CN110102286A - A kind of doped nano manganese dioxide-graphene/Al2O3Preparation method, catalyst and the application of catalyst - Google Patents
A kind of doped nano manganese dioxide-graphene/Al2O3Preparation method, catalyst and the application of catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 17
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 8
- 239000011572 manganese Substances 0.000 title claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 9
- 238000007873 sieving Methods 0.000 claims abstract description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000006385 ozonation reaction Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 25
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 11
- 150000004706 metal oxides Chemical class 0.000 abstract description 11
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 32
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 28
- 238000002474 experimental method Methods 0.000 description 20
- 238000012360 testing method Methods 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000008188 pellet Substances 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Substances [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 5
- 239000011324 bead Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- -1 hydroxyl radical free radical Chemical class 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 229910003320 CeOx Inorganic materials 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- 229910005084 FexOy Inorganic materials 0.000 description 1
- 241000264877 Hippospongia communis Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 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
- 239000000356 contaminant Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B01J35/40—
-
- B01J35/51—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of doped nano manganese dioxide-graphene/Al2O3Preparation method, catalyst and the application of catalyst, it is bright to be related to catalyst preparation technical field.It is excessively high for the simple metal oxide catalyst cost of solution, ratio does not often result in materials waste uniquely, there is also some intrinsic problems for supported catalyst, such as the determination of load capacity, the catalyst impregnated for a long time is often loosely organized, it is too fast to reuse behind efficiency reduction, leads to that use cannot be repeated as many times；Short with water body time of contact, degradation rate is low；Active principle, which incorporates in water, leads to loss etc., method provided by the invention are as follows: MnO is added in GO2Hybrid reaction is dried, and is ground, sieving；Al is added2O3Spherical shape is made in mixing, obtains catalyst after roasting.Preparation method provided by the invention is at low cost, and catalyst effect is good and can be recycled repeatedly.
Description
Technical field
The present invention relates to catalyst preparation technical fields.
Background technique
Heterogeneous catalytic ozonation system, which refers to, to be added catalyst during ozone oxidation and forms catalyst collaboration
The system of ozonidation reaches deep oxidation to reduce the activation energy of reaction process or change oxidation reaction process
Purpose, to remove removal organic polluter.Compared with homogeneous catalytic ozonation system, the system there are solid phase, liquid phase and
Gas phase, thus react more complicated.Typically, the oxidation efficiency of the technology and engineering application value by catalyst activity,
The influence of stability and service life
Metal oxide is often selected as the catalyst of catalytic ozonation system, and reaction mechanism is to be adsorbed in metal oxide
Ozone on surface, which is decomposed, generates the hydroxyl radical free radical (OH) with strong oxidizing property, and then in catalyst surface and solution
Middle generation free chain reaction.
The catalysis reaction of heterogeneous catalytic ozonation system is likely to occur in solution or solid catalyst surface.Catalyst
Be divided into two major classes: one is individual metal oxides；Another kind of is the metal or metal oxide on carrier.
The common metal oxide as catalyst has: MnO2、CeO2、TiO2、FexOyWith γ-Al2O3But because of load
Type catalyst carrier has the advantages that suitable pore structure and has become the catalysis of most study with large specific surface area
Agent.In addition to meeting conditions above, carrier is provided to the certain anti-pressure ability of the catalyst loaded thereon and good heat is steady
It is qualitative, active component dosage can be saved to a certain extent.Common carrier has titanium dioxide, active carbon, ceramic honey comb, three
Al 2 O.Common loaded catalyst has MnOX/MCM-41、CeOx/AC、TiO2/Al2O3With nanometer-TiO2/ zeolite molecules
Sieve etc..Simple metal oxide catalyst cost is excessively high, and ratio does not often result in materials waste uniquely, and supported catalyst is also deposited
In some intrinsic problems, such as the determination of load capacity, the catalyst impregnated for a long time is often loosely organized, reuses behind efficiency
Reduce it is too fast, cause cannot be repeated as many times use；Short with water body time of contact, degradation rate is low；Active principle, which incorporates in water, leads
Cause loss etc..
Summary of the invention
Excessively high to solve above-mentioned simple metal oxide catalyst cost, ratio does not often result in materials waste uniquely,
There is also some intrinsic problems, such as the determination of load capacity for supported catalyst, and the catalyst impregnated for a long time is often loosely organized,
It is too fast to reuse behind efficiency reduction, leads to that use cannot be repeated as many times；Short with water body time of contact, degradation rate is low；Effectively
Substance, which incorporates in water, leads to loss etc., and the present invention provides a kind of doped nano manganese dioxide-graphene/Al2O3Catalysis
The preparation method of agent.
Doped nano manganese dioxide-graphene/Al provided by the invention2O3The preparation method of catalyst uses reaction kettle
Hydrothermal synthesis method, specifically:
(1) graphene oxide (GO) is taken, adding water and stirring makes it be uniformly dispersed, and predecessor is added, and is uniformly mixed, by mixture
140~200 DEG C of 10~16h of reaction are placed in, after being cooled to room temperature, reactant is taken out, dries, grind, sieving；
(2) take step (1) products therefrom that Al is added2O3It is uniformly mixed, spherical shape is made, dry, after being cooled to room temperature, in nitrogen
In tubular type kiln roasting, natural cooling under gas atmosphere protection.
Further, step (1) graphene oxide and MnO2Mass ratio be 1:4~1:6.
Further, step (1) is described is uniformly mixed, and is to stir 4~8h at 60~70 DEG C to be allowed to uniformly mixed.
Further, step (1) drying, isolation air dries 1-10h at specially 80~93 DEG C.
Further, step (1) sieving was 60 meshes.
Further, step (2) the addition Al2O3, additional amount is to make graphene oxide and MnO2It the two quality and accounts for
Al2O3, graphene oxide and MnO2The 7%~10% of three's mass sum.
Further, step (2) is described is made spherical shape, and spherical diameter is 4mm~10mm.
Further, spherical catalyst is specially placed in 80 DEG C of 12~14h of drying by step (2) drying.
Further, step (2) maturing temperature is 300~700 DEG C, and calcining time is 3~5h；Preferably, it roasts
Temperature is 425~525 DEG C, and calcining time is 3.75~5h.
Furthermore the present invention also provides the catalyst for using the above method to prepare and its applications.
Beneficial effect
Method provided by the invention has used the graphene oxide that price constantly reduces in recent years, solves simple metal
The excessively high problem of oxide catalyst cost, meanwhile, the catalyst prepared using method provided by the invention, load capacity selection is relatively
Freely, and there is no impregnating rear catalyst structure for a long time to be easy loose problem, in addition catalyst reuse efficiency is steady,
It can repeatedly recycle, and since catalyst is heterogeneous catalyst, reclaimer operation is simple and easy.
This, which tests freshly prepared catalyst, following benefit: (1) using heterogeneous catalysis, catalyst sinks to water body bottom
A possibility that portion can be recycled after the test, ensure that practical implementation.(2) experiment materials save, it is used effectively at
Divide manganese oxide cheap, cost is gradually decreasing in recent years though graphene has certain values, therefore this method passes through
It is feasible in Ji.(3) catalyst effect is excellent, and by experiment, for target contaminant treatment effeciency close to 100%, salinity is good,
Belong to rare in existing catalyst.(4) it is still fine that multiple effect is recycled, by 10 times or more circulation experiments, discovery catalysis
The effect of agent still keeps 92%~95%.Illustrate that catalyst circulation uses hardly to be lost.(5) the durable use of catalyst, leaching
Intensity is no different with use for the first time after bubble.
Detailed description of the invention
Fig. 1 whether the catalyst containing graphene for quinoline removal effect；
Removal effect of Fig. 2 different catalysts for quinoline；
Influential effect of Fig. 3 different-grain diameter to catalyst；
Influence of Fig. 4 difference maturing temperature to catalyst effect；
Fig. 5 different MnO2Influence of the content for catalyst effect；
Influence of Fig. 6 difference calcining time to catalyst effect；
Fig. 7 difference GO:MnO2Influence of the mass ratio to catalyst effect；
Fig. 8 catalyst recycles effect；
Fig. 9 (a) native oxide graphene FTIR characterization；(b)GO:MnO2The catalyst of mass ratio 1:10 load graphene
FTIR characterization；(c)GO:MnO2Mass ratio 1:5 loads the catalyst FTIR characterization of graphene.
Specific embodiment
1 catalyst preparation of embodiment
(1) it takes graphene oxide (GO) on a small quantity in beaker, adds suitable quantity of water stirring that it is made to be uniformly dispersed, MnO is added2, institute
State graphene oxide and MnO2Mass ratio be 1:4, at 60 DEG C stir 4h to being mixed thoroughly, mixture is gone to instead
It answers in kettle and seals, be placed in 160 DEG C of reaction 12h, after being cooled to room temperature, take out reactant, the drying of isolation air, will dry at 80 DEG C
Powder afterwards is ground repeatedly in mortar, crosses 60 meshes；
(2) take step (1) products therefrom that Al is added2O3, additional amount is to make graphene oxide and MnO2It the two quality and accounts for
Al2O3, graphene oxide and MnO2The 7% of three's mass sum is uniformly mixed, is twisted into spherical shape, ball manually under the action of Aluminum sol
Shape diameter is 8mm, and uneven, the undesirable bead of partial size big for crack, spherical kneads again, and bead is uniformly put
In an oven in 80 DEG C of drying 12h on surface plate, after being cooled to room temperature, in tubular type kiln roasting, roasting under nitrogen atmosphere protection
Burning temperature is 300 DEG C, and calcining time 3h, natural cooling obtains catalyst pellet.
Comparative example 1
According to the ratio of metal oxide in embodiment 1, it is added without graphene oxide, directly metal oxide is mixed and is added
Catalyst pellet is made at drying roasting after bead in water kneading (operating condition parameter is same as Example 1).
Comparative example 2
Unlike comparative example 1, metal oxide uses single aluminium oxide, and catalyst pellet is made.
Comparative example 3
Unlike the first embodiment, it is added without manganese dioxide, other operations are identical, and catalyst pellet is made.
Catalyst effect verification test:
The ozone reaction device of use is made of three systems: ozone generation system, reaction system, tail gas concentration mensuration and
Processing system.Ozone generation system includes oxygen generator, ozone generator, gas flowmeter and ozone concentration detector group
At oxygen is that gas source occurs, and by the measurement of flow and ozone concentration, calculates ozone output.
The core of catalytic oxidation system is inner circulation reactor, and reactor is cylindrical body, internal diameter 50mm, and dischargeable capacity is
1.5L, design water level height are 700mm, and oxygen is occurred by oxygenerator, then enter ozone generator and generate ozone.When experiment,
Catalyst and quinoline water distribution are added in reactor, ozone and quinoline water distribution enter together by microbubble bubble generator is latter
In reactor, reaction solution circular response, to guarantee that catalyst, ozone and water come into full contact with.The reactor has water inlet and goes out
The mouth of a river can carry out batch run and long run test.Ozone tail gas is discharged outdoor after 5% KI solution decomposes.
The waste gas flow direction in exhaust system can be needed to change according to experiment, the utilization of ozone is calculated using ozone detector
Rate contains a small amount of ozone in tail gas, is discharged finally by the solution containing 5% potassium iodide, uses sodium thiosulfate after experiment
Residue KI solution is titrated, ozone surplus is calculated.
Before batch experiment uses a water intake mode, experiment to start, ozone generator and ozone testing machine are carried out first
Preheating, is first turned on oxygen, after stablizing 5~10min, connects ozonograph, air inflow needed for choice experiment and ozone hair
Raw device power.Water sample is added to reactor and adds catalyst (or not putting into catalyst), is passed through ozone, remembers according to experimental design
The reaction time is recorded, by 0.5~1mL sodium thiosulfate (0.01molL after sampling-1) be added to terminate ozone oxidation reaction.According to
It is required that tail gas is passed through ozone analyzer record residual ozone concentration, and absorbed with 5% liquor kalii iodide.Test end operation:
Stopping water inlet-adjusting ozone generator power is that 0-closing ozone generator-is continuously passed through 10~15min of oxygen-closing
Oxygen generator achievees the purpose that residual ozone in removal device and reactor.
Catalyst uses top to add, and sinks to the mode of bottom, using heterogeneous catalysis, bubble enters top by bottom
It overflows, flows through catalyst and react therewith.
Compliance test result is carried out to catalyst using above-mentioned apparatus and step:
1, whether the catalyst containing graphene compares the removal effect of quinoline: respectively using embodiment 1 (containing GO)
The catalyst pellet being prepared with comparative example 1 (being free of GO) controls experiment condition ([quinoline] as catalyst0=50mgL-1,[O3]=25mgmin-1, [catalyst]=40gL-1, partial size 8mm), experimental result is shown in Fig. 1, demonstrate graphene
In the presence of compared with not containing graphene, catalyst whole efficiency is improved.
2, different catalysts compliance test result: 1 (Al of embodiment is used respectively2O3/RGO/MnO2), 1 (Al of comparative example2O33/
MnO2), blank (catalyst is not added), 2 (Al of comparative example2O3), 3 (Al of comparative example2O3/ RGO) gained catalyst pellet conduct catalysis
Agent controls experiment condition ([quinoline]0=50mgL-1,[O3]=25mgmin-1, [catalyst]=40gL-1, partial size is
8mm), acquired results are shown in Fig. 2, demonstrate the validity of prepared catalyst again.
3, different-grain diameter verifies the influential effect of catalyst: by the bead partial size in embodiment 1 be respectively set to 4mm,
6mm, 8mm, 10mm prepare catalyst pellet as catalyst, control experiment condition ([quinoline]0=50mgL-1,[O3]=
25mg·min-1, [catalyst]=40gL-1), as a result see Fig. 3 the experiment has found that partial size is smaller, and effect is better, with partial size
Reduce, effect promoting is obvious.
4, influence verifying of the different maturing temperatures to catalyst removal effect: by step (2) maturing temperature in embodiment 1 point
It is not set as 300,400,450,500,600,700 DEG C, other conditions are constant, prepare catalyst, and control experiment condition control is real
Test condition ([quinoline]0=50mgL-1,[O3]=25mgmin-1, [catalyst]=40gL-1, partial size 4mm) and it carries out in fact
It tests, as a result sees Fig. 4, it is seen that 450 DEG C are optimum temperature.
5, different MnO2Influence of the content for quinoline removal rate: by MnO in embodiment 12Mass percent is accounted for be set as
0/3/6/9/12% primary preparation catalyst pellet, controls experiment condition ([quinoline]0=50mgL-1,[O3]=25mgmin-1, [catalyst]=40gL-1, partial size 4mm), the study found that best MnO2Throwing amount is 9%.As a result see Fig. 5, it can be seen that
Within the scope of manganese dioxide mass percent 0-12%, as manganese dioxide content rises, catalyst efficiency is increased accordingly, but works as
When manganese dioxide mass percent is 9%, catalyst efficiency highest does not meet global regularity, when manganese dioxide mass percent
A unexpected technical effect is obtained when being 9%.
6, influence verifying of the different calcining times to catalyst removal effect: the calcining time in embodiment 1 is set respectively
Be set to 3,4,5,6,7h prepare catalyst, control experiment condition ([quinoline]0=50mgL-1,[O3]=25mgmin-1, [urge
Agent]=40gL-1, partial size 4mm), as a result see Fig. 6 the experiment has found that the best calcining time of catalyst is 4h.
7, different graphene contents influences verifying to the treatment effect of catalyst: by the GO:MnO in embodiment 12Quality
Catalyst is prepared than being respectively set to 1:5,1:10,1:20, is controlled experiment condition ([quinoline]0=50mgL-1,[O3]=
25mg·min-1, [catalyst]=40gL-1, partial size 4mm), control MnO2Content is 8%, chooses different GO:MnO2Matter
Amount ratio is tested, and as a result sees Fig. 7, discovery graphene content is higher, and treatment effect is better.
8, the influence verifying of catalyst degradation quinoline effect: the parameter preparation catalysis of adjustment embodiment 1 is recycled and reused
Agent controls experiment condition ([quinoline]0=50mgL-1,[O3]=25mgmin-1, [catalyst]=40gL-1, partial size is
4mm), it is recycled and reused after the every use of catalyst is primary, is used a kind of catalyst 10 times under identical conditions, study 10 repetitions
Using the influence for catalyst treatment effect, Fig. 8 is as a result seen: finding that the stability of catalyst is fine from figure, by ten times
It reuses, quinoline removal rate can still keep 94% or more.
9, the FTIR characterization of catalyst
Experiment has carried out FTIR characterization to the catalyst of native oxide graphene, 1:10,1:5 load graphene respectively, number
See that Fig. 9: Fig. 9 is graphene oxide and MnO according to figure2The Fourier transform infrared spectrogram of/GR catalyst.
As can be seen from the figure, graphene oxide is in 3420cm-1Nearby there is a wider, stronger absorption peak, this is belonged to
The stretching vibration peak of O-H；1730cm-1Place is the stretching vibration peak of C=O on graphene oxide carboxyl；1620cm-1The absorption at place
Peak is considered as the absorption peak of the vibration of C=C in not oxidized graphite；In 1402cm-1The absorption peak at place may belong to C-OH
Bending vibration absorption peak；1210,1060cm-1The absorption peak at place is the vibration absorption peak of C-O-C and C-O respectively, shows institute
There is-OH ,-COOH, C-O-C and-C=O functional group on the graphene oxide used.
Load MnO2Afterwards, absorption peak everywhere, which weakens even to disappear, illustrates that GO is restored, and in 620,495cm-1Place
Then there is new characteristic peak, these peaks are considered as Mn-O-C vibration absorption peak from infrared analysis, graphite oxide
A large amount of oxygen-containing group is contained on alkene surface, they can with manganese by chemical bond in conjunction with make MnO2It is more conducive to load on GO,
And the dispersed for improving active component is also confirmed from this angle, chemistry has occurred in graphene and manganese and oxygen compound surface
The combination of key.
Claims (10)
1. a kind of doped nano manganese dioxide-graphene/Al2O3The preparation method of catalyst, it is characterised in that: including following
Step:
(1) graphene oxide (GO) is taken, adding water and stirring makes it be uniformly dispersed, and predecessor is added, and is uniformly mixed, on the surface of graphene
Load generates manganese dioxide, and mixture is placed in 140~200 DEG C of 10~16h of reaction, after being cooled to room temperature, takes out reactant, dries
It is dry, it grinds, sieving；
(2) take step (1) products therefrom that Al is added2O3It is uniformly mixed, spherical shape is made, dry, after being cooled to room temperature, in nitrogen gas
In tubular type kiln roasting, natural cooling under atmosphere protection.
2. method according to claim 1, it is characterised in that: step (1) graphene oxide and MnO2Mass ratio be
1:4~1:6.
3. method according to claim 1, it is characterised in that: be to stir 4~8h at 60~70 DEG C to be allowed to uniformly mixed.
4. method according to claim 1, it is characterised in that: step (1) described drying completely cuts off at specially 80~93 DEG C empty
Gas dries 1-10h.
5. method according to claim 1, it is characterised in that: step (2) the addition Al2O3, additional amount is to make graphite oxide
Alkene and MnO2The two quality and account for Al2O3, graphene oxide and MnO2The 7%~10% of three's mass sum.
6. method according to claim 1, it is characterised in that: step (2) is described to be made spherical shape, spherical diameter be 4mm~
10mm。
7. method according to claim 1, it is characterised in that: spherical catalyst is specially placed in by step (2) described drying
80 DEG C of 12~14h of drying.
8. method according to claim 1, it is characterised in that: step (2) maturing temperature is 300~700 DEG C, when roasting
Between be 3~5h；Preferably, maturing temperature is 425~525 DEG C, and calcining time is 3.75~5h.
9. a kind of catalyst of any one of -8 the method preparations according to claim 1.
10. a kind of application of the catalyst described in claim 9 in catalytic ozonation system.
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