CN110479358A - A kind of Cu-SAPO-34 molecular sieve denitrating catalyst and preparation method thereof that dysprosium is modified - Google Patents
A kind of Cu-SAPO-34 molecular sieve denitrating catalyst and preparation method thereof that dysprosium is modified Download PDFInfo
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- CN110479358A CN110479358A CN201910672945.0A CN201910672945A CN110479358A CN 110479358 A CN110479358 A CN 110479358A CN 201910672945 A CN201910672945 A CN 201910672945A CN 110479358 A CN110479358 A CN 110479358A
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- dysprosium
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- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 58
- 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 58
- 229910052692 Dysprosium Inorganic materials 0.000 title claims abstract description 55
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 66
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 52
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 45
- 239000010703 silicon Substances 0.000 claims abstract description 45
- 239000008367 deionised water Substances 0.000 claims abstract description 27
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 27
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 26
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 21
- QXPQVUQBEBHHQP-UHFFFAOYSA-N 5,6,7,8-tetrahydro-[1]benzothiolo[2,3-d]pyrimidin-4-amine Chemical compound C1CCCC2=C1SC1=C2C(N)=NC=N1 QXPQVUQBEBHHQP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 6
- -1 template Chemical compound 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 59
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 239000010949 copper Substances 0.000 claims description 18
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 8
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 2
- DVENVBCPDCQQGD-UHFFFAOYSA-N dysprosium(3+);trinitrate Chemical compound [Dy+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DVENVBCPDCQQGD-UHFFFAOYSA-N 0.000 claims 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract description 19
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 15
- 239000007789 gas Substances 0.000 abstract description 10
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 5
- 231100000572 poisoning Toxicity 0.000 abstract description 5
- 230000000607 poisoning effect Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 16
- 230000006872 improvement Effects 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 239000007848 Bronsted acid Substances 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical class [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 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
- B01J29/04—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
- B01J29/763—CHA-type, e.g. Chabazite, LZ-218
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of modified Cu-SAPO-34 molecular sieve denitrating catalysts and preparation method thereof of dysprosium, comprising: step 1, measures silicon source, silicon source, phosphoric acid, template, copper nitrate, dysprosium nitrate and deionized water, prepares and obtain uniform water solution A；Step 2, water solution A step 1 obtained carries out hydro-thermal reaction, 160~200 DEG C at a temperature of be aged, obtain reaction product B；Step 3, after reaction product B step 2 obtained carries out washing drying, in 450 DEG C or more of temperature lower calcination, the modified Cu-SAPO-34 molecular sieve denitrating catalyst of dysprosium is obtained.Preparation method of the invention can be used for preparing the modified Cu-SAPO-34 molecular sieve denitrating catalyst of the dysprosium of invention；The modified Cu-SAPO-34 molecular sieve denitrating catalyst of dysprosium of the invention can be used for the selective catalytic reduction removing of nitrogen oxides in exhaust gas from diesel vehicle, have certain anti-sulfur dioxide poisoning and good low-temperature catalyzed performance.
Description
Technical field
The invention belongs to environmental catalysis technical field and molecular sieve type catalyst technical fields, are related to a kind of Cu- of modification
SAPO-34 molecular sieve denitrating catalyst, in particular to a kind of dysprosium modified Cu-SAPO-34 molecular sieve denitrating catalyst and its system
Preparation Method.
Background technique
In recent years, the environmental problem that China faces is very severe, and wherein haze is one of environmental pollution of most serious；Nitrogen oxygen
Compound (NOx) it is one of main ingredient in haze composition.NOxHarm is extremely serious, in addition to causing haze problem, can also make
At environmental problems such as acid rain, photochemical fog and depletions of the ozone layer.NOxHave two big sources, first is that using power plant as generation
Produced by the fixation source device of table；Second is that using diesel vehicle as produced by the mobile source device of representative.Wherein, in exhaust gas from diesel vehicle
NOxIt is NO in cityxMain source, due to diesel car engine in normal work its internal temperature it is very high (be greater than 1800
DEG C), therefore NOxGeneration be difficult to avoid that, so need to carry out exhaust aftertreatment to reduce NOxDischarge.
Selective catalytic reduction (SCR) catalyst is widely used in diesel vehicle tail gas processor at present to carry out in tail gas
NOxRemoving；Selective catalytic reduction catalysts include noble metal type catalyst, metal-oxide catalyst and molecular sieve type
Catalyst.Wherein, molecular sieve type catalyst is shown one's talent with the advantage for being provided simultaneously with high activity, high stability and lower cost,
It is widely used in diesel vehicle tail gas processor.
Since chabasie (CHA) the type molecular sieve catalyst of Copper-cladding Aluminum Bar has good NOxIt is catalyzed reducing power, thus it is copper-based
SAPO-34 type molecular sieve denitrating catalyst in large scale investment practical application, shows good catalytic activity and hydro-thermal
Stability.And preparation method is then two-step solution method, and synthetic H-SAPO-34 molecular sieve is exchanged into NH first4-
SAPO-34, then Cu-SAPO-34 is converted by ion exchange, synthesis process is relatively complicated.Simultaneously when diesel quality is poor,
In addition to containing NO in exhaust gas from diesel vehiclexExcept, also contain a small amount of sulfur dioxide (SO2), and SO2It will lead to copper-based SAPO-34
Catalyst poisoning, to reduce its Reduction of NOxAbility.Meanwhile research hair is carried out to exhaust gas from diesel vehicle in real life
It is existing, though up to 1800 DEG C of diesel engine internal temperature, tail gas mean temperature then concentrates on 150-350 DEG C, especially diesel oil
When vehicle is cold-started, exhaust temperature can be maintained for a long time lower than 200 DEG C, and copper-based SAPO-34 type molecular sieve commercial at present is urged
The catalytic activity of agent (200 DEG C) at a lower temperature is not high, causes more NOxDischarge.
Summary of the invention
The purpose of the present invention is to provide a kind of modified Cu-SAPO-34 molecular sieve denitrating catalyst of dysprosium and its preparation sides
Method, to solve above-mentioned one or more technical problems.The modified Cu-SAPO-34 molecular sieve denitration of dysprosium of the invention is urged
Agent can be used for the selective catalytic reduction removing of nitrogen oxides in exhaust gas from diesel vehicle, have certain anti-sulfur dioxide poisoning
With good low-temperature catalyzed performance；Preparation method of the invention can be used for preparing the modified Cu-SAPO-34 molecule of the dysprosium of invention
Sieve denitrating catalyst.
In order to achieve the above objectives, the invention adopts the following technical scheme:
A kind of preparation method of the modified Cu-SAPO-34 molecular sieve denitrating catalyst of dysprosium of the invention, including following step
It is rapid:
Step 1, silicon source, silicon source, phosphoric acid, template, copper nitrate, dysprosium nitrate and deionized water are measured, prepares and obtains
Uniform water solution A；
In the water solution A of preparation, the molar ratio of various ions is silicon source: silicon source: phosphoric acid: template: copper nitrate: dysprosium
Nitrate: deionized water=1:(0.27~0.4): (0.73~0.91): (1.0~1.25): (0.08~0.12): (0.005~
0.015): (20~25)；
Step 2, water solution A step 1 obtained carries out hydro-thermal reaction, 160~200 DEG C at a temperature of be aged, obtain
Reaction product B；
Step 3, it after reaction product B step 2 obtained carries out washing drying, in 450 DEG C or more of temperature lower calcination, obtains
Obtain the modified Cu-SAPO-34 molecular sieve denitrating catalyst of dysprosium.
A further improvement of the present invention is that silicon source is one in aluminium oxide, aluminium hydroxide or sodium metaaluminate in step 1
Kind is a variety of；Silicon source is one of aqueous silica solution, silica ethylene glycol solution or SiO 2 powder or a variety of；
The mass concentration of phosphoric acid is 85%；
Template is one or both of tetraethylenepentamine and morpholine.
A further improvement of the present invention is that template includes tetraethylenepentamine and morpholine in step 1；Four ethylene five
The molar ratio of amine and morpholine is (1~2): (1~2).
A further improvement of the present invention is that the water solution A for obtaining step 1 carries out the process of hydro-thermal reaction in step 2
It specifically includes: being mixed into SAPO-34 in water solution A, after mixing evenly, then carry out hydro-thermal reaction；Wherein, SAPO-34 and deionization
The mass ratio of water is (1~5): 1000.
A further improvement of the present invention is that in step 2, specifically wrapped in 160~200 DEG C of the at a temperature of process that is aged
Include: 160~200 DEG C at a temperature of be aged 48~72h.
A further improvement of the present invention is that step 1 specifically includes:
Step 1.1, template, copper nitrate, dysprosium nitrate and deionized water are measured, prepares and obtains uniform aqueous solution a；
The molar ratio of various ions is template in aqueous solution a: copper nitrate: dysprosium nitrate: deionized water=(1.0~1.25):
(0.08~0.12): (0.005~0.015) (20~25)；
Step 1.2, silicon source and phosphoric acid are measured, and is added in the aqueous solution a of step 1.1 acquisition, is stirred evenly, water is obtained
Solution b；The molar ratio of ion, silicon source: phosphoric acid: template=1:(0.73~0.91 are pressed in aqueous solution b): (1.0~1.25)；
Step 1.3, silicon source is measured, and is added in the aqueous solution b of step 1.2 acquisition, is stirred evenly, water solution A is obtained；In
The molar ratio of ion, silicon source: silicon source=1:(0.27~0.4 are pressed in water solution A).
A further improvement of the present invention is that step 1 specifically includes:
Step 1.1, at room temperature, 0.50g copper nitrate, 0.0075g dysprosium nitrate, 4.30mL tetraethylenepentamine are dissolved in
In the deionized water of 20mL；
Step 1.2,2.20mL phosphoric acid and 3.10g aluminium hydroxide are added in the solution that step 1.1 obtains；
Step 1.3,30% aqueous silica solution of 2.60mL is added in the solution that step 1.2 obtains；
Step 1.4, the morpholine of 1.75mL and 25mg SAPO-34 crystal seed are added in the solution that step 1.3 obtains, are stirred
It mixes uniformly, obtains uniform water solution A.
A further improvement of the present invention is that step 2 specifically includes:
The water solution A that step 1.4 is obtained is placed in water heating kettle, in 160~200 DEG C of at a temperature of 48~72h of ageing, is obtained
Obtain reaction product B.
A kind of modified Cu-SAPO-34 molecular sieve denitrating catalyst of dysprosium of the invention, through the invention above-mentioned preparation side
Method obtains；
Specific surface area is greater than 500m after loaded Cu and Dy2/ g, wherein the ratio between micropore area and mesoporous area are 2:1；Dy
It is Dy:Cu=(0.05~0.1) with Cu molar ratio: 1；Dy therein is positive tetravalence.
Compared with prior art, the invention has the following advantages:
In catalyst of the invention, by one-step synthesis method target product, synthesis step is simplified.Obtained dysprosium changes
The Cu-SAPO-34 molecular sieve denitrating catalyst of property is conducive to the NO under its low temperature there are more low temperature acid adsorption sitesx
It is catalyzed reducing power, the temperature range of its catalysis reaction has been widened, 90% or more is kept in 200~500 DEG C of temperature range
Conversion ratio.In catalyst of the invention, the modification of dysprosium significantly improves the anti-sulfur dioxide poisoning ability of catalyst, 300
At a temperature of DEG C, be passed through sulfur dioxide for a long time, performance only declines 4%, and close performance after sulfur dioxide obtained it is extensive
It is multiple, extend the service life of catalyst.Wherein, in step 2,160~200 DEG C at a temperature of be aged, exceed this temperature model
Enclosing can make synthesized molecular sieve be converted to SAPO-5 or other structures, cannot get the SAPO-34 molecular sieve of CHA type.Step 3
In, in 450 DEG C or more of temperature lower calcination, will cause the organic formwork in framework of molecular sieve lower than this temperature can not be gone completely
It removes, cannot get target product.
In the present invention, the molar ratio of tetraethylenepentamine and morpholine is (1~2): (1~2), be will lead to point beyond this range
Son sieve configuration is become the mixture of SAPO-5, SAPO-18 and SAPO-34 from pure SAPO-34 type.
In the present invention, the mass ratio of SAPO-34 and deionized water is (1~5): 1000, product can be made to produce lower than this range
Rate is greatly lowered, and will cause product purity higher than this range and declines.
In catalyst of the invention, the modification of dysprosium improves reactivity of the catalyst at 200 DEG C or less, at 180 DEG C
When can reach 70% conversion ratio, be conducive to diesel vehicle cold start-up when reduce NOxDischarge.
In preparation method of the invention, synthetic method is relatively simple, and a step can introduce copper and dysprosium inside molecular sieve.Tradition
Synthetic method need to carry out calcination operation three times, and the present invention need to only carry out once calcining that final product can be obtained, more traditional
Two-step solution method simplifies synthesis step, has saved generated time.Meanwhile it avoiding caused by molecular sieve immersion in water
It is destructurized, it ensure that the integrality of its structure, have for the CHA type cellular structure and acidic site quantity that retain molecular sieve
Advantageous effect.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, below to embodiment or existing
Attached drawing needed in technical description does simple introduction；It should be evident that the accompanying drawings in the following description is of the invention
Some embodiments to those skilled in the art without creative efforts, can also be according to this
A little attached drawings obtain other attached drawings.
Fig. 1 is the Cu-SAPO-34 molecular sieve denitrating catalyst pattern schematic diagram that the dysprosium that the embodiment of the present invention 1 obtains is modified
(stereoscan photograph)；
Fig. 2 is the denitration performance for the Cu-SAPO-34 molecular sieve denitrating catalyst that the dysprosium that the embodiment of the present invention 1 obtains is modified
Test result schematic diagram；
Fig. 3 is the ammonia journey for the Cu-SAPO-34 molecular sieve type denitrating catalyst that the dysprosium that the embodiment of the present invention 1 obtains is modified
Sequence desorption by heating test result schematic diagram；
Fig. 4 is the anti-titanium dioxide for the Cu-SAPO-34 molecular sieve denitrating catalyst that the dysprosium that the embodiment of the present invention 2 obtains is modified
Sulphur poisons the performance test results schematic diagram.
Specific embodiment
To keep the purpose, technical effect and technical solution of the embodiment of the present invention clearer, implement below with reference to the present invention
Attached drawing in example, technical scheme in the embodiment of the invention is clearly and completely described；Obviously, described embodiment
It is a part of the embodiment of the present invention.Based on embodiment disclosed by the invention, those of ordinary skill in the art are not making creation
Property labour under the premise of other embodiments obtained, all should belong to the scope of protection of the invention.
A kind of preparation method of the modified Cu-SAPO-34 molecular sieve denitrating catalyst of dysprosium of the invention, including following step
It is rapid:
Step 1, at room temperature by 0.5~0.55g copper nitrate, 0.005~0.01g dysprosium nitrate, 3.4~5.3mL, tetra- ethylene
Five amine are dissolved in the deionized water of 20mL, stir 60min；
Step 2,2.0~2.5mL phosphoric acid and 2.7~3.5g aluminium hydroxide are added in the above solution, continues to stir
60min；
Step 3, above-mentioned solution is added in 30% aqueous silica solution of 2.0~3.0mL, stirs 30min；
Step 4, the morpholine and 20~100mg SAPO-34 crystal seed that 1.4~2.0mL is then added enter above-mentioned solution,
Stir 2h；
Step 5, the above-mentioned solution stirred evenly is added in the stainless steel water heating kettle of polytetrafluoroethyllining lining, 160~
48~72h is aged at a temperature of 200 DEG C；
Step 6, reaction product is taken out from polytetrafluoroethylliner liner, is repeatedly washed with deionized water and dry, then
With 450 DEG C or more (550 DEG C of calcining 6h) in Muffle furnace.Obtain the modified Cu-SAPO-34 molecular sieve denitrating catalyst of dysprosium.
The catalyst is the modified Cu-SAPO-34 molecular sieve catalyst of the dysprosium of one-step synthesis method, by silicon source, silicon when synthesis
Source, phosphorus source, template (SDA), metal nitrate and water are with 1:(0.27~0.4): (0.73~0.91): (1.0~1.25):
(0.09~0.11): the molar ratio of (20~25) and a small amount of SAPO-34 crystal seed are added in water heating kettle and are reacted, wherein SDA
It is made of tetraethylenepentamine and morpholine by the molar ratio of 1:1.Specifically it is also possible that the molar ratio of various ions is aluminium
Source: silicon source: phosphoric acid: template: copper nitrate: dysprosium nitrate: deionized water=1:(0.27~0.4): (0.73~0.91):
(1.0~1.25): (0.08~0.12): (0.005~0.015): (20~25)；；The molar ratio of tetraethylenepentamine and morpholine
For (1~2): (1~2).
Specific surface area is greater than 500m after the catalyst of method preparation of the invention, loaded Cu and Dy2/ g, wherein micropore face
The ratio between long-pending and mesoporous area about 2:1；Dy and Cu molar ratio is Dy:Cu=(0.05~0.1): 1；Dy therein is positive tetravalence.
Method for preparing catalyst of the invention is characterized in that: using tetraethylenepentamine and morpholine as template, using water
One step of thermal method prepares the modified Cu-SAPO-34 molecular sieve denitrating catalyst of dysprosium.
In the present invention, the Cu-SAPO-34 molecular sieve denitrating catalyst that is modified as of dysprosium brings more low temperature acid absorption
Site is conducive to the NO under its low temperaturexIt is catalyzed reducing power, the temperature range of its catalysis reaction has been widened, at 200~500 DEG C
Temperature range in keep 90% or more conversion ratio.The modification of dysprosium significantly improves the anti-sulfur dioxide poisoning energy of catalyst
Power, 300 DEG C at a temperature of, be passed through sulfur dioxide for a long time, performance only declines 4%, and closes performance after sulfur dioxide
Restored, extends the service life of catalyst.It is living that the modification of dysprosium improves reaction of the catalyst at 200 DEG C or less
Property, it can reach 70% conversion ratio at 180 DEG C, be conducive to diesel vehicle and reduce NO in cold start-upxDischarge.
Synthetic method of the invention is relatively simple, and a step can introduce copper and dysprosium inside molecular sieve, and more traditional ion is handed over
The method of changing has saved generated time, and preparation is very fast.
New catalyst of the invention, the modified Cu-SAPO-34 molecular sieve denitrating catalyst of specifically a kind of dysprosium,
The catalyst can be used for the selective catalytic reduction removing of nitrogen oxides in exhaust gas from diesel vehicle.
Embodiment 1
A kind of preparation method of the modified Cu-SAPO-34 molecular sieve denitrating catalyst of dysprosium of the embodiment of the present invention 1, including
Following steps:
(1) 0.50g copper nitrate, 0.0075g dysprosium nitrate, 4.30mL tetraethylenepentamine are dissolved in going for 20mL at room temperature
In ionized water, 60min is stirred；
(2) 2.20mL phosphoric acid and 3.10g aluminium hydroxide are added in the above solution, continues to stir 60min；
(3) above-mentioned solution is added in 30% aqueous silica solution of 2.60mL, stirs 30min；
(4) morpholine and 100mg SAPO-34 crystal seed that 1.75mL is then added enter above-mentioned solution, stir 2h；
(5) the above-mentioned solution stirred evenly is added in the stainless steel water heating kettle of polytetrafluoroethyllining lining, in 200 DEG C of temperature
Degree is lower to be aged 60h.
(6) reaction product is taken out from polytetrafluoroethylliner liner, is repeatedly washed with deionized water and dry, then in horse
Not with 550 DEG C of calcining 6h in furnace.Obtain the modified Cu-SAPO-34 molecular sieve denitrating catalyst of dysprosium.
Catalyst morphology structure is as shown in Figure 1.Dy, Cu molar ratio are Dy:Cu after tested in catalyst prepared by embodiment 1
=1:25 tests discovery Dy:Cu=1:1.2 by x-ray photoelectron spectroscopy, shows that Dy element is more dispersed in outer surface,
Cu2+/ CuO is 34.71%；Catalyst contains more 1~3nm microcellular structure, while having more central hole structure, compares table
Area is 506.20m2/g；Meanwhile catalyst contains a large amount of lewis acidity site and bronsted acid site, is conducive to
It is catalyzed the generation of reaction.
Catalyst activity test uses fixed bed reactors, and air inlet group becomes NO:500ppm；NH3: 500ppm；O2:
10.0%；Nitrogen is Balance Air, and the additional amount 0.06g of catalyst, reaction compartment rate is 36000h-1。
The catalyst is in 200~500 DEG C of temperature range, and the conversion ratio of nitrogen oxides is maintained at 90% or more, such as Fig. 2
It is shown；The ammonia gas absorption ability of its low-temperature range has obtained larger promotion, as shown in figure 3, being able to maintain it still at 180 DEG C
70% transformation efficiency.
Embodiment 2
A kind of preparation method of the modified Cu-SAPO-34 molecular sieve denitrating catalyst of dysprosium of the embodiment of the present invention 2, including
Following steps:
(1) 0.55g copper nitrate, 0.0100g dysprosium nitrate, 4.60mL tetraethylenepentamine are dissolved in going for 20mL at room temperature
In ionized water, 60min is stirred；
(2) 2.45mL phosphoric acid and 2.85g aluminium hydroxide are added in the above solution, continues to stir 60min；
(3) above-mentioned solution is added in 30% aqueous silica solution of 2.60mL, stirs 30min；
(4) morpholine and 50mg SAPO-34 crystal seed that 1.90mL is then added enter above-mentioned solution, stir 2h；
(5) the above-mentioned solution stirred evenly is added in the stainless steel water heating kettle of polytetrafluoroethyllining lining, in 180 DEG C of temperature
Degree is lower to be aged 48h.
(6) reaction product is taken out from polytetrafluoroethylliner liner, is repeatedly washed with deionized water, and is dry, then in horse
Not with 550 DEG C of calcining 6h in furnace.Obtain the modified copper-based molecular sieve denitrating catalyst of dysprosium.
Dy, Cu molar ratio are Dy:Cu=1:18 after tested in catalyst prepared by embodiment 2, by x-ray photoelectron energy
Spectrum test discovery Dy:Cu=1:0.97, shows that Dy element is more dispersed in outer surface, has good resistance for sulfur dioxide
Effect, Cu2+/ CuO is 32.53%；Catalyst contains more 1~3nm microcellular structure, while having more central hole structure,
Its specific surface area is 479.49m2/g；Meanwhile catalyst contains a large amount of lewis acidity site and bronsted acid site,
Be conducive to the generation of catalysis reaction.
Catalyst activity test uses fixed bed reactors, and air inlet group becomes NO:500ppm；NH3: 500ppm；O2:
10.0%；Nitrogen is Balance Air, and the additional amount 0.06g of catalyst, reaction compartment rate is 36000h-1。
For the catalyst in 210~450 DEG C of temperature range, the conversion ratio of nitrogen oxides is maintained at 90% or more；300
At a temperature of DEG C, it is passed through the SO that 8h concentration is 50ppm2Afterwards, reactivity only declines 4%, as shown in Figure 4.
Embodiment 3
A kind of preparation method of the modified Cu-SAPO-34 molecular sieve denitrating catalyst of dysprosium of the embodiment of the present invention, including with
Lower step:
Step 1, silicon source, silicon source, phosphoric acid, template, copper nitrate, dysprosium nitrate, deionized water and crystal seed are measured, is prepared
Obtain uniform water solution A；
According to the molar ratio, silicon source: silicon source: phosphoric acid: template: copper nitrate: dysprosium nitrate: deionized water=1:0.27:
0.91:1.0:0.08:0.005:20；In mass ratio, SAPO-34: above-mentioned solution is added in deionized water=1:1000 to crystal seed；
Step 2, water solution A step 1 obtained carries out hydro-thermal reaction, 160 DEG C at a temperature of be aged, obtain reaction and produce
Object B；
Step 3, it after reaction product B step 2 obtained carries out washing drying, in 450 DEG C or more of temperature lower calcination, obtains
Obtain the modified Cu-SAPO-34 molecular sieve denitrating catalyst of dysprosium.
Wherein, silicon source is aluminium oxide；Silicon source is the mixture of silica ethylene glycol solution and aqueous silica solution；
The mass concentration of phosphoric acid is 85%；
Template is molar ratio tetraethylenepentamine: morpholine=1:2.
Embodiment 4
A kind of preparation method of the modified Cu-SAPO-34 molecular sieve denitrating catalyst of dysprosium of the embodiment of the present invention, including with
Lower step:
Step 1, silicon source, silicon source, phosphoric acid, template, copper nitrate, dysprosium nitrate, deionized water and crystal seed are measured, is prepared
Obtain uniform water solution A；
According to the molar ratio, silicon source: silicon source: phosphoric acid: template: copper nitrate: dysprosium nitrate: deionized water=1:0.4:
0.73:1.25:0.12:0.015:25；In mass ratio, SAPO-34: above-mentioned solution is added in deionized water=5:1000 to crystal seed；
Step 2, water solution A step 1 obtained carries out hydro-thermal reaction, 200 DEG C at a temperature of be aged, obtain reaction and produce
Object B；
Step 3, it after reaction product B step 2 obtained carries out washing drying, in 450 DEG C or more of temperature lower calcination, obtains
Obtain the modified Cu-SAPO-34 molecular sieve denitrating catalyst of dysprosium.
Wherein, silicon source is aluminium oxide and sodium metaaluminate mixture；Silicon source is SiO 2 powder；
The mass concentration of phosphoric acid is 85%；
Template is molar ratio tetraethylenepentamine: morpholine=2:1.
Embodiment 5
A kind of preparation method of the modified Cu-SAPO-34 molecular sieve denitrating catalyst of dysprosium of the embodiment of the present invention, including with
Lower step:
Step 1, silicon source, silicon source, phosphoric acid, template, copper nitrate, dysprosium nitrate, deionized water and crystal seed are measured, is prepared
Obtain uniform water solution A；
According to the molar ratio, silicon source: silicon source: phosphoric acid: template: copper nitrate: dysprosium nitrate: deionized water=1:0.35:
0.86:1.0:0.11:0.01:22；In mass ratio, SAPO-34: above-mentioned solution is added in deionized water=3:1000 to crystal seed；
Step 2, water solution A step 1 obtained carries out hydro-thermal reaction, 180 DEG C at a temperature of be aged, obtain reaction and produce
Object B；
Step 3, it after reaction product B step 2 obtained carries out washing drying, in 450 DEG C or more of temperature lower calcination, obtains
Obtain the modified Cu-SAPO-34 molecular sieve denitrating catalyst of dysprosium.
Wherein, silicon source is aluminium hydroxide；Silicon source is SiO 2 powder；
The concentration of phosphoric acid is 85%；
Template is molar ratio tetraethylenepentamine: morpholine=2:1.
The above embodiments are merely illustrative of the technical scheme of the present invention and are not intended to be limiting thereof, although referring to above-described embodiment pair
The present invention is described in detail, those of ordinary skill in the art still can to a specific embodiment of the invention into
Row modification perhaps equivalent replacement these without departing from any modification of spirit and scope of the invention or equivalent replacement, applying
Within pending claims of the invention.
Claims (9)
1. a kind of preparation method of the modified Cu-SAPO-34 molecular sieve denitrating catalyst of dysprosium, which is characterized in that including following step
It is rapid:
Step 1, silicon source, silicon source, phosphoric acid, template, copper nitrate, dysprosium nitrate and deionized water are measured, prepares and obtains uniformly
Water solution A；
In the water solution A of preparation, the molar ratio of various ions is silicon source: silicon source: phosphoric acid: template: copper nitrate: dysprosium nitric acid
Salt: deionized water=1:(0.27~0.4): (0.73~0.91): (1.0~1.25): (0.08~0.12): (0.005~
0.015): (20~25)；
Step 2, water solution A step 1 obtained carries out hydro-thermal reaction, 160~200 DEG C at a temperature of be aged, reacted
Product B；
Step 3, after reaction product B step 2 obtained carries out washing drying, in 450 DEG C or more of temperature lower calcination, dysprosium is obtained
Modified Cu-SAPO-34 molecular sieve denitrating catalyst.
2. a kind of preparation method of the modified Cu-SAPO-34 molecular sieve denitrating catalyst of dysprosium according to claim 1,
It is characterized in that,
In step 1, silicon source is one of aluminium oxide, aluminium hydroxide or sodium metaaluminate or a variety of；Silicon source is that silica is water-soluble
One of liquid, silica ethylene glycol solution or SiO 2 powder are a variety of；
The mass concentration of phosphoric acid is 85%；
Template is one or both of tetraethylenepentamine and morpholine.
3. a kind of preparation method of the modified Cu-SAPO-34 molecular sieve denitrating catalyst of dysprosium according to claim 1,
It is characterized in that,
In step 1, template includes tetraethylenepentamine and morpholine；The molar ratio of tetraethylenepentamine and morpholine is (1~2):
(1~2).
4. a kind of preparation method of the modified Cu-SAPO-34 molecular sieve denitrating catalyst of dysprosium according to claim 1,
It is characterized in that, in step 2, the process that the water solution A that step 1 obtains carries out hydro-thermal reaction is specifically included:
It is mixed into SAPO-34 in water solution A, after mixing evenly, then carries out hydro-thermal reaction；
Wherein, SAPO-34 and the mass ratio of deionized water are (1~5): 1000.
5. a kind of preparation method of the modified Cu-SAPO-34 molecular sieve denitrating catalyst of dysprosium according to claim 1,
It is characterized in that, in step 2, is specifically included in 160~200 DEG C of the at a temperature of process that is aged:
160~200 DEG C at a temperature of be aged 48~72h.
6. a kind of preparation method of the modified Cu-SAPO-34 molecular sieve denitrating catalyst of dysprosium according to claim 1,
It is characterized in that, step 1 specifically includes:
Step 1.1, template, copper nitrate, dysprosium nitrate and deionized water are measured, prepares and obtains uniform aqueous solution a；In water
The molar ratio of various ions is template in solution a: copper nitrate: dysprosium nitrate: deionized water=(1.0~1.25):
(0.08~0.12): (0.005~0.015) (20~25)；
Step 1.2, silicon source and phosphoric acid are measured, and is added in the aqueous solution a of step 1.1 acquisition, is stirred evenly, aqueous solution is obtained
b；The molar ratio of ion, silicon source: phosphoric acid: template=1:(0.73~0.91 are pressed in aqueous solution b): (1.0~1.25)；
Step 1.3, silicon source is measured, and is added in the aqueous solution b of step 1.2 acquisition, is stirred evenly, water solution A is obtained；Water-soluble
The molar ratio of ion, silicon source: silicon source=1:(0.27~0.4 are pressed in liquid A).
7. a kind of preparation method of the modified Cu-SAPO-34 molecular sieve denitrating catalyst of dysprosium according to claim 1,
It is characterized in that, step 1 specifically includes:
Step 1.1, at room temperature, 0.50g copper nitrate, 0.0075g dysprosium nitrate, 4.30mL tetraethylenepentamine are dissolved in 20mL's
In deionized water；
Step 1.2,2.20mL phosphoric acid and 3.10g aluminium hydroxide are added in the solution that step 1.1 obtains；
Step 1.3,30% aqueous silica solution of 2.60mL is added in the solution that step 1.2 obtains；
Step 1.4, the morpholine of 1.75mL and 25mg SAPO-34 crystal seed are added in the solution that step 1.3 obtains, stirring is equal
It is even, obtain uniform water solution A.
8. a kind of preparation method of the modified Cu-SAPO-34 molecular sieve denitrating catalyst of dysprosium according to claim 7,
It is characterized in that, step 2 specifically includes:
The water solution A that step 1.4 is obtained is placed in water heating kettle, in 160~200 DEG C of at a temperature of 48~72h of ageing, is obtained anti-
Answer product B.
9. a kind of modified Cu-SAPO-34 molecular sieve denitrating catalyst of dysprosium, which is characterized in that by appointing in claim 1 to 8
Preparation method described in one obtains；
Specific surface area is greater than 500m after loaded Cu and Dy2/ g, wherein the ratio between micropore area and mesoporous area are 2:1；Dy and Cu rub
You are than being Dy:Cu=(0.05~0.1): 1；Dy therein is positive tetravalence.
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