CN109999901A - A kind of porous graphene-molecular sieve complex carries denitrating catalyst and preparation method thereof - Google Patents
A kind of porous graphene-molecular sieve complex carries denitrating catalyst and preparation method thereof Download PDFInfo
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- CN109999901A CN109999901A CN201910388210.5A CN201910388210A CN109999901A CN 109999901 A CN109999901 A CN 109999901A CN 201910388210 A CN201910388210 A CN 201910388210A CN 109999901 A CN109999901 A CN 109999901A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910021389 graphene Inorganic materials 0.000 claims description 17
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 12
- 230000002378 acidificating effect Effects 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 239000003546 flue gas Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 2
- 239000010410 layer Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 claims 3
- 150000001336 alkenes Chemical class 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 229910016978 MnOx Inorganic materials 0.000 abstract description 4
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000007654 immersion Methods 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 8
- 239000012300 argon atmosphere Substances 0.000 description 7
- 239000011572 manganese Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-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 compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium nitrate Inorganic materials [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229940126678 chinese medicines Drugs 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 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
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Biomedical Technology (AREA)
- Optics & Photonics (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to atmosphere polluting controling technology field, it is related to a kind of porous graphene-molecular sieve complex carries denitrating catalyst and preparation method thereof.Catalyst carrier is graphene-molecular sieve complex carries, active component MnOx-CeO2.Catalyst produced by the present invention reaches 240 in temperature oCAfterwards, denitrification rate has reached 90%.This is compared with traditional denitrating catalyst, the advantage with apparent low-temperature catalytic activity.Catalyst shows that the reason of low temperature high activity may have the following, catalyst reference area with higher itself and Kong Rong, so that the effective adsorption area of catalyst increases；Due to the immersion treatment of catalyst carrier acid solution, so that catalyst carrier has certain acidity；Since catalyst itself has excellent electron transfer orbital so that MnOx and CeO2With excellent reducing power and significant oxygen storage capacity, so that catalyst has higher activity at low temperature.
Description
Technical field
The invention belongs to atmosphere polluting controling technology field, it is related to a kind of denitrating catalyst and preparation method thereof, specifically relates to
And a kind of porous graphene-molecular sieve complex carries denitrating catalyst and preparation method thereof.
Background technique
The nitrogen oxides that burning city domestic garbage and coal-fired power plant generate can cause photochemical fog, acid rain, small
Many environmental problems such as Particulate Pollution and ozone hole are one of maximum pollutants of air pollution damage.China pair
The discharged nitrous oxides of nitric acid industry clearly require, and provide me in GB26131-2010 " nitric acid industry emission standard "
For enterprise, state since on April 1st, 2013, the pollutant NOx emission intensity in atmosphere was single no more than 300 milligrams every cubic metre
Position product benchmark discharge amount is 3400 cubic metres per ton.There are many ways to administering nitrogen oxides in effluent at present, from substance shape
State is divided, and can be divided into dry and wet two major classes, be divided by technical process, can be divided into catalytic reduction method, absorption process and absorption method
Three categories.
Research at present and the more denitration technology of application are the selective oxidation reduction technique using ammonia as reducing agent, should
Technology is comparatively mature and effective, is the mainstream technology of the pollution sources such as Industrial Boiler, thermal power plant, very widely used.Wherein
Using titanium dioxide as carrier, vanadic anhydride as active component V2O5/TiO2Catalyst is the most general for commercial applications
Time.Since the catalyst is in 300-400oThere is relatively high activity, temperature is higher, removes if being disposed at flue gas between C
After dirt and desulfurizer, then flue-gas temperature can drop to 300oC is hereinafter, can even drop to 200oC is hereinafter, lead to catalyst
Activity decline.And if in order to adapt to the active breeding ground range of catalyst, flue gas is heated again, it will cause the energy wave
Take.Therefore in order to energy saving, it usually needs being arranged denitrification apparatus in flue gas ash removal and desulfurizer front, but another party
Face, since flue gas at this time is also without desulfurization operations, a large amount of SO for containing in flue gas2, the substances such as flying dust be easy to cause catalyst
Inactivation.
Summary of the invention
The present invention proposes a kind of novel porous graphene-molecular sieve for the problem of traditional denitrating flue gas process
Complex carries denitrating catalyst and preparation method thereof.
In order to achieve the above object, the present invention is realized using following technical solutions:
A kind of porous graphene-molecular sieve complex carries denitrating catalyst, the catalyst carrier, which is that graphene-molecular sieve is double, to be carried
Body, active component MnOx-CeO2。
Preferably, the graphene is acidic activated single-layer or multi-layer graphene, the molecular sieve is SAPO-11 points
Son sieve.
Porous graphene-molecular sieve complex carries denitrating catalyst preparation method, includes the following steps:
(1) sulfuric acid solution of the nitric acid solution of 3mol/L and 2mol/L are mixed according to the ratio of volume ratio 1:1, obtains acid work
Change liquid；
(2) it is impregnated in after grinding graphene film in acidic activated liquid, activation 8-10h is stirred at room temperature；
(3) SAPO-11 molecular sieve is added, it is 5-10 minutes ultrasonic, obtain mixed liquor；
(4) it after filtering mixed liquor, is dried, obtains support powder；
(5) by Ce (NO3)3•6H2O and mass fraction are that 50% manganese nitrate solution is dissolved into ethyl alcohol, and deionized water, mixing is added
It is uniformly rear that support powder is added, reaction 5-8h is stood after ultrasonic 30-50min, filtering, filter residue progress temperature programmed control is dry, then
It roasts under inert gas atmosphere, catalyst is obtained after natural cooling.
There is following electronic transfer process during catalyst:
The catalyst has excellent electron transfer orbital, Ce+4With Ce+3Between, Mn+4With Mn+6Between electronics transfer and big
The Lacking oxygen of amount makes MnOx and CeO2With excellent reducing power and significant oxygen storage capacity, so that catalyst is at low temperature
With higher activity.
Preferably, partial size is 200-300 microns after graphene film grinding in the step (2)；Graphene and acidity are living
Change liquid mass ratio is 1:(100-150), stirring rate 100-120rpm.
Preferably, graphene film and SAPO-11 molecular sieve quality ratio are 3:1.
Preferably, Ce (NO in the step (5)3)3•6H2O and mass fraction are that 50% manganese nitrate solution mass ratio is 1:
2.8；Ce(NO3)3•6H2O and ethyl alcohol mass ratio are 1:50, and ethyl alcohol and deionized water volume ratio are 1:2, Ce (NO3)3•6H2O and load
Body powder quality ratio is 1:4.6.
Preferably, ultrasonic time is 35min in the step (5), the standing reaction time is 6h；Filter residue temperature programmed control is dry
Dry process is two freeze-day with constant temperature stages: first stage 50-55 under nitrogen atmosphereoDry 2h under C, with 2oThe rate of C/min
It is warming up to second stage, second stage 70-80oDry 3h under C；Inert gas is argon gas or nitrogen, maturing temperature 300-
350oC, preferably 320oC；Calcining time is 3-4h, preferably 3.5h.
Above-mentioned porous graphene-application of molecular sieve complex carries denitrating catalyst during denitrating flue gas.
Compared with prior art, the advantages and positive effects of the present invention are:
Catalyst produced by the present invention is in 90-240 oCIn temperature range, as the temperature rises, catalyst activity is gradually risen,
Reach 240 in temperature oCAfterwards, denitrification rate has reached 90%.This compared with traditional denitrating catalyst there is apparent low temperature to urge
Change active advantage.Catalyst shows that low temperature high activity reason may have the following, first is that catalyst itself have it is higher
Reference area and Kong Rong so that the effective adsorption area of catalyst increases；Second is that due to the immersion of catalyst carrier acid solution
Processing, so that catalyst carrier has certain acidity；Third is that since catalyst itself has excellent electron transfer orbital, Ce+4
With Ce+3Between, Mn+4With Mn+6Between electronics transfer and a large amount of Lacking oxygen make MnOx and CeO2With excellent also proper energy
Power and significant oxygen storage capacity, so that catalyst has higher activity at low temperature.
Detailed description of the invention
Fig. 1 is catalyst denitration testing result made from embodiment 1-3.
Specific embodiment
To better understand the objects, features and advantages of the present invention, right combined with specific embodiments below
The present invention is described further.It should be noted that in the absence of conflict, the spy in embodiments herein and embodiment
Sign can be combined with each other.
In the following description, numerous specific details are set forth in order to facilitate a full understanding of the present invention, still, the present invention may be used also
To be implemented using other modes described herein are different from, therefore, the present invention is not limited to the specific of specification is described below
The limitation of embodiment.
Embodiment 1
SAPO-11 molecular screen primary powder is prepared using following steps: successively by 5gAl2O3Powder (purity 80wt% or more), 80ml phosphorus
Acid (Chinese medicines group is analyzed pure), 25ml silica solution (30wt.% aqueous solution), 30ml di-n-propylamine and 200ml pure water successively add
Enter in crystallizing kettle, SAPO-11 molecular sieve is synthesized using Situ Hydrothermal crystallization method.Each substance is added brilliant according to aforementioned proportion and sequence
After changing kettle, sealing, and with 5oThe speed of C/min is warming up to 220 oC, it is then allowed to stand crystallization 48h or more.The solid product that will be obtained
Three times with pure water, it is subsequently placed in 55 under argon atmosphere oC1h is dried to get SAPO-11 molecular sieve is arrived.
Take the nitric acid solution 50ml(density 1.3 or so of 3mol/L) and 2mol/L sulfuric acid solution (density 1.4 or so)
50ml mixing, obtains acidic activated liquid.40-70 mesh (200-300 microns) are crossed after graphene film grinding, 1.5g is then weighed and adds
Enter in acidic activated liquid, at room temperature stir-activating 8h, mixing speed 100rpm.SAPO-11 molecular sieve 0.5g obtained is added,
Then ultrasound 10 minutes, obtain mixing suspension.Mixing suspension is filtered, filter residue is placed in drying under nitrogen atmosphere, does
40 degrees Celsius of dry temperature, drying time 2h obtain support powder.Weigh Ce (NO3)3•6H2O solid 1g, 50% manganese nitrate solution
2.8g is added sequentially to 50g(62.5ml) in ethyl alcohol, 125ml deionized water is added, it is uniformly mixed, 4.6g carrier is then added
Powder stands reaction 6h after ultrasonic 30min.Then it filters, goes filter residue dry according to following temperature programmed control: under argon atmosphere,
First in 50-55oDry 2h under C, then with 2oThe rate of C/min is warming up to 70-80oDry 3h under C.Then in argon atmospher
It is roasted under enclosing, maturing temperature 320oC；Calcining time is 3.5h, after roasting under argon atmosphere natural cooling,
Obtain MnOx-CeO2@graphene-molecular sieve catalyst.
Embodiment 2
SAPO-11 molecular sieve is made using 1 same procedure of embodiment.
Take the nitric acid solution 50ml(density 1.3 or so of 3mol/L) and 2mol/L sulfuric acid solution (density 1.4 or so)
50ml mixing, obtains acidic activated liquid.40-70 mesh (200-300 microns) are crossed after graphene film grinding, 1.5g is then weighed and adds
Enter in acidic activated liquid, at room temperature stir-activating 8h, mixing speed 100rpm.SAPO-11 molecular sieve 0.5g obtained is added,
Then ultrasound 5 minutes, obtain mixing suspension.Mixing suspension is filtered, filter residue is placed under nitrogen atmosphere dry, drying
40 degrees Celsius of temperature, drying time 2h obtains support powder.Weigh Ce (NO3)3•6H2O solid 1g, 50% manganese nitrate solution
2.8g is added sequentially to 50g(62.5ml) in ethyl alcohol, 125ml deionized water is added, it is uniformly mixed, 4.6g carrier is then added
Powder stands reaction 8h after ultrasonic 40min.Then it filters, goes filter residue dry according to following temperature programmed control: under argon atmosphere,
First in 50-55oDry 2h under C, then with 2oThe rate of C/min is warming up to 70-80oDry 3h under C.Then in argon atmospher
It is roasted under enclosing, maturing temperature 320oC；Calcining time is 4h, after roasting under argon atmosphere natural cooling, i.e.,
Obtain MnOx-CeO2@graphene-molecular sieve catalyst.
Embodiment 3
SAPO-11 molecular sieve is made using 1 same procedure of embodiment.
Take the nitric acid solution 50ml(density 1.3 or so of 3mol/L) and 2mol/L sulfuric acid solution (density 1.4 or so)
50ml mixing, obtains acidic activated liquid.40-70 mesh (200-300 microns) are crossed after graphene film grinding, 1.5g is then weighed and adds
Enter in acidic activated liquid, at room temperature stir-activating 8h, mixing speed 100rpm.SAPO-11 molecular sieve 0.5g obtained is added,
Then ultrasound 10 minutes, obtain mixing suspension.Mixing suspension is filtered, filter residue is placed in drying under nitrogen atmosphere, does
40 degrees Celsius of dry temperature, drying time 2h obtain support powder.Weigh Ce (NO3)3•6H2O solid 1g, 50% manganese nitrate solution
2.8g is added sequentially to 50g(62.5ml) in ethyl alcohol, 125ml deionized water is added, it is uniformly mixed, 4.6g carrier is then added
Powder stands reaction 8h after ultrasonic 40min.Then it filters, goes filter residue dry according to following temperature programmed control: under argon atmosphere,
First in 50-55oDry 2h under C, then with 2oThe rate of C/min is warming up to 70-80oDry 3h under C.Then in argon atmospher
It is roasted under enclosing, maturing temperature 300oC；Calcining time is 3h, after roasting under argon atmosphere natural cooling, i.e.,
Obtain MnOx-CeO2@graphene-molecular sieve catalyst.
The detection of catalyst physical and chemical performance
1. specific surface area and hole hold test
Specific surface area is carried out to catalyst made from embodiment 1-3 and hole holds test, testing result is as shown in table 1.
Catalyst made from 1 embodiment 1-3 of table carries out specific surface area and Kong Rong
From the point of view of testing result, the specific surface area with higher of catalyst made from embodiment 1-3 and biggish Kong Rong, Gao Bibiao
Area and hole, which have, effectively adsorbs gas conducive to catalyst, helps to improve the catalytic activity of catalyst.
2. catalyst denitration performance
It is carried out in simulation SCR denitration device using catalyst made from embodiment 1-3.The loading pipeline diameter of catalyst is
3.5 millimeters, the dosage for testing catalyst every time is 0.1g.It is as follows to simulate gas composition: NO 1.115g/m3,NH3It is 0.688
g/m3, O2For 0.49.853g/m3, remaining is nitrogen, when detecting the sulfur resistance of catalyst, increases sulfur dioxide gas 0.235
g/m3.Exit gas detection is using infrared gas analyser detection outlet sulfur dioxide and nitric oxide production gas concentration.Experiment
Temperature is 90-210 in the processoC, gas flow 7.5-48.5L/h.To avoid catalyst physical absorption to the shadow of experimental result
It rings, catalyst is pre-processed before experiment: 80 oCIt is lower to use nitrogen to catalyst purge 1.5h.From 90-240 oCTemperature range
It is interior, every 30oC is a temperature test point, and each temperature test point testing time is 1h, to obtain stable denitrification rate P
(%), calculation formula is as follows.
NO concentration before denitrification rate P=(NO concentration after NO concentration-denitration before denitration)/denitration, concentration unit g/m3, in order to
Reduce error, when calculating can be by concentration according to mg/m3It is calculated.
Testing result is as shown in Figure 1, as testing result it is found that catalyst made from embodiment 1-3 is in 90-240 oCTemperature
It spends in section, as the temperature rises, catalyst activity gradually rises, and reaches 240 in temperature oCAfterwards, denitrification rate has reached
90%.This is compared with traditional denitrating catalyst, the advantage with apparent low-temperature catalytic activity.Catalyst shows low temperature height
The reason of activity may have the following, first is that catalyst reference area with higher itself and Kong Rong, so that catalyst has
Adsorption area is imitated to increase；Second is that due to the immersion treatment of catalyst carrier acid solution, so that catalyst carrier has certain acid
Property；Third is that since catalyst itself has excellent electron transfer orbital, Ce+4With Ce+3Between, Mn+4With Mn+6Between electronics
Transfer and a large amount of Lacking oxygen make MnOx and CeO2With excellent reducing power and significant oxygen storage capacity, so that catalyst
There is higher activity at low temperature.
The above described is only a preferred embodiment of the present invention, being not that the invention has other forms of limitations, appoint
What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc.
It imitates embodiment and is applied to other fields, but without departing from the technical solutions of the present invention, according to the technical essence of the invention
Any simple modification, equivalent variations and remodeling to the above embodiments, still fall within the protection scope of technical solution of the present invention.
Claims (8)
1. a kind of porous graphene-molecular sieve complex carries denitrating catalyst, which is characterized in that the catalyst carrier is graphite
Alkene-molecular sieve complex carries, active component MnOx-CeO2。
2. porous graphene according to claim 1-molecular sieve complex carries denitrating catalyst, which is characterized in that the stone
Black alkene is acidic activated single-layer or multi-layer graphene, and the molecular sieve is SAPO-11 molecular sieve.
3. porous graphene as claimed in claim 1 or 2-molecular sieve complex carries denitrating catalyst preparation method, which is characterized in that
Include the following steps:
(1) sulfuric acid solution of the nitric acid solution of 3mol/L and 2mol/L are mixed according to the ratio of volume ratio 1:1, obtains acid work
Change liquid；
(2) it is impregnated in after grinding graphene film in acidic activated liquid, activation 8-10h is stirred at room temperature；
(3) SAPO-11 molecular sieve is added, it is 5-10 minutes ultrasonic, obtain mixed liquor；
(4) it after filtering mixed liquor, is dried, obtains support powder；
(5) by Ce (NO3)3·6H2O and mass fraction are that 50% manganese nitrate solution is dissolved into ethyl alcohol, and deionized water, mixing is added
It is uniformly rear that support powder is added, reaction 5-8h is stood after ultrasonic 30-50min, filtering, filter residue progress temperature programmed control is dry, then
It roasts under inert gas atmosphere, catalyst is obtained after natural cooling.
4. porous graphene-molecular sieve complex carries denitrating catalyst preparation method, feature exist according to claim 3
In partial size is 200-300 microns after graphene film grinding in the step (2)；Graphene and acidic activated liquid mass ratio are 1:
(100-150), stirring rate 100-120rpm.
5. porous graphene-molecular sieve complex carries denitrating catalyst preparation method, feature exist according to claim 3
In graphene film and SAPO-11 molecular sieve quality ratio are 3:1.
6. porous graphene-molecular sieve complex carries denitrating catalyst preparation method, feature exist according to claim 3
In Ce (NO in the step (5)3)3·6H2O and mass fraction are that 50% manganese nitrate solution mass ratio is 1:2.8；Ce(NO3)3·
6H2O and ethyl alcohol mass ratio are 1:50, and ethyl alcohol and deionized water volume ratio are 1:2, Ce (NO3)3·6H2O and support powder quality
Than for 1:4.6.
7. porous graphene-molecular sieve complex carries denitrating catalyst preparation method, feature exist according to claim 3
In ultrasonic time is 35min in the step (5), and the standing reaction time is 6h；Filter residue temperature programmed control drying process is nitrogen atmosphere
Enclose lower two freeze-day with constant temperature stages: first stage 50-55oDry 2h under C, with 2oThe rate of C/min is warming up to second stage,
Second stage is 70-80oDry 3h under C；Inert gas is argon gas or nitrogen, maturing temperature 300-350oC, preferably 320oC；
Calcining time is 3-4h, preferably 3.5h.
8. porous graphene as claimed in claim 1 or 2-molecular sieve complex carries denitrating catalyst answering during denitrating flue gas
With.
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