CN108273549A - The preparation method and application of SAPO-18 loaded Cus and La composite catalysts - Google Patents
The preparation method and application of SAPO-18 loaded Cus and La composite catalysts Download PDFInfo
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- CN108273549A CN108273549A CN201810093573.1A CN201810093573A CN108273549A CN 108273549 A CN108273549 A CN 108273549A CN 201810093573 A CN201810093573 A CN 201810093573A CN 108273549 A CN108273549 A CN 108273549A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000002808 molecular sieve Substances 0.000 claims abstract description 44
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000005342 ion exchange Methods 0.000 claims abstract description 17
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 230000000694 effects Effects 0.000 claims abstract description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract 4
- 238000000034 method Methods 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910002339 La(NO3)3 Inorganic materials 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 206010013786 Dry skin Diseases 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims 2
- 239000011261 inert gas Substances 0.000 claims 2
- 239000012495 reaction gas Substances 0.000 claims 2
- 238000005406 washing Methods 0.000 claims 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 28
- 239000010949 copper Substances 0.000 abstract description 21
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 241000269350 Anura Species 0.000 abstract 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 abstract 1
- LNUFLCYMSVYYNW-ZPJMAFJPSA-N [(2r,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[[(3s,5s,8r,9s,10s,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-3-yl]oxy]-4,5-disulfo Chemical compound O([C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1C[C@@H]2CC[C@H]3[C@@H]4CC[C@@H]([C@]4(CC[C@@H]3[C@@]2(C)CC1)C)[C@H](C)CCCC(C)C)[C@H]1O[C@H](COS(O)(=O)=O)[C@@H](OS(O)(=O)=O)[C@H](OS(O)(=O)=O)[C@H]1OS(O)(=O)=O LNUFLCYMSVYYNW-ZPJMAFJPSA-N 0.000 abstract 1
- 229910021529 ammonia Inorganic materials 0.000 abstract 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 abstract 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 abstract 1
- 230000008569 process Effects 0.000 description 9
- 229910002089 NOx Inorganic materials 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000008280 blood Substances 0.000 description 4
- 210000004369 blood Anatomy 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- WFPZPJSADLPSON-UHFFFAOYSA-N dinitrogen tetraoxide Chemical compound [O-][N+](=O)[N+]([O-])=O WFPZPJSADLPSON-UHFFFAOYSA-N 0.000 description 4
- 108010061951 Methemoglobin Proteins 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 2
- 108010054147 Hemoglobins Proteins 0.000 description 2
- 102000001554 Hemoglobins Human genes 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- 206010037423 Pulmonary oedema Diseases 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 210000004072 lung Anatomy 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 208000005333 pulmonary edema Diseases 0.000 description 2
- 210000002345 respiratory system Anatomy 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 206010002660 Anoxia Diseases 0.000 description 1
- 241000976983 Anoxia Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000007953 anoxia Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000036772 blood pressure Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000010339 dilation Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 231100000567 intoxicating Toxicity 0.000 description 1
- 230000002673 intoxicating effect Effects 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 230000004199 lung function Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 208000005135 methemoglobinemia Diseases 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 208000023504 respiratory system disease Diseases 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 230000002792 vascular Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Combustion & Propulsion (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The preparation method and application of SAPO 18 loaded Cu and La composite catalysts are used for catalytic removal nitrogen oxides.18 molecular sieves of SAPO are prepared by hydro-thermal method, by itself and NH4Cl is exchanged, and prepares ammonia type NH418 molecular sieves of/SAPO, then by NH4Copper nitrate is added in 18 molecular sieves of/SAPO and lanthanum nitrate hexahydrate prepares high-specific surface area (550m by multiple ion-exchange2/ g~600m2/ g) compound 18 molecular sieve catalysts of La CuSAPO.Made catalyst is in wider temperature (150 DEG C~600 DEG C) range, to high-speed (10,000h‑1~200,000h‑1), high O2Concentration (10vl.%~20vl.%), high H2O content (5wt%~10wt%), NH3Content (300ppm~1000ppm) and low NO concentration (300ppm~1000ppm) pollutant have high catalytic removal effect (NO conversion ratios 30%~95%).And the catalyst keeps NO initial conversions under wider temperature range in 100 hours.
Description
Technical field
The SAPO-18 that the present invention relates to a kind of for catalytic removal NO adulterate Cu and La composite catalysts preparation method and
Its selective catalysis eliminates the application of NO.
Background technology
Current automobile also becomes the primary pollution source of city environmental pollution while walking-replacing tool convenient as people
One of.Early in nineteen fifties and the seventies, Los Angeles,U.S has occurred photochemical fog event twice and successively leads
The people's illness for causing the whole city 3/4ths, because its serious social destructiveness be referred to as " ten overall situation hazardous accidents of twentieth century " it
One, and the exhaust gas of vehicular emission is to cause one of principal element of this accident.In recent years with each big city vapour in China
The quick increase of vehicle ownership, tail gas pollution have resulted in strong influence to people's lives.The composition of vehicle exhaust is various,
Main includes oxycarbide (CO), hydrocarbon (CH) and nitrogen oxides (NOx) etc. Multiple components.Wherein nitrogen oxides can
To enter internal, main harm, the alveolar and ramuscule gas for damaging lung airways deep by the eyes of human body or respiratory tract
Pipe.Since the surface moisture content of alveolar is higher, after nitrogen oxides enters alveolar, nitrogen oxides can be rapidly dissolved in alveolar
On, and in alveolar accumulation 80% meltage, other part nitrogen oxides can be converted into dinitrogen tetroxide.Wherein nitrogen dioxide
It can be with the water function and then generation nitric acid and nitrous acid substance on human respiratory tract surface, strong impulse with dinitrogen tetroxide
With the lung tissue of corrosion human body, keeps the permeability of human body alveolar membrane and capillary greatly impacted, lead to pulmonary edema.In addition,
The nitrite formed at alveolar can penetrate into blood of human body, cause vascular dilation and blood pressure to reduce, and nitrite
It is reacted with hemoglobin and generates ferrihemoglobin, reduce the oxygen content in blood.In addition, there are an oxygen of high concentration in blood
Change nitrogen also can be melted into ferrihemoglobin by hemoglobin oxygen, also result in body anoxic.Therefore, as nitrogen oxides pollution owner
In the presence of will be with nitrogen dioxide, the lung function of human body can be mainly influenced, human body is caused to suffer from the lesions such as pulmonary edema；And work as nitrogen oxidation
Object pollutant mainly with nitric oxide in the presence of, can mainly cause in human body anoxia, blood ferrihemoglobin content to increase, and
And body intoxicating phenomenon is quickly grown at this time, it may appear that methemoglobinemia and nervous centralis damage symptom, are caused to human body
Greatly injury.Finally, NOxIt is a large amount of discharge not only result in human respiratory system's disease, also result in depletion of the ozone layer, light
Chemical fumes and greenhouse effects, and NOxWith SO2The formation that acid rain can equally be caused, causes cultivated land degradation and damage of building etc.,
Therefore reducing the discharge capacity of nitrogen oxides is particularly important.
Due to administering NOxDifficulty is big, control and improvement NOxPollution have become in current environmental protection research most active project it
One.There are many eliminate NO both at home and abroad at presentxMethod, wherein NH3Selective Catalytic Reduction of NOxMethod comparative maturity, answered
For vehicle exhaust (stationary source) and thermal power plant (moving source) NOxThe improvement of pollution.NH3- SCR catalysis materials mainly have expensive
4 kinds of metallic catalyst, metal oxide catalyst, molecular sieve catalyst and other catalysis materials systems, wherein V2O5-WO3-
TiO2System is most widely used, and the system has been commercialized at present, but the exhaust temperature model when operation of diesel vehicle actual load
It is 150~700 DEG C to enclose, V2O5-WO3-TiO2There are low temperature active deficiency, high high-temp stability difference and high temperature V (vanadium) for catalyst system and catalyzing
Volatilization generates secondary pollution problems.
SAPO-18 molecular sieve catalysts 1984, U.S. combinating carbide company (UCC) develop silicoaluminophosphate series point
Son sieve (SAPO-n, n representative structure model).Wherein, what people were attracted attention the most is SAPO-18 molecular sieves.This molecular sieve
MTO catalytic performances are excellent, become the object for falling over each other to develop on catalysis circle, mesh due to its unique structure and physicochemical properties
Before be widely used to the catalytic fields such as coal chemical industry, PETROLEUM PROCESSING and fine chemistry industry.This patent selects thermal stability higher
SAPO-18 molecular sieves are carrier, by SAPO-18, adulterate Cu and La, by ion-exchange be prepared into SAPO-18 loaded Cus and
La composite catalysts obtain the catalytic removal NO in good wide temperature range (150 DEG C~600 DEG C)xHigh activity and height are steady
Qualitative energy.It is most of using single although CuSAPO-18 also has preferable activity from the point of view of the document just being had been reported that at present
Only copper supported catalyst, reaction temperature is relatively narrow, and stability is poor, and the La-CuSAPO-18 catalyst prepared by this patent has
Preferable activity and stability are prepared into support type by ion-exchange and urge moreover, SAPO-18 adulterates Cu and La at present
The research of agent is less.
This project implementation obtains：Project of national nature science fund project (number：21277008；20777005)；Country's weight
Point research and development plan (No.2017YFC0209905), the subsidy of Beijing's Nsfc Projects (No.8082008) and this
The research contents of a little projects.
Invention content
Disappear the object of the present invention is to provide the preparation of a kind of SAPO-18 loaded Cus and La composite catalysts and its for being catalyzed
Except NO pollutants.The catalyst provided can under wide reaction temperature (150 DEG C~600 DEG C), efficiently eliminate NO (30%~
95% NO conversion ratios).Moreover, this catalyst has higher stability.This catalyst preparation process is simple.
The present invention provides a kind of preparation method of the SAPO-18 doping Cu and La composite catalysts for catalytic removal NO.
(1) by SAPO-18 molecular sieves and 0.05~0.2molL-1NH4Cl solution is in 60~80 DEG C of ion exchanges 2~10
H, wherein SAPO-18 molecular sieves and NH4The ratio of Cl is 100g：(0.6mol~3.0mol), the above process repeat 1~3 time,
It is filtered, washed 3~5 times, 100~140 DEG C of dryings 10~obtain NH for 24 hours4/ SAPO-18 molecular sieves.Then uniformly mixing
0.001mol·L-1~0.02molL-1La(NO3)3And 0.01molL-1~0.1molL-1Cu (NO3)2Solution, wherein
La(NO3)3With Cu (NO3)2Molar ratio is (0.01~2)：1, by NH made above4/ SAPO-18 molecular sieves are added above-mentioned mixed
It closes in liquid, 50~80 DEG C of 2~5h of ion exchange, wherein NH4/ SAPO-18 molecular sieves and Cu (NO3)2Ratio is 100g：
(0.03mol~0.3mol) is repeated 0~2 time according to the above process, be filtered, washed 3~5 times, 100~140 DEG C of dryings 10~
For 24 hours, 450~600 DEG C of 4~8h of roasting, are made support type La-CuSAPO-18 composite catalysts.
(2) catalyst of the present invention is normal pressure 1atm in reaction pressure, (10,000h under high-speed-1~200,000h-1)、
High O2Concentration (10vl.%~20vl.%), high H2O content (0vl.%~10vl.%), NH3Concentration (300ppm~
1000ppm), NO concentration (300ppm~1000ppm) and Balance Air are N2Under the conditions of, in wide temperature range (150 DEG C~600
DEG C) in, there is high catalytic activity (NO conversion ratio=30%~95%)；It is normal pressure 1atm in reaction pressure, under high-speed
(10,000h-1~200,000h-1), high O2Concentration (10vl.%~20vl.%), high H2O content (0vl.%~10vl.%),
NH3Concentration (300ppm~1000ppm), NO concentration (300ppm~1000ppm) and Balance Air are N2Under the conditions of, investigate support type
Compound La-CuSAPO-18 catalyst, in a temperature spot of wide temperature section (150 DEG C~600 DEG C), NO turns in 100 hours
Rate, under the temperature range studied, catalytic activity still maintains high stability, shows high stability.
Description of the drawings
Fig. 1 is La-CuSAPO-18-I, La-CuSAPO-18-II, La- prepared by the embodiment of the present invention 1,2,3 and 4
The XRD diagram of CuSAPO-18-III, La-CuSAPO-18-IV catalyst.
Fig. 2 is La-CuSAPO-18-I, La-CuSAPO-18-II, La- prepared by the embodiment of the present invention 1,2,3 and 4
The N of CuSAPO-18-III, La-CuSAPO-18-IV catalyst2Absorption/desorption figure.
Fig. 3 is La-CuSAPO-18-I, La-CuSAPO-18-II, La- prepared by the embodiment of the present invention 1,2,3 and 4
NH on CuSAPO-18-III, La-CuSAPO-18-IV catalyst3Selective Catalytic Reduction of NO activity.
Fig. 4 is La-CuSAPO-18-I, La-CuSAPO-18-II, La-CuSAPO-18- prepared by the present invention 1,2,3 and 4
The stability of 450 DEG C of reactions 100 hours of III, La-CuSAPO-18-IV catalyst.
Specific implementation mode
Embodiment 1
(1) silica alumina ratio of the SAPO-18 molecular sieves prepared by is 0.1mol:1mol, by SAPO-18 molecular sieves and 0.05
mol·L-1NH4Cl solution is in 60 DEG C of ion exchange 2h, wherein SAPO-18 molecular sieves and NH4The ratio of Cl is 100g：
0.6mol, the above process are repeated 1 times, be filtered, washed 3 times, 100 DEG C of dry 10h obtain NH4/ SAPO-18 molecular sieves.Then
Even mixing 0.001molL-1La(NO3)3And 0.01molL-1Cu (NO3)2Solution, wherein La (NO3)3With Cu (NO3)2It rubs
Your ratio is 0.1：1, by NH made above4/ SAPO-18 molecular sieves are added in above-mentioned mixed liquor, 50 DEG C of ion exchange 2h,
Wherein NH4/ SAPO-18 molecular sieves and Cu (NO3)2Ratio is 100g：0.03mol is filtered, washed 3 times, 100 DEG C of dry 10h,
450 DEG C of roasting 4h, are made support type La-CuSAPO-18-I composite catalysts.
(2) catalyst of the present invention is normal pressure 1atm in reaction pressure, 10,000h under air speed-1, high O2Concentration 10vl.%,
High H2O content 5wt%, NH3A concentration of 300ppm, NH3A concentration of 300ppm and N2Under the conditions of Balance Air, in wide temperature
In range (150 DEG C~600 DEG C), there is high catalytic activity (NO conversion ratio=45%~95%)；It is normal pressure in reaction pressure
1atm, 10,000h under air speed-1, high O2Concentration 10vl.%, high H2O content 5wt%, NH3A concentration of 300ppm, NH3It is a concentration of
300ppm and N2Under the conditions of Balance Air, in wide temperature range (150 DEG C~600 DEG C), there is high catalytic activity
(NO conversion ratio=45%~95%)；The compound La-CuSAPO-18-I catalyst of support type is investigated, in (150 DEG C of wide temperature section
~600 DEG C) a temperature spot, NO conversion ratios in 100 hours, under the temperature range studied, catalytic activity still maintains
High stability shows high stability.
Embodiment 2
(1) silica alumina ratio of the SAPO-18 molecular sieves prepared by is 0.2mol:1mol, by SAPO-18 molecular sieves and 0.075
mol·L-1NH4Cl solution is in 70 DEG C of ion exchange 3h, wherein SAPO-18 molecular sieves and NH4The ratio of Cl is 100g：
1.2mol, the above process are repeated 2 times, be filtered, washed 4 times, 120 DEG C of dry 15h obtain NH4/ SAPO-18 molecular sieves.Then
Even mixing 0.005molL-1La(NO3)3And 0.02molL-1Cu (NO3)2Solution, wherein La (NO3)3With Cu (NO3)2It rubs
Your ratio is 0.25：1, by NH made above4/ SAPO-18 molecular sieves are added in above-mentioned mixed liquor, 55 DEG C of ion exchange 3h,
Wherein NH4/ SAPO-18 molecular sieves and Cu (NO3)2Ratio is 100g：0.06mol is repeated 1 times according to the above process, is filtered, washed
4 times, 120 DEG C of dry 15h, 500 DEG C of roasting 5h, are made support type La-CuSAPO-18-II composite catalysts.
(2) catalyst of the present invention, in the case where reaction pressure is normal pressure 1atm, high-speed 360,00h-1, high O2Concentration (15
Vl.%), high H2O content (7vl.%), NH3Under the conditions of a concentration of a concentration of 500ppm and He of 500ppm, NO is as Balance Air,
In wide temperature range (150 DEG C~600 DEG C), there is high catalytic activity (NO conversion ratio=45%~95%)；In reaction pressure
Power is 360,00h under normal pressure 1atm, high-speed-1, high O2Concentration (15vl.%), high H2O content (7vl.%), NH3It is a concentration of
Under the conditions of 500ppm, NO a concentration of 500ppm and He are as Balance Air, the compound Ce-CuSAPO-18-II catalysis of support type is investigated
Agent, in a temperature spot of wide temperature section (150 DEG C~600 DEG C), NO conversion ratios in 100 hours, in the temperature model studied
Under enclosing, catalytic activity still maintains high stability, shows high stability.
Embodiment 3
(1) silica alumina ratio of the SAPO-18 molecular sieves prepared by is 0.2mol:1mol, by SAPO-18 molecular sieves and 0.1
mol·L-1NH4Cl solution is in 75 DEG C of ion exchange 6h, wherein SAPO-18 molecular sieves and NH4The ratio of Cl is 100g：
2.0mol, the above process are repeated 2 times, be filtered, washed 4 times, 120 DEG C of dry 20h obtain NH4/ SAPO-18 molecular sieves.Then
Even mixing 0.0075molL-1La(NO3)3And 0.05molL-1Cu (NO3)2Solution, wherein La (NO3)3With Cu (NO3)2It rubs
Your ratio is 0.15：1, by NH made above4/ SAPO-18 molecular sieves are added in above-mentioned mixed liquor, 60 DEG C of ion exchange 4h,
Wherein NH4/ SAPO-18 molecular sieves and Cu (NO3)2Ratio is 100g：0.15mol is repeated 1 times according to the above process, is filtered, washed
4 times, 120 DEG C of dry 20h, 500 DEG C of roasting 6h, are made support type La-CuSAPO-18-III composite catalysts.
(2) catalyst of the present invention, in the case where reaction pressure is normal pressure 1atm, high-speed 66,000h-1, high O2Concentration
(18vl.%) and high H2O content (8vl.%), NH3A concentration of a concentration of 800ppm and N of 800ppm, NO2As Balance Air condition
Under, in wide temperature range (150 DEG C~600 DEG C), there is high catalytic activity (NO conversion ratio=45%~95%)；Anti-
It is 66,000h under normal pressure 1atm, high-speed to answer pressure-1, high O2Concentration (18vl.%) and high H2O contents (8vl.%), NH3It is dense
Degree is 800ppm, NO a concentration of 800ppm and N2Under the conditions of Balance Air, in wide temperature range (150 DEG C~600 DEG C),
With high catalytic activity (NO conversion ratio=45%~95%), the compound La-CuSAPO-18-III catalyst of support type is investigated,
In a temperature spot of wide temperature section (150 DEG C~600 DEG C), NO conversion ratios in 100 hours, in the temperature range studied
Under, catalytic activity still maintains high stability, shows high stability.
Embodiment 4
(1) silica alumina ratio of the SAPO-18 molecular sieves prepared by is 0.3mol:1mol, by SAPO-18 molecular sieves and 0.2
mol·L-1NH4Cl solution is in 80 DEG C of ion exchange 10h, wherein SAPO-18 molecular sieves and NH4The ratio of Cl is 100g：
3.0mol, the above process are repeated 3 times, be filtered, washed 5 times, 140 DEG C of dryings obtain NH for 24 hours4/ SAPO-18 molecular sieves.Then
Even mixing 0.02molL-1La(NO3)3And 0.1molL-1Cu (NO3)2Solution, wherein La (NO3)3With Cu (NO3)2Mole
Ratio is 0.2：1, by NH made above4/ SAPO-18 molecular sieves are added in above-mentioned mixed liquor, 80 DEG C of ion exchange 5h,
Middle NH4/ SAPO-18 molecular sieves and Cu (NO3)2Ratio is 100g：0.3mol is repeated 2 times according to the above process, is filtered, washed 5
For 24 hours, support type La-CuSAPO-18-IV composite catalysts are made in 600 DEG C of roasting 8h for secondary, 140 DEG C of dryings.
(2) catalyst of the present invention, in the case where reaction pressure is normal pressure 1atm, high-speed 200,000h-1, high O2Concentration
20vl.% and high H2Under the conditions of O content 10vl.%, NH3A concentration of a concentration of 1000ppm and He of 1000ppm, NO is as Balance Air
Under the conditions of, in wide temperature range (150 DEG C~600 DEG C), there is high catalytic activity (NO conversion ratio=45%~95%)；
The 200,000h in the case where reaction pressure is normal pressure 1atm, high-speed-1, high O2Concentration 20vl.% and high H2O content 10vl.% conditions
Under, NH3Under the conditions of a concentration of a concentration of 1000ppm and He of 1000ppm, NO is as Balance Air, investigates support type and answer La-
CuSAPO-18-IV catalyst, in a temperature spot of wide temperature section (150 DEG C~600 DEG C), NO conversion ratios in 100 hours,
Under the temperature range studied, catalytic activity still maintains high stability, shows high stability.
Claims (5)
1. a kind of preparation method of SAPO-18 doping Cu and La composite catalysts, which is characterized in that include the following steps：
By SAPO-18 molecular sieves and 0.05~0.2molL-1NH4Cl solution in 60~80 DEG C of 2~10h of ion exchange, wherein
SAPO-18 molecular sieves and NH4The ratio of Cl is 100g：(0.6mol~3.0mol), ion exchange process repeat 1~3 time, mistake
Filter, washing 3~5 times, 100~140 DEG C of dryings 10~obtain NH for 24 hours4/ SAPO-18 molecular sieves；Then uniformly mixing
0.001mol·L-1~0.02molL-1La(NO3)3And 0.01molL-1~0.1molL-1Cu (NO3)2Solution, wherein
La(NO3)3With Cu (NO3)2Molar ratio is (0.01~2)：1, by NH made above4/ SAPO-18 molecular sieves are added above-mentioned mixed
It closes in liquid, 50~80 DEG C of 2~5h of ion exchange, wherein NH4/ SAPO-18 molecular sieves and Cu (NO3)2Ratio is 100g：
(0.03mol~0.3mol), ion exchange process repeat 0~2 time, be filtered, washed 3~5 times, 100~140 DEG C of dryings 10~
For 24 hours, 450~600 DEG C of 4~8h of roasting, are made support type La-CuSAPO-18 composite catalysts.
2. according to the method described in claim 1, it is characterized in that：The silica alumina ratio of SAPO-18 molecular sieves be (0.1mol~
0.3mol):1mol。
3. support type La-CuSAPO-18 composite catalysts prepared by application method as described in claim 1 are in the application for eliminating NO
In, it is characterised in that：Catalyst is placed in continuous flow fixed bed device and is passed through containing (300ppm~1000ppm) NH3、
(300ppm~1000ppm) NO, (10vl.%~20vl.%) O2(0vl.%~10vl.%) H2It is carried out in the gaseous mixture of O anti-
It answers, the remaining gas of the above gaseous mixture is inert gas；Reaction pressure is normal pressure 1atm, reaction velocity 10,000h-1~200,
000h-1, reaction temperature is 150 DEG C~600 DEG C；Ultimate density after a concentration of gas mixing of all gas, concentration are all
Volumn concentration.
4. application according to claim 3, which is characterized in that NH in reaction gas3It is equal with the concentration of NO, in reaction gas
Balanced gas be inert gas He or N2。
5. application according to claim 3, which is characterized in that the compound La-CuSAPO-18 catalyst of test load type it is steady
It is qualitative, in 150 DEG C~600 DEG C temperature ranges, keep a temperature spot, test La-CuSAPO-18 catalyst reactions 100 small
When activity.
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