CN110508319A - A kind of cerium dopping CuCex-SAPO-18 molecular sieve catalyst and preparation method - Google Patents
A kind of cerium dopping CuCex-SAPO-18 molecular sieve catalyst and preparation method Download PDFInfo
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- CN110508319A CN110508319A CN201910851975.8A CN201910851975A CN110508319A CN 110508319 A CN110508319 A CN 110508319A CN 201910851975 A CN201910851975 A CN 201910851975A CN 110508319 A CN110508319 A CN 110508319A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 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 41
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 40
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 23
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000010703 silicon Substances 0.000 claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 17
- 150000001412 amines Chemical class 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 239000011574 phosphorus Substances 0.000 claims abstract description 9
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims abstract description 7
- 238000002425 crystallisation Methods 0.000 claims abstract description 4
- 230000008025 crystallization Effects 0.000 claims abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 230000009977 dual effect Effects 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000012043 crude product Substances 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical group CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 229910001593 boehmite Inorganic materials 0.000 claims description 5
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical group O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 5
- 150000000703 Cerium Chemical class 0.000 claims description 4
- 238000001879 gelation Methods 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 55
- 239000010949 copper Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000007789 gas Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- SKEYZPJKRDZMJG-UHFFFAOYSA-N cerium copper Chemical compound [Cu].[Ce] SKEYZPJKRDZMJG-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical group NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 206010002660 Anoxia Diseases 0.000 description 1
- 241000976983 Anoxia Species 0.000 description 1
- 241000269350 Anura Species 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- -1 Cu2+ cation Chemical class 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010054147 Hemoglobins Proteins 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000007953 anoxia Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
-
- 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
- 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
- B01J35/64—Pore diameter
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of preparation methods of cerium dopping Cu-SAPO-18 molecular sieve catalyst, wherein, using phosphorus source, silicon source, silicon source as precursor material, using two kinds of organic amines as dual mould plate agent, using anhydrous cupric sulfate and cerous nitrate as the precursor material of active component, prepared through one-step method hydro-thermal process crystallization: by CuCex-SAPO-18 molecular sieve catalyst prepared by the present invention in NH3There is good catalytic performance and good water-resistance in-SCR reaction, and chemical stability is good, there is huge application potential.
Description
Technical field
The invention belongs to nitrogen oxide catalyst technical field more particularly to a kind of molecular sieve catalyst and preparation methods.
Background technique
Nitrogen oxides (NOx) is a kind of important atmosphere pollution.The discharge of NOx is to human production life and natural ring
Bring great harm in border.In terms of human health, NO is easy to combine hemoglobin, causes human body anoxia；NO2 mainly stimulates people
Body lung and respiratory tract cause the corrosion-damaged etc. of human organ.In terms of ecological environment, NOx can cause acid rain, acid mist and light
Chemical fumes promotes global warming.In addition, the increase of nitrogen deposition amount, will lead to surface water eutrophication and land, wetland,
The acidification of lithic drainage and poison.Its coverage develops into regional pollution via locality pollution, or even becomes the whole world
Contact scar.It endangers in view of NOx existing for the mankind and ecological environment, the generation and discharge for controlling NOx are particularly significant problems.
Currently, the technology of control NOx emission refers mainly to low NOx combusting technology and flue gas NOx removing sulfuldioxide.And skill is removed in flue gas NOx
Selective catalytic reduction (Selective catalytic reduction, SCR) is currently to be most widely used in the world in art
Gas denitrifying technology, mainly using NH3 as reducing agent, key problem in technology be selection efficient stable catalyst.
The source of nitrogen oxides is generated in addition to various industrial activities, special also from the discharge of gasoline car exhaust gas from diesel vehicle
It is not the nitrogen oxides (NOx) generated in the process for the high-temp combustion of diesel engine.Processing for this partial tail gas, copper
The aperture CHA material of exchange can be used as one of preferred catalyst, such as alumino-silicate (Cu-SSZ-13) or silicoaluminophosphate
(Cu-SAPO-34) (SAPO is molecular sieve structure name of code).(such as with the zeolites with larger hole of other previous research
Cu-Beta or Cu-ZSM-5 etc.) it compares, aperture Cu-CHA shows higher catalytic activity and hydrothermally stable to the SCR of NOx
Property.This point is most important for SCR reaction existing for steam under high temperature (being higher than 400 DEG C).Usually in these exacting terms
Under, Cu-Beta or Cu-ZSM-5 zeolite can be by permanent deactivation.By by the three of Cu2+ cation outside skeleton and double 6 rings (D6R)
A oxygen atom ligand can solve stability problem, this is considered as the catalytic activity and hydrothermally stable for improving Cu-CHA catalyst
The main reason for property.
Other than Cu exchanges CHA, other Cu- for containing D6R exchange aperture alumino-silicate has been reported as the SCR's of NOx
Effective catalyst, such as Cu-SSZ-16 and Cu-SSZ-39.In particular, the Cu-SSZ-39 that AEI structure is presented shows the SCR of NOx
Very high catalytic activity and hydrothermal stability out, even higher than business Cu-SSZ-13 catalyst.But SSZ-39 prepares item
Part range is very limited.Another AEI structure molecular screen, such as SAPO-18, SAPO-18 have been widely used as urging for MTO reaction
Agent, but the description of few SCR about the SAPO-18 for using Cu to exchange.Cu-SAPO-18 is main as SCR catalyst
If since it has excellent SCR performance, wide temperature window and high N2 selectivity at low temperature.However, Cu-SAPO-18 is urged
The catalytic activity of agent at high temperature is there is still a need for improving to adapt to 500 DEG C or more of diesel engine exhaust condition, because NO turns
Rate is decreased sharply above at 450 DEG C.Since Ce has excellent oxygen storage capacity and unique redox property, contain cerium
Catalyst has been widely studied to react for various catalysis, and addition Ce can improve Cu base by inhibiting the formation of Cu oxide
The activity and thermal stability of catalyst.
Summary of the invention
Technical problems to be solved by the inivention
The object of the present invention is to provide a kind of aperture AEI structure molecular screens with stronger water-resistance, copper doped cerium
Catalyst, while there is the catalyst of good removing NOx and nitrogen selective energy.
Method for solving technical problem
In view of the above-mentioned problems, the invention proposes a kind of preparation method of cerium dopping Cu-SAPO-18 molecular sieve catalyst,
It is using phosphorus source, silicon source, silicon source as precursor material, using two kinds of organic amines as dual mould plate agent, using mantoquita and cerium salt as activity
The precursor material of component is prepared through one-step method hydro-thermal process crystallization.
A kind of embodiment is, comprising the following steps:
(1) anhydrous cupric sulfate and cerous nitrate are dissolved with water, the first organic amine template is added, obtains mixed liquor 1；
(2) phosphorus source, water and silicon source are added in mixed liquor 1 and obtain mixed liquor 2；
(3) silicon source is added in mixed liquor 2 and obtains mixed liquor 3；
(4) the second organic amine template gelation is added in mixed liquor 3, obtains mixed liquor 4；
(5) mixed liquor 4 is reacted in a high pressure reaction kettle and obtains crude product；
(6) crude product high-temperature roasting is obtained into catalyst.
A kind of embodiment is, wherein the ratio of each precursor material is (molar ratio): 0.9~1.1Al2O3:0.85~
0.95P2O5:1.15~1.25SiO2:1.55DIPEA:0.05~0.15Cu-TEPA:0.002~0.006Ce:45H2O.
A kind of embodiment is that phosphorus source is selected from phosphoric acid, and silicon source is selected from AS-40, and silicon source is selected from boehmite, and mantoquita is selected from
Copper sulphate, cerium salt are selected from cerous nitrate.
A kind of embodiment is, wherein the first organic amine template is selected from tetraethylenepentamine (TEPA)；Second organic amine mould
Plate agent is selected from N, N- diisopropylethylamine (DIPEA).
A kind of embodiment is, wherein in step (5), 90~100h is reacted at 180-200 DEG C.
A kind of embodiment is that wherein in step (6), crude product roasts 4~5h at 550-650 DEG C.
An embodiment according to the present invention, provides a kind of cerium dopping Cu-SAPO-18 molecular sieve catalyst, basis
Above-mentioned preparation method is made.
An embodiment according to the present invention, provides a kind of cerium dopping Cu-SAPO-18 molecular sieve catalyst, has
AEI structure indicates that wherein x represents Ce/Al molar ratio with following formula CuCex-SAPO-18, and value is 0.0005~0.08；It is preferred that
0.003~0.02.
Beneficial effects of the present invention
1, CuCex-SAPO-18 molecular sieve catalyst simple synthetic method prepared by the present invention, material water-resistance is strong, hydro-thermal
Stability improves, and is easy to be mass produced, have broad application prospects in exhaust gas from diesel vehicle process field.
2, the CuCex-SAPO-18 molecular sieve catalyst that the present invention synthesizes is (substantially to be hung down by two groups in the hole with AEI structure
Straight each cross sectional dimensions is aboutChannel limited) small pore molecular sieve, surface area is up to 360m2/ g, in NH3-SCR
There is good activity and N in reaction2Selectivity.
3, for copper doped of the present invention as active component, the surface acidity that carrier itself contains can increase nitrogen oxides
Absorption, the dispersion that the evenly dispersed cerium of doping in addition of active component improves copper species inhibit the generation of copper oxide to improve oxidation also
Former power, this synergistic effect enhance the activity of catalyst entirety.
From the description of following exemplary embodiment, further characteristic of the invention will become obvious.
Detailed description of the invention
Fig. 1 is the XRD diagram of the CuCex-SAPO-18 molecular sieve of the embodiment of the present invention 1~3；
Fig. 2 is the ICP result table of the CuCex-SAPO-18 molecular sieve of the embodiment of the present invention 1~3；
Fig. 3 is the SEM figure of the CuCex-SAPO-18 molecular sieve of the embodiment of the present invention 1~3；
Fig. 4 is NH of the CuCex-SAPO-18 molecular sieve of the embodiment of the present invention 1~3 in obstructed water3- SCR reaction
Middle conversion rate of NOx curve graph；
Fig. 5 is NH of the CuCex-SAPO-18 molecular sieve of the embodiment of the present invention 1~3 in water flowing3In-SCR reaction
Conversion rate of NOx curve graph.
Specific embodiment
An embodiment of the disclosure is specifically described below, but the disclosure is not limited to this.
The CuCex-SAPO-18 molecular sieve catalyst that the present invention adulterates, by silicon source, phosphorus source and silicon source presoma with it is organic
Structure directing agent agent has obtained the Cu- of the highly crystalline of the cerium dopping with AEI structure by one-step method hydro-thermal process crystallization
SAPO-18 molecular sieve, sample has the pattern of cube and surface is smooth.The water-resistance of skeleton is improved after cerium dopping, simultaneously
With certain hydrothermal stability.The catalyst can be used for the elimination of nitrogen oxides in exhaust gas from diesel vehicle, in wider temperature window
Within the scope of mouthful 166-470 DEG C, the conversion ratio of nitrogen oxides 80% or more and is still maintaining greater activity under saturation state.It should
Catalyst is in NH3There is good catalytic performance in-SCR reaction, and chemical stability is good.
The preparation method, mainly comprises the steps that
Anhydrous cupric sulfate and cerous nitrate are proportionally added in container, a small amount of water is added to dissolve, Organic amine template is added
2~4h is sufficiently stirred in agent；Phosphorus source, water and silicon source is added, 1~2h is sufficiently stirred；Silicon source is added, it is sufficiently stirred 1 at room temperature~
2h；Another template is added, 1~2h is sufficiently stirred at room temperature and forms gel mixed solution；Mixed solution is transferred to high pressure
90~100h is reacted in reaction kettle at 180-200 DEG C, it is cooling, reaction solution is filtered, dries, obtains blue powder shape solids crude
Product；Crude product is roasted to 4~5h at 550-650 DEG C to get cerium dopping Cu-SAPO-18 molecular sieve catalyst.
Embodiment 1
It weighs 0.8g anhydrous cupric sulfate and the dissolution of 40ml water is added in container, 1mlTEPA is added, 2~4h is sufficiently stirred, adds
Enter 5ml phosphoric acid, 6.5g boehmite is added, 1~2h is sufficiently stirred, is slowly added dropwise into 8.6g AS-40, it is sufficiently stirred 1~
2h is added dropwise to 12ml DIPEA, and 1~2h is sufficiently stirred and forms gel, then this mixed solution is transferred in autoclave
90~100h is reacted at 180-200 DEG C, it is cooling, reaction solution is filtered, dries, obtains blue powder shape solid crude product, with
4~5h is roasted at 550-650 DEG C afterwards to get molecular sieve catalyst, and is named as Cu-SAPO-18 molecular sieve catalyst.
Embodiment 2
It weighs 0.8g anhydrous cupric sulfate, 0.13g cerous nitrate and the dissolution of 40ml water is added in container, 1mlTEPA is added, sufficiently
2~4h is stirred, 5ml phosphoric acid is added, 6.5g boehmite is added, 1~2h is sufficiently stirred, is slowly added dropwise into 8.6g AS-40,
1~2h is sufficiently stirred, is added dropwise to 12ml DIPEA, 1~2h is sufficiently stirred and forms gel, then shifts this mixed solution supreme
It presses and reacts 90~100h in reaction kettle at 180-200 DEG C, it is cooling, reaction solution is filtered, dries, obtains blue powder shape solid
Crude product roasts 4~5h at 550-650 DEG C then to get cerium dopping molecular sieve catalyst, and is named as CuCe0.003-
SAPO-18 molecular sieve catalyst.
Embodiment 3
It weighs 0.8g anhydrous cupric sulfate, 0.86g cerous nitrate and the dissolution of 40ml water is added in container, 1mlTEPA is added, sufficiently
2~4h is stirred, 5ml phosphoric acid is added, 6.5g boehmite is added, 1~2h is sufficiently stirred, is slowly added dropwise into 8.6g AS-40,
1~2h is sufficiently stirred, is added dropwise to 12ml DIPEA, 1~2h is sufficiently stirred and forms gel, then shifts this mixed solution supreme
It presses and reacts 90~100h in reaction kettle at 180-200 DEG C, it is cooling, reaction solution is filtered, dries, obtains blue powder shape solid
Crude product roasts 4~5h at 550-650 DEG C then to get molecular sieve catalyst, and is named as CuCe0.02-SAPO-18 points
Sub- sieve catalyst.
Phenetic analysis:
X-ray powder diffraction (XRD): the XRD diagram picture of sample using Dutch Panaco company X'Pert3
Powder diffractometer measures.
Inductively-coupled plasma spectrometer (ICP): copper cerium content contained by sample uses Thermo Fisher
The iCAP 7000Series spectrometer of Scientific company is tested.
Field emission scanning electron microscope (SEM): pattern variation passes through Japan after the pattern of sample and water flowing test
The S-4800 scanning electron microscope of Hitachi company carries out shooting observation.
As shown in Figure 1, being the XRD diagram of present example 1~3, pass through the CuCex- of one-step synthesis method difference cerium content
SAPO-18 molecular sieve all has the structure diffraction peak (PDF#45-0118) of AEI.Apparent dioxy is not found from diffracting spectrum
The diffraction maximum for changing cerium and Cu oxide kind illustrates ceria and Cu oxide kind is well dispersed in molecular sieve or amount is very little
And it can not detect.In addition, structure is unchanged after copper cerium is introduced into the crystal framework of molecular sieve, illustrate that the introducing of copper cerium will not influence
Skeleton crystal degree.
Table 2 is the ICP test result list of present example 1~3, it can be seen that the molecular sieve copper content of one-step synthesis method
It is consistent, containing the copper of 1.8wt% or so in sample, it is different that cerium content in the different finally obtained samples of cerium content is added.
Fig. 3 is the SEM image of present example 1~3, and SEM, can from figure commonly used in the apparent form of observation sample
The crystal structure that three fresh samples all have cube out, having a size of 0.8~2 μm, crystal relative smooth and shape is uniform.It is right
It undopes the molecular sieve of cerium in 1 sample of example that water flowing was tested, shows apparent surface damage and irregular shape,
But identical cubic morphology and surface texture are still kept after doping cerium, highly crystalline is still maintained, this is CuCex-SAPO-
18 molecular sieves keep the positive evidence compared with enhanced water resistance.
NH3Selective catalytic reduction (NH3- SCR) performance test: CuCex-SAPO-18 molecular sieve prepared in the above embodiments
40~60 mesh particles are screened into for NH3The evaluation of SCR activity.Test condition is as follows: loaded catalyst 0.12g, raw material
Gas is by 500ppmNO, 500ppmNH3, 5%O2With Balance Air nitrogen composition (5%H2O is added when testing in water flowing), feed gas flow rates
For 300mL/min, unstripped gas air speed (GHSV) is 79000h-1, reaction temperature is 150~550 DEG C.
The catalyst of each embodiment preparation is applied to NH3In-SCR reaction, NO conversion ratio calculation formula is as follows:
Fig. 4 is the CuCex-SAPO-18 molecular sieve catalyst of the embodiment of the present invention 1~3 in NH3NOx turns in-SCR reaction
Rate curve graph；From in figure it is recognised that temperature window is within the scope of 200-433 DEG C, catalyst prepared by Examples 1 to 3
NO conversion ratio reaches 80% or more, reduces as cerium content increases, wherein CuCe0.003- SAPO-18 molecular sieve catalyst exists
The conversion ratio that 80% or more is had reached within the scope of 160-470 DEG C, shows optimum activity.
Fig. 5 is the CuCex-SAPO-18 molecular sieve catalyst of the embodiment of the present invention 1~3 in NH3In water flowing in-SCR reaction
Under the conditions of conversion rate of NOx curve graph；From in figure it is recognised that activity is substantially reduced after Cu-SAPO-18 molecular sieve water flowing,
And the CuCe of optimum activity0.003- SAPO-18 molecular sieve catalyst activity after water flowing is still kept, and the activity under high temperature increases
By force, the reason is that the presence of vapor can inhibit the oxidation of NH3 under high temperature.
Industrial applicibility
By CuCex-SAPO-18 molecular sieve catalyst prepared by the present invention in NH3There is good catalysis in-SCR reaction
Performance and good water-resistance, and chemical stability is good, has huge application potential.
This embodiment is merely preferred embodiments of the present invention, but scope of protection of the present invention is not limited thereto,
In the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with scope of protection of the claims
Subject to.
Claims (9)
1. a kind of preparation method of cerium dopping Cu-SAPO-18 molecular sieve catalyst, which is characterized in that with phosphorus source, silicon source, silicon source
It, using mantoquita and cerium salt as the precursor material of active component, is passed through for precursor material using two kinds of organic amines as dual mould plate agent
The preparation of one-step method hydro-thermal process crystallization.
2. preparation method according to claim 1, including following steps:
(1) anhydrous cupric sulfate and cerous nitrate are dissolved with water, the first organic amine template is added, obtains mixed liquor 1；
(2) phosphorus source, water and silicon source are added in mixed liquor 1 and obtain mixed liquor 2；
(3) silicon source is added in mixed liquor 2 and obtains mixed liquor 3；
(4) the second organic amine template gelation is added in mixed liquor 3, obtains mixed liquor 4；
(5) mixed liquor 4 is reacted in a high pressure reaction kettle and obtains crude product；
(6) crude product high-temperature roasting is obtained into catalyst.
3. according to claim 1 or preparation method described in one of any one of 2, wherein the ratio of each precursor material is (to rub
That ratio): 0.9~1.1Al2O3:0.85~0.95P2O5:1.15~1.25SiO2:1.55DIPEA:0.05~0.15Cu-
TEPA:0.002~0.006Ce:45H2O.
4. preparation method described in one of any one of -3 according to claim 1, phosphorus source is selected from phosphoric acid, and silicon source is selected from AS-40, aluminium
Source is selected from boehmite, and mantoquita is selected from copper sulphate, and cerium salt is selected from cerous nitrate.
5. the preparation method according to one of any one of claim 2 or 4, wherein the first organic amine template is selected from tetrem
Five amine of alkene (TEPA)；Second organic amine template is selected from N, N- diisopropylethylamine (DIPEA).
6. the preparation method according to one of any one of claim 2-5 is reacted at 180-200 DEG C wherein in step (5)
90~100h.
7. the preparation method according to one of any one of claim 2-6, wherein in step (6), crude product is in 550-650
4~5h is roasted at DEG C.
8. a kind of cerium dopping Cu-SAPO-18 molecular sieve catalyst, system described in one of any one of -7 according to claim 1
Preparation Method is made.
9. a kind of cerium dopping Cu-SAPO-18 molecular sieve catalyst is indicated with AEI structure with following formula CuCex-SAPO-18,
Wherein x represents Ce/Al molar ratio, and value is 0.0005~0.08；It is preferred that 0.003~0.02.
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