CN110385124A - One kind passing through segmentation reaction preparation MnOx-CeO2The method of mixed oxide catalyst - Google Patents
One kind passing through segmentation reaction preparation MnOx-CeO2The method of mixed oxide catalyst Download PDFInfo
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- CN110385124A CN110385124A CN201810335611.XA CN201810335611A CN110385124A CN 110385124 A CN110385124 A CN 110385124A CN 201810335611 A CN201810335611 A CN 201810335611A CN 110385124 A CN110385124 A CN 110385124A
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 129
- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 230000011218 segmentation Effects 0.000 title claims abstract description 7
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 39
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 18
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 15
- -1 cerium ion Chemical class 0.000 claims abstract description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 11
- 230000001376 precipitating effect Effects 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 15
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 238000001994 activation Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 230000001788 irregular Effects 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims 2
- 230000032683 aging Effects 0.000 claims 1
- 229910000027 potassium carbonate Inorganic materials 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000012855 volatile organic compound Substances 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 238000007254 oxidation reaction Methods 0.000 abstract description 13
- 230000003647 oxidation Effects 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 10
- 238000004886 process control Methods 0.000 abstract description 3
- 239000002244 precipitate Substances 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 33
- 239000000243 solution Substances 0.000 description 33
- 239000011572 manganese Substances 0.000 description 17
- 229910052760 oxygen Inorganic materials 0.000 description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- 239000001301 oxygen Substances 0.000 description 15
- 238000009938 salting Methods 0.000 description 14
- 238000006555 catalytic reaction Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 2
- 229910016978 MnOx Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000005118 spray pyrolysis Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- 150000000703 Cerium Chemical class 0.000 description 1
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- QNEFNFIKZWUAEQ-UHFFFAOYSA-N carbonic acid;potassium Chemical compound [K].OC(O)=O QNEFNFIKZWUAEQ-UHFFFAOYSA-N 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
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- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- B01D2257/708—Volatile organic compounds V.O.C.'s
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- B01J2219/00851—Additional features
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- B01J2219/0086—Dimensions of the flow channels
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- B01J2219/00889—Mixing
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Abstract
The present invention relates to one kind to pass through segmentation reaction preparation MnOx‑CeO2The method of mixed oxide catalyst, belongs to field of catalyst preparation.The present invention provides a kind of MnOx‑CeO2Mixed oxide catalyst preparation process, including the first conversion zone and the second conversion zone, the outlet of the first conversion zone and the intake channel of the second conversion zone are connected directly.It is continuously injected into reaction solution and precipitating reagent containing cerium ion respectively in intake channel A, B of the first conversion zone, II section of reaction is entered after short stay, the reaction was continued with reaction solution with manganese ions is continuously injected by intake channel D.Reaction precipitate obtains the MnO with good VOCs complete oxidation catalytic activity after subsequent processingx‑CeO2Mixed oxide catalyst.Above-mentioned preparation MnOx‑CeO2The technique of mixed oxide catalyst, have it is easy to operate, it is at low cost, the features such as process control, the catalyst of high activity can be made.
Description
Technical field
The invention belongs to field of catalyst preparation, are related to a kind of using microreactor preparation MnOx-CeO2Mixed oxide is urged
The method of agent.
Background technique
Volatile organic compounds (VOCs) is one of main source of atmosphere pollution, and VOCs's effectively dispels always ring
The important directions of border Controlling research, current main VOCs processing method include flame combustion method, catalytic oxidation, absorption method,
Absorption process, lower temperature plasma technology etc..Catalytic oxidation be compared with other methods low with treatment temperature, treatment effeciency is high,
Dispel thoroughly, convenient for continuous operation, treating capacity is big the advantages that, be widely used in industrial waste gas, VOCs in the gases such as vehicle exhaust
Dispel.Catalyst is the core in VOCs catalysis oxidation field.VOCs catalyst for catalytic oxidation can be divided into noble metal catalyst and
Non-precious metal catalyst two major classes.Although noble metal catalyst such as Pt, Pd etc. have the low-temperature catalytic oxidation reaction of VOCs very high
Catalytic activity, but its higher cost and sensitivity vulnerable to the weakness poisoned limit noble metal catalyst in actual VOCs
Application in subtractive process, and lower-cost non-precious metal catalyst have always been considered as be noble metal excellent replacer.
Non-precious metal catalyst main active includes the transition metal such as Fe, Co, Ni, Cu, Mn, Ce.In these substances
In, Mn oxide is one of most study, most widely used component due to its high ligancy and variable valence.Cerium oxide by
Have the function of good storage oxygen in its oxygen vacancies, can be used as " the oxygen cabin " of catalyst, be most common cocatalyst component.
Synergistic effect between Ce and Mn enhances the redox property of catalyst, it is made to possess higher electric conductivity and stronger
Surface acidity, therefore, MnOx-CeO2Mixed oxide catalyst has a wide range of applications in terms of the oxidation of VOCs.
For MnOx-CeO2There are many research of mixed oxide catalyst, and technology of preparing is broadly divided into vapor phase method and liquid phase
Two class of method.In " the Catalytic oxidation of benzene over Ce-Mn that " Particuology " is delivered
Flame spray pyrolysis method is used in oxides synthesized by flame spray pyrolysis " is prepared for MnOx-
CeO2Mixed oxide forms strong interaction, will form partial size more under the flame injection of high temperature between Ce-Mn
Small catalyst granules, and the catalyst is preferable to the catalytic oxidation performance of benzene at low temperature.But this method synthetic catalyst mistake
Due to that can generate very high temperature in journey, thus its process is difficult to control, and can generate the case where partial catalyst is reunited.
" the MnO delivered in " Applied Catalysis B "x-CeO2mixed oxide catalysts for
complete oxidation of formaldehyde:Effect of preparation method and
Sol-gal process has been used to be prepared for MnO in calcination temperature "x-CeO2Mixed oxide, but use the method
The sample of preparation, there are catalyst surface area, pore volume and the lesser problem of average pore radius, and the Mn on its surface4+'s
Ratio is smaller, and the Lattice Oxygen on surface is also on the low side, since higher manganese valence and more lattice surface oxygen are catalyzed raising
The reactivity of agent is critically important, so lower using example reaction activity prepared by sol-gal process.Meanwhile making in the publication
With coprecipitation as a comparison, the results show that the MnO prepared using coprecipitationx-CeO2Mixed oxide has bigger
Pore volume, bigger catalyst surface area, and bigger pore radius, the activity of catalysis are also significantly better than collosol and gel legal system
Standby sample.
Literature research is summarized it can be found that in MnOx-CeO2In mixed oxide catalyst, Mn is main active component,
Need higher dispersibility to improve contact interface and catalytic activity.CeO2There is both sides to act on as co-catalyst, first is that
Promote MnOxDispersion to improve activity, second is that transmitting the elemental oxygen of high activity using Lattice Oxygen and Lacking oxygen, promote the oxygen of Mn
Change reduction circulation, accelerates catalytic reaction process.Since Lattice Oxygen and Lacking oxygen are present in CeO2Crystal structure in, control CeO2
Scale be to guarantee existing appropriate Lattice Oxygen and oxygen vacancy concentration, and have biggish MnOx-CeO2Contact surface, and promote MnOx
Fine dispersion key.However, due to Mn2+、Ce2+Precipitation process be all the reaction process being exceedingly fast, common coprecipitation process
In it is extremely difficult to the distribution of the component of sediment, the control of crystal structure.
Summary of the invention
For MnOx-CeO2Catalyst, there are two design feature is most important to its activity.First, CeO2With crystal habit
In the presence of, can for catalysis reaction the Lattice Oxygen of high activity be provided；Second, the mutual degree of scatter of two components of Mn-Ce it is high, in conjunction with tight
It is close, effectively play synergistic effect.However, the two require to be embodied in CeO existing for crystal habit there are certain conflict2Drop
The low mutual dispersibility of the two.The present invention provides one kind to pass through segmentation reaction preparation MnOx-CeO2The method of catalyst is led to
It crosses by the way of segmentation reaction, regulates and controls the microstructure characteristic of two kinds of components, guarantee giving full play to for each component function.It is described micro-
Reactor includes the first conversion zone and the second conversion zone, the MnO of preparationx-CeO2Mixed oxide catalyst is catalyzed for VOCs
Oxidative degradation, easy to operate, the catalyst of high activity can be made at low cost, process control.The present invention uses following technology thus
Scheme:
One kind passing through segmentation reaction preparation MnOx-CeO2The method of mixed oxide catalyst, which is characterized in that containing cerium from
Reaction solution and with manganese ions continuously flows into two closely coupled conversion zones of microreactor front and back respectively, successively and containing precipitating
The solution reaction of agent, sediment obtain the MnO with good VOCs complete oxidation catalytic activity through subsequent processesx-CeO2It is mixed
Close oxide catalyst.
Microreactor needed for this method includes closely coupled the first conversion zone and the second conversion zone:
First conversion zone is set there are two intake channel A, B and one outlet channel, and A, channel B are respectively used to be added containing cerium
Ionic reaction liquid and precipitant solution；
Second conversion zone is set there are two intake channel C, D and one outlet channel, and channel C and the outlet of the first conversion zone are logical
Road is connected directly, and channel D is for being added reaction solution containing manganese ion.
Further, microreactor the first conversion zone intake channel A is connected with storage tank P-1, intake channel B and storage
Batch can P-2 is connected, and the second conversion zone intake channel D is connected with storage tank P-3, controls its flow velocity for entering microreactor.Second
Conversion zone exit passageway is connected with storage tank P-4, for collecting the reaction solution of outflow.
Further, microreactor intake channel A, B length is preferably 20~50mm, more preferably 30~40mm,
Its angle is preferably 30~90 °, more preferably 45~90 °, most preferably 60~90 °.The Outlet Passage Length of first conversion zone
Preferably 30~60mm, more preferably 36~48mm.Second conversion zone intake channel C, D length is preferably 20~50mm, more excellent
It is selected as 30~40mm, angle is preferably 30~90 °, more preferably 45~90 °, most preferably 60~90 °.The outlet of second conversion zone
The length in channel is preferably 36~60mm, more preferably 45~60mm.
Further, cross section characteristic scale (sectional area/perimeter of section) In of the first conversion zone and the second conversion zone
0.05~1.00mm, more preferably 0.30~0.60mm, channel cross-sectional shape is preferably circular, rectangle and Else Rule and
Irregular geometry, the more preferably regular shapes such as circle, rectangle, most preferably rectangle.
Further, microreactor of the present invention, which is characterized in that mixing point of the reaction mass in the first conversion zone
It is 5~1500ms to the mean residence time between the mixing point of the second conversion zone.
Further, the range of choice of the reaction solution of the present invention containing cerium ion includes but is not limited to the nitric acid of cerium ion
Salting liquid, Acetate Solution, chloride solution and their mixture solution.Preferably Ce (NO3)3·6H2O or Ce
(Ac)3·5H2O or CeCl3·7H2O salting liquid, more preferably Ce (NO3)3·6H2O salting liquid.
Further, the range of choice of the reaction solution of the present invention containing manganese ion includes but is not limited to the nitric acid of manganese ion
Salting liquid, Acetate Solution, chloride solution and their mixture solution.Preferably Mn (NO3)2·4H2O or Mn
(Ac)2·4H2O or MnSO4·H2The salting liquids such as O, more preferably Mn (NO3)2·4H2O salting liquid.
Further, the range of choice of precipitant solution of the present invention includes but is not limited to sodium carbonate liquor, carbonic acid
Potassium solution, sodium hydroxide solution, potassium hydroxide solution and their mixture solution, preferably Na2CO3Or the precipitating such as NaOH
Agent, more preferably Na2CO3Precipitating reagent.
Further, preparation method of the present invention, which is characterized in that the pH for reflecting oral fluid is preferably 6.5~9.5, more excellent
It is selected as 8.2~8.4.
Further, preparation method of the present invention, which is characterized in that reaction solution containing cerium ion and reaction solution containing manganese ion mole
The ratio between concentration is preferably (0.2~9): 1, more preferably (1~6): 1, most preferably (1~4): 1.
Further, preparation method of the present invention, which is characterized in that the concentration of precipitating reagent preferably contain cerium ion reaction solution with
0.8~5 times of the sum of the molar concentration of reaction solution containing manganese ion, more preferably 1.3~3 times, most preferably 1.4~1.6 times.
Further, it some or all of sediment last handling process, including following process described in this method: was aged
Journey, roasting process, activation process.
The present invention provides a kind of MnO based on the above-mentioned technical proposalx-CeO2The preparation method of mixed oxide catalyst,
The following steps are included:
A. in molar ratio (0.2~9) by cerium salt and manganese salt: 1 is dissolved in aliquots of deionized water respectively and obtains containing cerium ion
With reaction solution with manganese ions, corresponding precipitating reagent is prepared with 0.8~5 times of metal ion total concentration in two kinds of reaction solutions；
B. it will contain cerium ion reaction solution, reaction solution containing manganese ion and precipitating reagent and be preheated to 50~90 DEG C, and using flat
Stream pump is continuously injected into reaction solution containing cerium ion and precipitating reagent to A, B intake channel of the first conversion zone of microreactor respectively.Through
Enter the second conversion zone C intake channel after the stop precipitating of linkage section certain time, in the D import of the second conversion zone of microreactor
It is continuously injected into reaction solution containing manganese ion, so that the salting liquid is carried out further precipitating with the suspension to come from the first conversion zone anti-
It answers.Through the above technical solutions, adjusting reaction mass in the first conversion zone mixing point to putting down between the second conversion zone mixing point
The equal residence time is 5~1500ms, while the pH for adjusting the second conversion zone outlet suspension is preferably 6.5~9.5；
C. obtained sediment is aged under 80 DEG C of water-baths, preferably digestion time 6h；
D. obtained presoma tabletting is placed on Muffle kiln roasting, preferably roasts 4h at 500 DEG C.Then in room temperature
Lower natural cooling obtains MnOx-CeO2Mixed oxide catalyst.
Catalyst is restored before catalysis examination, oxide is ground and sieves to obtain the component of 40~60 mesh, is being contained
It is restored under hydrogen gaseous mixture, wherein hydrogen content is 10%, and nitrogen content 90%, activation temperature is 300 DEG C, and pressure is
1MPa, volume space velocity 5000h-1, activation time 2h；
Catalyst made from 100mg this method (40~60 mesh) is taken, is fixed in quartz tube reactor with silica wool
(internal diameter 6mm), 1000ppm is through mixing air (20vol%O2And 80vol%N2) balance benzene vapor be passed into pipe reaction
In device, total flow rate 100mL/min, product is detected with gas-chromatography；
The present invention does not have special requirement to material used in microreactor, using material well known to those skilled in the art
Matter, such as stainless steel.
The present invention utilizes the quick mixed characteristic of microreactor, by targetedly runner design, regulates and controls Mn2+、Ce2+'s
Precipitation reaction process, preparation structure rationally, the MnO with good catalytic activityx-CeO2Mixed oxide catalyst.It is of the invention first
First allow CeO2Small particles are formed, CeO is then re-formed2、MnO2The mixture combined closely, such CeO2In Lattice Oxygen can
Quickly pass to activated centre MnO2,, reaction precipitate obtains having good VOCs complete oxidation catalytic activity after subsequent processing
MnOx-CeO2Mixed oxide catalyst.Above-mentioned preparation MnOx-CeO2The technique of mixed oxide catalyst has operation letter
It is single, it is at low cost, the features such as process control, the catalyst of high activity can be made.
Detailed description of the invention
Attached drawing 1 prepares catalyst equipment therefor schematic diagram to be provided by the invention.
Specific implementation method
Combined with specific embodiments below to a kind of microreactor of the present invention and based on the MnO of microreactorx-CeO2
The preparation method of mixed oxide catalyst is further described in detail, but is not to be construed as to the scope of the present invention
Limitation, person skilled in art is according to the content of aforementioned present invention to some nonessential improvement of the invention made and tune
It is whole, still fall within protection scope of the present invention.
Embodiment 1
Used microreactor feature are as follows: first conversion zone intake channel A, B length is 30mm.Its angle is 60 °,
First conversion zone Outlet Passage Length is 30mm, and intake channel C, D length of II section of reaction is 30mm, and angle is 60 °, the
The Outlet Passage Length of two conversion zones is 40mm.The cross-sectional shape of the microreactor is square, and sectional area is
0.36mm2.Preheating temperature maintains 80 DEG C, is continuously passed through molar concentration in the intake channel A of the first conversion zone of microreactor and is
Ce (the NO of 0.15mol/L3)3·6H2The salting liquid of O, flow velocity 0.3m/s are continuously passed through in the intake channel B of the first conversion zone
Molar concentration is the Na of 0.48mol/L2CO3Precipitating reagent, flow velocity 0.3m/s.In the intake channel D of the second conversion zone of microreactor
Continuously it is passed through the Mn (NO that molar concentration is 0.15mol/L3)2·4H2The salting liquid of O, flow velocity 0.6m/s.Measure microreactor
The reaction suspension pH=8.3 of exit passageway, reaction mass is in the first conversion zone mixing point between the second conversion zone mixing point
Mean residence time be 90ms, with storage tank P-4 collect about 100ml reaction suspension sample, 6h is aged at 80 DEG C, be aged
After, sample is washed with deionized 3 times, and the sample after drying for 24 hours, is finally put into 480 DEG C by drying in an oven
Muffle kiln roasting 4h, obtain MnOx-CeO2Mixed oxide catalyst.Catalyst is characterized, XRD, H2-TPR、EDS
Display catalyst made from this method has to interact between higher dispersibility and stronger Mn, Ce, and BET is then shown should
The specific surface area of catalyst is 126.2m2/ g is greater than pure CeO233.4m2/ g and pure Mn3O441.6m2/g.With urging for benzene
Change oxidation to check and rate the catalytic performance of the catalyst, by catalyst in 10% hydrogen before catalysis examination, 90% nitrogen
The lower 300 DEG C of reductase 12 h of atmosphere.Catalysis examination specific implementation step are as follows: take catalyst (60-40 made from 100mg this method
Mesh), it is fixed in quartz tube reactor (internal diameter 6mm) with silica wool, 1000ppm is through mixing air (20vol%O2With
80vol%N2) balance benzene vapor be passed into tubular reactor, total flow rate 100mL/min, product is carried out with gas-chromatography
Detection, the results show that the conversion ratio of benzene is up to 96% when reaction temperature is 250 DEG C.
Embodiment 2
Used microreactor feature are as follows: first conversion zone intake channel A, B length is 30mm.Its angle is 90 °,
Reacting I section of Outlet Passage Length is 40mm, and intake channel C, D length of the second conversion zone is 40mm, and angle is 90 °, instead
The Outlet Passage Length for answering II section is 40mm.The cross-sectional shape of the microreactor is square, and sectional area is
0.36mm2.Subsequent operation includes solution concentration, flow, and the step of post-processing is same as Example 1 with condition.Reactant
Material is 110ms, obtained catalysis in the first conversion zone mixing point to the mean residence time between the second conversion zone mixing point
Agent is through XRD, H2- TPR, EDS characterization show dispersibility with higher, and BET shows that the specific surface area of the catalyst is 118.4m2/
G is greater than pure CeO233.4m2/ g and pure Mn3O441.6m2/g.It is same as Example 1 to be catalyzed characteristic manner, the results show that
When reaction temperature is 250 DEG C, the conversion ratio of benzene is up to 89%.
Embodiment 3
Used microreactor is circle, cross-sectional area 0.36mm in addition to cross section2Except other feature with reality
It is identical to apply the used microreactor of example 1.Subsequent operation includes solution concentration, flow, and the step of post-processing and condition and reality
It is identical to apply example 1.Reaction mass is to the mean residence time between the second conversion zone mixing point in the first conversion zone mixing point
90ms, obtained catalyst is through XRD, H2- TPR, EDS characterization show dispersibility with higher, and BET shows the catalyst
Specific surface area is 122.6m2/ g is greater than pure CeO233.4m2/ g and pure Mn3O441.6m2/g.It is catalyzed characteristic manner and reality
It is identical to apply example 1, the results show that the conversion ratio of benzene is up to 92% when reaction temperature is 250 DEG C.
Embodiment 4
Used microreactor is same as Example 1, only changes the concentration for being passed through solution, concrete operations are as follows: micro- anti-
The intake channel A of the first conversion zone of device is answered continuously to be passed through the Ce (NO that molar concentration is 0.20mol/L3)3·6H2The salting liquid of O,
Flow velocity is 0.3m/s, is continuously passed through the Na that molar concentration is 0.48mol/L in the intake channel B of the first conversion zone2CO3Precipitating reagent,
Flow velocity is 0.3m/s.The Mn that molar concentration is 0.10mol/L is continuously passed through in the intake channel D of the second conversion zone of microreactor
(NO3)2·4H2The salting liquid of O, flow velocity 0.6m/s.Subsequent operation parameter is same as Example 1, and reaction mass is anti-first
Answer section mixing point to the mean residence time between the second conversion zone mixing point be 90ms, obtained catalyst is through XRD, H2-
TPR, EDS characterization show dispersibility with higher, and BET shows that the specific surface area of the catalyst is 112.0m2/ g is greater than pure
CeO233.4m2/ g and pure Mn3O441.6m2/g.It is same as Example 1 to be catalyzed characteristic manner, the results show that when reaction temperature
When degree is 250 DEG C, the conversion ratio of benzene is up to 86%.
Embodiment 5
Used microreactor is same as Example 1, only changes the linear velocity for being passed through solution, concrete operations are as follows: micro-
The intake channel A of the first conversion zone of reactor is continuously passed through the Ce (NO that molar concentration is 0.20mol/L3)3·6H2The salt of O is molten
Liquid, flow velocity 0.2m/s are continuously passed through the Na that molar concentration is 0.48mol/L in I section of intake channel B of reaction2CO3Precipitating reagent,
Flow velocity is 0.2m/s.The Mn that molar concentration is 0.10mol/L is continuously passed through in the intake channel D of the second conversion zone of microreactor
(NO3)2·4H2The salting liquid of O, flow velocity 0.4m/s, subsequent operation parameter is same as Example 1, and reaction mass is anti-first
Answer section mixing point to the mean residence time between the second conversion zone mixing point be 130ms, obtained catalyst is through XRD, H2-
TPR, EDS characterization show dispersibility with higher, and BET shows that the specific surface area of the catalyst is 119.1m2/ g is greater than pure
CeO233.4m2/ g and pure Mn3O441.6m2/g.It is same as Example 1 to be catalyzed characteristic manner, the results show that when reaction temperature
When degree is 250 DEG C, the conversion ratio of benzene is up to 90%.
Embodiment 6
Used microreactor is same as Example 1, only changes the type for being passed through salting liquid and precipitating reagent, concrete operations
Are as follows: the Ce (Ac) that molar concentration is 0.20mol/L is continuously passed through in the intake channel A that microreactor reacts I section3·5H2The salt of O
It is heavy to be continuously passed through the NaOH that molar concentration is 0.48mol/L in the intake channel B of the first conversion zone by solution, flow velocity 0.3m/s
Shallow lake agent, flow velocity 0.3m/s.Continuously being passed through molar concentration in the intake channel D of the second conversion zone of microreactor is 0.10mol/L
Mn (Ac)2·4H2The salting liquid of O, flow velocity 0.6m/s, reaction mass are mixed in the first conversion zone mixing point to the second conversion zone
Mean residence time between chalaza is 90ms, and obtained catalyst is through XRD, H2- TPR, EDS characterization display dispersibility are lower
In former embodiments, BET shows that the specific surface area of the catalyst is 98.5m2/ g is greater than pure CeO233.4m2/ g and pure
Mn3O441.6m2/g.It is same as Example 1 to be catalyzed characteristic manner, the results show that benzene turns when reaction temperature is 250 DEG C
Rate is 82%.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
When being considered as protection scope of the present invention.
Claims (10)
1. one kind passes through segmentation reaction preparation MnOx-CeO2The method of mixed oxide catalyst, which is characterized in that contain cerium ion
Two closely coupled conversion zones of microreactor front and back are continuously flowed into respectively with reaction solution with manganese ions, successively and containing precipitating reagent
Solution reaction, sediment obtains MnO through subsequent processesx-CeO2Mixed oxide catalyst.
2. according to the method described in claim 1, it is characterized in that the microreactor includes the first conversion zone and the second reaction
Section:
First conversion zone includes two intake channels A, B and one outlet channel, and two intake channels A, B are respectively used to be added
Reaction solution and precipitant solution containing cerium ion；
Second conversion zone includes two intake channels C, D and one outlet channel, and intake channel C and the outlet of the first conversion zone are logical
Road is connected directly, and intake channel D is for being added reaction solution with manganese ions.
3. according to the method described in claim 2, it is characterized in that, reaction mass is anti-to second in the mixing point of the first conversion zone
Answering the mean residence time between the mixing point of section is 5~1500ms.
4. according to the method described in claim 2, it is characterized in that, the first conversion zone and the second conversion zone cross section characteristic scale
For 0.1~2mm, form includes round, rectangle or irregular geometry.
5. the method according to claim 1, wherein the range of choice of the reaction solution containing cerium ion includes cerium ion
Nitrate solution, Acetate Solution, chloride solution and their mixture solution.
6. the method according to claim 1, wherein the range of choice of the reaction solution containing manganese ion includes manganese ion
Nitrate solution, Acetate Solution, chloride solution and their mixture solution.
7. the method according to claim 1, wherein the range of choice of the precipitant solution includes sodium carbonate
Solution, solution of potassium carbonate, sodium hydroxide solution, potassium hydroxide solution and their mixture solution.
8. the method according to claim 1, wherein reflecting the pH of oral fluid between 6.5~9.5.
9. the method according to claim 1, wherein reaction solution containing cerium ion and reaction solution containing manganese ion mole are dense
The ratio between degree is (0.2~9): 1.
10. the method according to claim 1, wherein sediment last handling process, the part including following process
Or all: ageing process, washing process, roasting process, activation process.
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