial phosphorus oxygen tetrahedron (SAPO-34)
White carbon, boehmite, phosphoric acid, the auxiliary element cerium in tetraethylenepentamine and main active component copper and co-catalyst
Molar ratio be to be obtained by test of many times, be：1Al：1P：0.25Si：0.06Cu-TEPA： (0.01/0.04/0.06/
0.08)Ce：1.6PA：40H2O.
The present invention is in existing Cu-SAPO-34NH3On the basis of SCR catalyst, less toxic thulium cerium portion is introduced
Divide substitution copper as the main active in catalyst, in this way, on catalyst performance, due to the valence electron of Ce elements
Can between different valence state phase co-conversion, to show CeO2、Ce2O3、Ce2O5Etc. different oxide types, in reaction temperature and
Under the action of reactant composition, different oxides can be converted mutually, and the free oxygen and free electron of generation can further promote
It is catalyzed the progress of reaction, so as to further widen Cu-SAPO-34NH3The low temperature active window of SCR catalyst, ensures to urge
The selectivity of low temperature and high temperature is improved while the wide Temperature Activity window of agent
It being also known as the method that one kettle way prepares above-mentioned catalyst, specific method by one-step synthesis the invention also includes a kind of
Include the following steps：
The synthesis of first, Cu-TEPA complex compound：
2 hours are mixed until being completely dissolved in the CuSO4 solution of 20wt% and tetraethylenepentamine TEPA.
The synthesis of second, CuCe-TEPA complex compound：
Ce (NO3) 36H2O of four kinds of different proportions is added into the solution, 2 hours are mixed, until the two is filled
Divide mixing, forms the CuCe-TEPA complex compounds of four kinds of difference Ce ratios.
Third, the determination of sial phosphorus oxygen tetrahedron (SAPO-34) carrier element predecessor quality：
It is according to synthesized element ratio：1Al：1P：0.25Si：0.06Cu-TEPA：(0.01/0.04/0.06/0.08)Ce：
1.6PA：40H2O generates 51g Al2O3 according to every 72.85g boehmites respectively, and 98g is generated per 115.3g phosphoric acid solutions
H3PO4 generates 15gSiO2 per 15g white carbons, water is added to generate 48g copper-baths per 15g cupric sulfate pentahydrates, molten per 96g propylamine
Needed for liquid generation 94.576g propylamine and the ratiometric conversion for generating 3.2622g cerous nitrates per 4.3422g cerium nitrates go out
Boehmite, phosphoric acid solution, white carbon, cupric sulfate pentahydrate, propylamine solution, cerium nitrate and the water of experimental drug
Quality.
4th, the formation of catalyst carrier and the load of active element：
Weigh boehmite and phosphoric acid solution according to the calculated quality of step 3, by it is both above-mentioned be added quantitatively go from
Sub- water is simultaneously sufficiently mixed, and is placed on magnetic stirring apparatus, is sufficiently stirred 6 hours, until there is homogeneous gel, then according to step
Rapid three calculated quality weighs Cu-TEPA and six nitric hydrate cerium Ce (NO3) 36H2O are mixed to form according to step 3
CuCe-TEPA complex solutions are placed on magnetic stirring apparatus and fully stir before being slowly added into the homogeneous gel of gained
Mix two hours to form solution A until being thoroughly mixed.Then it weighs white carbon according to the calculated quality of step 3 and propylamine is molten
The two is sufficiently mixed and is added quantitative deionized water, is sufficiently stirred by liquid.It is then added into solution A before, and
It is sufficiently stirred.Then said mixture solution gel is transferred to the polytetrafluoroethylliner liner of stainless steel water thermal synthesis reaction kettle
In, it is put into baking oven, oven temperature is adjusted to 180 degrees Celsius, the mixing in the environment of 180 degrees Celsius of temperature makes hydrothermal reaction kettle
Object crystallization, time have altogether 72 hours.Then by hydrothermal reaction kettle natural cooling, it is molten to pump the crystal in filtering kettle using vacuum filtration
Crystal after being then washed with deionized repeatedly, is put into baking oven, 100 degrees Celsius of setting temperature is dry by the solution in liquid mixture
It is dry whole night.Then the crystal after drying is put into Muffle furnace, 500-800 degrees Celsius of 5 hours of roasting of setting temperature.Roasting is produced
Grinding and tabletting after object cooling, are made final CuCe-SAPO-34 molecular sieve SCR catalysts.
Using the catalyst of the present invention, in diesel engine simulated exhaust gas NOxVolume concentration range：100~1500ppm, diesel oil
Volume concentration range is shared by machine simulated exhaust gas oxygen：0%~20%, reducing agent NH3With NO in diesel engine simulated exhaust gasxRub
You are at equivalence ratio range：0.7-1.2, reaction temperature are 100~550 DEG C, and space velocity range is：5000~30000 h-1It can make tail gas
In have the NO of 60%-98%xRemoval.Reducing agent is NH3, the requirement of reducing agent is NO in aforementioned tail gasx0.7-1.2 times.
Compared with prior art, the present invention have the advantages that for：
First, copper cerium molecular sieve CuCe-SAPO-34 catalyst of the invention has more broad active temperature windows,
Especially under diesel exhaust gas temperature worst cold case (100~250 DEG C), NH is greatly improved3- SCR is to NOxRemoval effect
Rate is arranged in the wide reaction temperature window of temperature significantly to reach to be realized using the multicomponent catalyst in 100~550 DEG C of diesel engines
Reduce NOxPurpose, especially suitable for China's urban road pass through condition；
Second, catalyst of the invention not only has high activity, stability in (100~550 DEG C) of wide reaction temperature window,
And N is taken into account2Generate selectivity, it is therefore prevented that greenhouse gases N2A large amount of generations of O；
Third, catalyst carrier of the invention is using the V for not having virose molecular sieve SAPO-34 substitutions high poison substantially2O5,
The environmental hazard of catalyst is reduced, copper has very good oxidisability and low temperature as active element introducted on carrier
Activity, and the valence electron of Ce elements can between different valence state phase co-conversion, to show CeO2、Ce2O3、Ce2O5Etc. different oxygen
Compound type, under the action of reaction temperature and reactant composition, different oxides can be converted mutually, the free oxygen of generation and from
The progress that catalysis is reacted, the NO to accelerate catalyst surface can be further promoted to be converted into NO by electronics2Speed,
So that more NO are converted to N via " quick SCR " reaction path2, reaction rate and NO when effectively increasing low temperaturexRemoval effect
Rate, meanwhile, cerium, in China's rich reserves, can ensure multi-element metal oxide Novel diesel engine completely as a kind of rare earth element
The raw material supply and cost control of SCR catalyst large-scale production；
4th, catalyst of the invention selects common metal copper cerium as active constituent, sial phosphorus oxygen tetrahedron (SAPO-
34) it is used as carrier, prepares that raw material is cheap to be easy to get, catalyst preparation process is simple, non-toxic, harmless and pollution-free, easy to operate.
5th, it need not additionally increase NH when using the catalyst3The auxiliary device and cost of SCR system, it is practical to promote
It is more convenient.
Description of the drawings
Fig. 1 is the catalyst for the present invention for NH3- SCR removes diesel engine NOxThe structural representation of device for evaluating performance
Figure；
Wherein：1, NO/He diluent gas bottle, 2, O2/ He diluent gas bottles, 3, NH3/ He diluent gas bottles, 4, SO2/He
Diluent gas bottle, 5, He bottles high-purity, 6, mass flow controller, 7, manual ball valve, 8, water bath device, 9, NH3-SCR quartz ampoules
Reactor, 10, powdered SCR catalyst, 11, temperature display controller, 12, swinging tube type resistance furnace, 13, gas-chromatography
Instrument, 14, Fourier Transform Infrared Spectrometer.
Specific implementation mode
It elaborates below in conjunction with the accompanying drawings to the embodiment of the present invention, before the present embodiment is with technical solution of the present invention
It carries, gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following embodiments.
Case study on implementation
As shown in Figure 1, the evaluating apparatus of the present invention includes NO/He diluent gas bottle 1, O2/ He diluent gas bottle 2, NH3/He
Diluent gas bottle 3, SO2/ He diluent gas bottle 4, high-purity He bottles 5, mass flow controller 6, manual ball valve 7, water bath device 8,
NH3-SCR quartz tube reactors 9, powdered SCR catalyst 10, temperature display controller 11, swinging tube type resistance furnace 12, gas
Chromatography 13, Fourier Transform Infrared Spectrometer 14, in NO/He diluent gas bottle 1, O2/ He diluent gas bottle 2, NH3/He
Diluent gas bottle 3, SO2/ He diluent gas bottle 4, high-purity He bottles 5 gas exhaust piping on manual ball valve 7 and quality stream are installed respectively
Amount controller 6；After gas mixing in five gas cylinders, some flows directly into NH3-SCR quartz tube reactors 9, there is one
Lease making is crossed flows into NH3-SCR quartz tube reactors 9 again after water bath device 8；Powdered SCR catalyst 10 is arranged in NH3-SCR stones
In English pipe reactor 9, swinging tube type resistance furnace 12 is arranged in the periphery of NH3-SCR quartz tube reactors 9, temperature display control
Device 11 processed is connected with swinging tube type resistance furnace 12, and gas chromatograph 13, Fourier Transform Infrared Spectrometer 14 are arranged in
The tail portion of NH3-SCR quartz tube reactors 9.
Embodiment 1
Synthesis ratio 1Al：1P：0.25Si：0.06Cu-TEPA：0.01Ce：1.6PA：40H2O
The synthesis of first, Cu-TEPA complex compound：
The CuSO4 solution 48g and tetraethylenepentamine TEPA solution 12.62g for weighing 20wt%, the two is mixed, is placed on
2 hours are stirred on magnetic stirring apparatus until being completely dissolved；
The synthesis of second, CuCe-TEPA complex compound：
Ce (NO3) 36H2O weighed is added into the solution, quality 4.34g is placed on magnetic stirring apparatus,
2 hours are mixed, until the two is sufficiently mixed, form the CuCe-TEPA complex compounds of 0.01Ce ratios.
Third, the determination of sial phosphorus oxygen tetrahedron (SAPO-34) carrier element predecessor quality：
It is according to synthesized element ratio：1Al：1P：0.25Si：0.06Cu-TEPA：0.01Ce：1.6PA：40H2O.Respectively
51g Al2O3 are generated according to every 72.85g boehmites, 98g H3PO4 are generated per 115.3g phosphoric acid solutions, per 15g white carbons
15gSiO2 is generated, water is added to generate 48g copper-baths per 15g cupric sulfate pentahydrates, 94.576g propylamine is generated per 96g propylamine solution
The ratiometric conversion that 3.2622g cerous nitrates are generated with every 4.3422g cerium nitrates goes out the quasi- thin water of required experimental drug
The quality of aluminium stone, phosphoric acid solution, white carbon, cupric sulfate pentahydrate, propylamine solution, cerium nitrate and water.
4th, the formation of catalyst carrier and the load of active element：
Boehmite 72.85g and phosphoric acid solution 115.3g are weighed according to the calculated quality of step 3, it will be both above-mentioned
Quantitative deionized water is added and is sufficiently mixed, is placed on magnetic stirring apparatus, is sufficiently stirred 6 hours, it is uniformly solidifying until occurring
Glue is placed on magnetic force and stirs before being then slowly added into the CuCe-TEPA complex compounds that step 2 obtains in the homogeneous gel of gained
It mixes and is sufficiently stirred two hours on device to form solution A until being thoroughly mixed.Then it is weighed according to the calculated quality of step 3 white
The two is sufficiently mixed and the quantitative deionized water (deionized water that attention is added in total is added by carbon black 15g and propylamine solution 96g
Amount is 638.7g), it is sufficiently stirred.It is then added into solution A before, and is sufficiently stirred.Then by above-mentioned mixing
Object solution gel is transferred in the polytetrafluoroethylliner liner of stainless steel water thermal synthesis reaction kettle, is put into baking oven, and oven temperature is adjusted to
180 degrees Celsius, the mixture crystallization in the environment of 180 degrees Celsius of temperature makes hydrothermal reaction kettle, the time has altogether 72 hours.So
Afterwards by hydrothermal reaction kettle natural cooling, the solution in the crystalloid solution mixture in filtering kettle is pumped using vacuum filtration, is then used
After deionized water washing repeatedly, crystal is put into baking oven, the 100 degrees Celsius of dryings of setting temperature are whole night.Then by the crystalline substance after drying
Body is put into Muffle furnace, 500-800 degrees Celsius of 5 hours of roasting of setting temperature.Grinding and tabletting after product of roasting is cooled down, system
At final CuCe-SAPO-34 molecular sieve SCR catalysts.
With NH shown in FIG. 13-SCR removes diesel engine NOxDevice for evaluating performance evaluates catalyst B in NH3In-SCR reactions
Catalytic performance.In evaluation experimental, NO in diesel engine vent gas is simulatedxVolumetric concentration is 600ppm, and the volumetric concentration of oxygen is
10%, reducing agent NH3With NOxMolar equivalent ratio be 1:1, reaction temperature is 100~550 DEG C, air speed 10770h-1.NO and
NH3Fourier Transform Infrared Spectrometer 14 and its gas cell attachment is used to measure, NH3The N that-SCR reactions generate2Concentration be use
Gas chromatograph 13 measures.(100~550 DEG C) catalyst restores NO at a temperature of differential responsesxEfficiency and N2Selectivity point
Tables 1 and 2 is not seen.
Embodiment 2
Synthesis ratio 1Al：1P：0.25Si：0.06Cu-TEPA：0.04Ce：1.6PA：40H2O
The synthesis of first, Cu-TEPA complex compound：
The CuSO4 solution 48g and tetraethylenepentamine TEPA solution 12.62g for weighing 20wt%, the two is mixed, is placed on
2 hours are stirred on magnetic stirring apparatus until being completely dissolved；
The synthesis of second, CuCe-TEPA complex compound：
Ce (NO3) 36H2O weighed is added into the solution, quality 17.37g is placed on magnetic stirring apparatus,
2 hours are mixed, until the two is sufficiently mixed, form the CuCe-TEPA complex compounds of 0.01Ce ratios.
Third, the determination of sial phosphorus oxygen tetrahedron (SAPO-34) carrier element predecessor quality：
It is according to synthesized element ratio：1Al：1P：0.25Si：0.06Cu-TEPA：0.01Ce：1.6PA：40H2O.Respectively
51g Al2O3 are generated according to every 72.85g boehmites, 98g H3PO4 are generated per 115.3g phosphoric acid solutions, per 15g white carbons
15gSiO2 is generated, water is added to generate 48g copper-baths per 15g cupric sulfate pentahydrates, 94.576g propylamine is generated per 96g propylamine solution
The ratiometric conversion that 3.2622g cerous nitrates are generated with every 4.3422g cerium nitrates goes out the quasi- thin water of required experimental drug
The quality of aluminium stone, phosphoric acid solution, white carbon, cupric sulfate pentahydrate, propylamine solution, cerium nitrate and water.
4th, the formation of catalyst carrier and the load of active element：
Boehmite 72.85g and phosphoric acid solution 115.3g are weighed according to the calculated quality of step 3, it will be both above-mentioned
Quantitative deionized water is added and is sufficiently mixed, is placed on magnetic stirring apparatus, is sufficiently stirred 6 hours, it is uniformly solidifying until occurring
Glue is placed on magnetic force and stirs before being then slowly added into the CuCe-TEPA complex compounds that step 2 obtains in the homogeneous gel of gained
It mixes and is sufficiently stirred two hours on device to form solution A until being thoroughly mixed.Then it is weighed according to the calculated quality of step 3 white
The two is sufficiently mixed and the quantitative deionized water (deionized water that attention is added in total is added by carbon black 15g and propylamine solution 96g
Amount is 635.4g), it is sufficiently stirred.It is then added into solution A before, and is sufficiently stirred.Then by above-mentioned mixing
Object solution gel is transferred in the polytetrafluoroethylliner liner of stainless steel water thermal synthesis reaction kettle, is put into baking oven, and oven temperature is adjusted to
180 degrees Celsius, the mixture crystallization in the environment of 180 degrees Celsius of temperature makes hydrothermal reaction kettle, the time has altogether 72 hours.So
Afterwards by hydrothermal reaction kettle natural cooling, the solution in the crystalloid solution mixture in filtering kettle is pumped using vacuum filtration, is then used
After deionized water washing repeatedly, crystal is put into baking oven, the 100 degrees Celsius of dryings of setting temperature are whole night.Then by the crystalline substance after drying
Body is put into Muffle furnace, 500-800 degrees Celsius of 5 hours of roasting of setting temperature.Grinding and tabletting after product of roasting is cooled down, system
At final CuCe-SAPO-34 molecular sieve SCR catalysts.
With NH shown in FIG. 13-SCR removes diesel engine NOxDevice for evaluating performance evaluates catalyst B in NH3In-SCR reactions
Catalytic performance.In evaluation experimental, NO in diesel engine vent gas is simulatedxVolumetric concentration is 600ppm, and the volumetric concentration of oxygen is
10%, reducing agent NH3With NOxMolar equivalent ratio be 1:1, reaction temperature is 100~550 DEG C, air speed 10770h-1.NO and
NH3Fourier Transform Infrared Spectrometer 14 and its gas cell attachment is used to measure, NH3The N that-SCR reactions generate2Concentration be use
Gas chromatograph 13 measures.(100~550 DEG C) catalyst restores NO at a temperature of differential responsesxEfficiency and N2Selectivity point
Tables 1 and 2 is not seen.
Embodiment 3
Synthesis ratio 1Al：1P：0.25Si：0.06Cu-TEPA：0.06Ce：1.6PA：40H2O
The synthesis of first, Cu-TEPA complex compound：
The CuSO4 solution 48g and tetraethylenepentamine TEPA solution 12.62g for weighing 20wt%, the two is mixed, is placed on
2 hours are stirred on magnetic stirring apparatus until being completely dissolved；
The synthesis of second, CuCe-TEPA complex compound：
Ce (NO3) 36H2O weighed is added into the solution, quality 26.05g is placed on magnetic stirring apparatus,
2 hours are mixed, until the two is sufficiently mixed, form the CuCe-TEPA complex compounds of 0.01Ce ratios.
Third, the determination of sial phosphorus oxygen tetrahedron (SAPO-34) carrier element predecessor quality：
It is according to synthesized element ratio according to described in claims 3：1Al：1P：0.25Si：0.06Cu-TEPA：
0.01Ce：1.6PA：40H2O.51g Al2O3 are generated according to every 72.85g boehmites respectively, per 115.3g phosphoric acid solution lifes
At 98g H3PO4,15gSiO2 is generated per 15g white carbons, adds water to generate 48g copper-baths per 15g cupric sulfate pentahydrates, often
96g propylamine solution generates 94.576g propylamine and generates the ratio of 3.2622g cerous nitrates per 4.3422g cerium nitrates
Converse boehmite, phosphoric acid solution, white carbon, cupric sulfate pentahydrate, propylamine solution, six nitric hydrates of required experimental drug
The quality of sub- cerium and water.
4th, the formation of catalyst carrier and the load of active element：
Boehmite 72.85g and phosphoric acid solution 115.3g are weighed according to the calculated quality of step 3, it will be both above-mentioned
Quantitative deionized water is added and is sufficiently mixed, is placed on magnetic stirring apparatus, is sufficiently stirred 6 hours, it is uniformly solidifying until occurring
Glue is placed on magnetic force and stirs before being then slowly added into the CuCe-TEPA complex compounds that step 2 obtains in the homogeneous gel of gained
It mixes and is sufficiently stirred two hours on device to form solution A until being thoroughly mixed.Then it is weighed according to the calculated quality of step 3 white
The two is sufficiently mixed and the quantitative deionized water (deionized water that attention is added in total is added by carbon black 15g and propylamine solution 96g
Amount is 633.3g), it is sufficiently stirred.It is then added into solution A before, and is sufficiently stirred.Then by above-mentioned mixing
Object solution gel is transferred in the polytetrafluoroethylliner liner of stainless steel water thermal synthesis reaction kettle, is put into baking oven, and oven temperature is adjusted to
180 degrees Celsius, the mixture crystallization in the environment of 180 degrees Celsius of temperature makes hydrothermal reaction kettle, the time has altogether 72 hours.So
Afterwards by hydrothermal reaction kettle natural cooling, the solution in the crystalloid solution mixture in filtering kettle is pumped using vacuum filtration, is then used
After deionized water washing repeatedly, crystal is put into baking oven, the 100 degrees Celsius of dryings of setting temperature are whole night.Then by the crystalline substance after drying
Body is put into Muffle furnace, 500-800 degrees Celsius of 5 hours of roasting of setting temperature.Grinding and tabletting, are made after product of roasting is cooled down
Final CuCe-SAPO-34 molecular sieve SCR catalysts.
With NH shown in FIG. 13-SCR removes diesel engine NOxDevice for evaluating performance evaluates catalyst B in NH3In-SCR reactions
Catalytic performance.In evaluation experimental, NO in diesel engine vent gas is simulatedxVolumetric concentration is 600ppm, and the volumetric concentration of oxygen is
10%, reducing agent NH3With NOxMolar equivalent ratio be 1:1, reaction temperature is 100~550 DEG C, air speed 10770h-1.NO and
NH3Fourier Transform Infrared Spectrometer 14 and its gas cell attachment is used to measure, NH3The N that-SCR reactions generate2Concentration be use
Gas chromatograph 13 measures.(100~550 DEG C) catalyst restores NO at a temperature of differential responsesxEfficiency and N2Selectivity point
Tables 1 and 2 is not seen.
Embodiment 4
Synthesis ratio 1Al：1P：0.25Si：0.06Cu-TEPA：0.08Ce：1.6PA：40H2O
The synthesis of first, Cu-TEPA complex compound：
The CuSO4 solution 48g and tetraethylenepentamine TEPA solution 12.62g for weighing 20wt%, the two is mixed, is placed on
2 hours are stirred on magnetic stirring apparatus until being completely dissolved；
The synthesis of second, CuCe-TEPA complex compound：
Ce (NO3) 36H2O weighed is added into the solution, quality 34.74g is placed on magnetic stirring apparatus,
2 hours are mixed, until the two is sufficiently mixed, form the CuCe-TEPA complex compounds of 0.01Ce ratios.
Third, the determination of sial phosphorus oxygen tetrahedron (SAPO-34) carrier element predecessor quality：
It is according to synthesized element ratio：1Al：1P：0.25Si：0.06Cu-TEPA：0.01Ce：1.6PA：40H2O.Respectively
51g Al2O3 are generated according to every 72.85g boehmites, 98g H3PO4 are generated per 115.3g phosphoric acid solutions, per 15g white carbons
15gSiO2 is generated, water is added to generate 48g copper-baths per 15g cupric sulfate pentahydrates, 94.576g propylamine is generated per 96g propylamine solution
The ratiometric conversion that 3.2622g cerous nitrates are generated with every 4.3422g cerium nitrates goes out the quasi- thin water of required experimental drug
The quality of aluminium stone, phosphoric acid solution, white carbon, cupric sulfate pentahydrate, propylamine solution, cerium nitrate and water.
4th, the formation of catalyst carrier and the load of active element：
Boehmite 72.85g and phosphoric acid solution 115.3g are weighed according to the calculated quality of step 3, it will be both above-mentioned
Quantitative deionized water is added and is sufficiently mixed, is placed on magnetic stirring apparatus, is sufficiently stirred 6 hours, it is uniformly solidifying until occurring
Glue is placed on magnetic force and stirs before being then slowly added into the CuCe-TEPA complex compounds that step 2 obtains in the homogeneous gel of gained
It mixes and is sufficiently stirred two hours on device to form solution A until being thoroughly mixed.Then it is weighed according to the calculated quality of step 3 white
The two is sufficiently mixed and the quantitative deionized water (deionized water that attention is added in total is added by carbon black 15g and propylamine solution 96g
Amount is 631.13g), it is sufficiently stirred.It is then added into solution A before, and is sufficiently stirred.Then by above-mentioned mixing
Object solution gel is transferred in the polytetrafluoroethylliner liner of stainless steel water thermal synthesis reaction kettle, is put into baking oven, and oven temperature is adjusted to
180 degrees Celsius, the mixture crystallization in the environment of 180 degrees Celsius of temperature makes hydrothermal reaction kettle, the time has altogether 72 hours.So
Afterwards by hydrothermal reaction kettle natural cooling, the solution in the crystalloid solution mixture in filtering kettle is pumped using vacuum filtration, is then used
After deionized water washing repeatedly, crystal is put into baking oven, the 100 degrees Celsius of dryings of setting temperature are whole night.Then by the crystalline substance after drying
Body is put into Muffle furnace, 500-800 degrees Celsius of 5 hours of roasting of setting temperature.Grinding and tabletting after product of roasting is cooled down, system
At final CuCe-SAPO-34 molecular sieve SCR catalysts.
With NH shown in FIG. 13-SCR removes diesel engine NOxDevice for evaluating performance evaluates catalyst B in NH3In-SCR reactions
Catalytic performance.In evaluation experimental, NO in diesel engine vent gas is simulatedxVolumetric concentration is 600ppm, and the volumetric concentration of oxygen is
10%, reducing agent NH3With NOxMolar equivalent ratio be 1:1, reaction temperature is 100~550 DEG C, air speed 10770h-1.NO and
NH3Fourier Transform Infrared Spectrometer 14 and its gas cell attachment is used to measure, NH3The N that-SCR reactions generate2Concentration be use
Gas chromatograph 13 measures.(100~550 DEG C) catalyst restores NO at a temperature of differential responsesxEfficiency and N2Selectivity point
Tables 1 and 2 is not seen.
(100~550 DEG C) catalyst restores NO at a temperature of 1 differential responses of tablexActivity evaluation
(100~550 DEG C) catalyst restores NO at a temperature of 2 differential responses of tablexSelective evaluation result
Example the above is only the implementation of the present invention is not intended to limit the scope of the invention, every to utilize this hair
Equivalent structure or equivalent flow shift made by bright specification and accompanying drawing content is applied directly or indirectly in other relevant skills
Art field, is included within the scope of the present invention.
Claims (6)
1. one kind being used for low temperature NH3- SCR removes the copper-based molecular sieve catalyst of Diesel NOx, which is characterized in that carrier component is
Sial phosphorus oxygen tetrahedron (SAPO-34), main active component are Cu, Supplementary active compounds Ce.
2. according to claim 1, be used for low temperature NH3- SCR removes diesel engine NOxCopper-based molecular sieve catalyst, it is special
Sign is the carrier component sial phosphorus oxygen tetrahedron (SAPO-34) and main active component is Cu and Supplementary active compounds are
Ce, the element ratio used in building-up process for：1Al：1P：0.25Si：0.06Cu-TEPA：(0.01/0.04/0.06/0.08)
Ce：1.6PA：40H2O.
3. the copper-based molecular sieve catalyst according to claim 2, for low temperature NH3-SCR removal Diesel NOx,
It is characterized in that the main active component be the presoma of Cu elements is Salzburg vitriol, Supplementary active compounds are the presoma of Ce
For six nitric hydrate ceriums, the presoma of carrier component sial phosphorus oxygen tetrahedron (SAPO-34) is respectively that boehmite, phosphoric acid are molten
Liquid, white carbon and propylamine.
4. according to claim 2, be used for low temperature NH3- SCR removes diesel engine NOxCopper-based molecular sieve catalyst, it is special
Sign is catalyst particle size obtained ranging from：40~60 mesh.
5. according to claim 3, be used for low temperature NH3- SCR removes diesel engine NOxCopper cerium based molecular sieve catalyst,
It is characterized in that its specific surface area of finished catalyst obtained in 400-480m2Between/g.
6. a kind of preparation method of catalyst as claimed in claim 1, it is characterised in that preparation method is one-step synthesis, tool
Body technology includes the following steps：
The synthesis of first, Cu-TEPA complex compound：
2 hours are mixed until being completely dissolved in the CuSO4 solution of 20wt% and tetraethylenepentamine TEPA；
The synthesis of second, CuCe-TEPA complex compound：
Ce (NO3) 36H2O of four kinds of different proportions is added into the solution, 2 hours are mixed, until the two is fully mixed
It closes, forms the CuCe-TEPA complex compounds of four kinds of difference Ce ratios；
Third, the determination of sial phosphorus oxygen tetrahedron (SAPO-34) carrier element predecessor quality：
It is according to synthesized element ratio according to described in claims 2：1Al：1P：0.25Si：0.06Cu-TEPA：(0.01/
0.04/0.06/0.08)Ce：1.6PA：40H2O generates 51gAl2O3 according to every 72.85g boehmites respectively, per 115.3g
Phosphoric acid solution generates 98g H3PO4, generates 15gSiO2 per 15g white carbons, water is added to generate 48g copper sulphate per 15g cupric sulfate pentahydrates
Solution generates 94.576g propylamine per 96g propylamine solution and generates 3.2622g cerous nitrates per 4.3422g cerium nitrates
Ratiometric conversion go out boehmite, phosphoric acid solution, white carbon, cupric sulfate pentahydrate, propylamine solution, six water of required experimental drug
Close the quality of cerous nitrate and water；
4th, the formation of catalyst carrier and the load of active element：
Boehmite and phosphoric acid solution are weighed according to the calculated quality of step 3, quantitative deionized water is added by both above-mentioned
And be sufficiently mixed, it is placed on magnetic stirring apparatus, is sufficiently stirred 6 hours, until there is homogeneous gel, then according to step 3
Calculated quality weighs the CuCe- that Cu-TEPA and six nitric hydrate cerium Ce (NO3) 36H2O are mixed to form according to step 2
TEPA complex solutions are placed on magnetic stirring apparatus before being slowly added into the homogeneous gel of gained and are sufficiently stirred two
A hour to form solution A until being thoroughly mixed；Then white carbon and propylamine solution are weighed according to the calculated quality of step 3, it will
The two is sufficiently mixed and is added quantitative deionized water, is sufficiently stirred.It is then added into solution A before, and fully
Stirring.Then said mixture solution gel is transferred in the polytetrafluoroethylliner liner of stainless steel water thermal synthesis reaction kettle, is put
Enter baking oven, oven temperature is adjusted to 180 degrees Celsius, keeps the mixture in hydrothermal reaction kettle brilliant in the environment of 180 degrees Celsius of temperature
Change, the time has altogether 72 hours；Then by hydrothermal reaction kettle natural cooling, it is mixed to pump the crystalloid solution in filtering kettle using vacuum filtration
The solution in object is closed, after being then washed with deionized repeatedly, crystal is put into baking oven, setting 100 degrees Celsius of dryings of temperature are whole
Night；Then the crystal after drying is put into Muffle furnace, 500-800 degrees Celsius of 5 hours of roasting of setting temperature.Product of roasting is cold
But grinding and tabletting afterwards, is made final CuCe-SAPO-34 molecular sieve SCR catalysts.
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