CN109926048A - A kind of one pack system double activated position Cu2O-CuO nanometers of mixed phase structure copper oxide catalysts, preparation method and application - Google Patents
A kind of one pack system double activated position Cu2O-CuO nanometers of mixed phase structure copper oxide catalysts, preparation method and application Download PDFInfo
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Abstract
The invention belongs to catalysis material technical fields, provide a kind of one pack system double activated position Cu2O-CuO nanometers of mixed phase structure copper oxide catalysts, preparation method and application.Catalyst can be used for ammine selective catalytic oxidation reaction.By adjusting catalyst pretreatment condition, realizes the control to cuprous particle surface restructuring procedure, form purpose to reach regulation copper oxide surface outer wall.It finally obtains with Cu2O nano particle is core, the Cu of outside package CuO shell2O-CuO nanometers of mixed phase structure composite copper oxide materials.The catalyst has outstanding ammoxidation activity and N2Selectivity and good reaction stability.Preparation method is simple and efficient reliably, and raw material is easy to get, and is easy to magnanimity preparation.
Description
Technical field
The invention belongs to catalysis material technical fields, and in particular to a kind of one pack system double activated position Cu2O-CuO nanometers of mixed phases
Structure copper oxide catalyst, preparation method and application.
Background technique
In recent years, the features such as heterogeneous catalysis technology is with quick, efficiently, energy saving, simple process, in processing polluted gas discharge
Application in widely paid close attention to.Wherein, ammine selective catalytic oxidation method (NH3- SCO) as effectively removing extra ammonia
Important process link becomes important research object.
The considerations of in practical application, is directed to NH at present3The research of catalyst system is mainly with oxo transition metal in-SCO
Based on compound catalyst, such as Cu, Mn, Fe, Co etc..Wherein Cu oxide is in ammonia conversion ratio and N2Performance in production quantity is especially prominent
Out, it is considered having good application prospect.Chmielarz et al. synthesizes Cu-ZSM-5 supported catalyst using Zeolite modifying technology
Agent, and it is applied to NH3- SCO reaction, as a result, it has been found that the redox characteristic of CuO species and the acidic site base of offer directly affect
Ammoxidation activity can convert completely ammonia at 380 DEG C, while the N generated2Yield reaches 90% or more, and the catalyst is in height
Stable conversion ratio (Microp.&Mesop.Mater., 2017,246:193-206) can be kept under the conditions of temperature.Qu seminar is
The ammoxidation performance for promoting CuO base catalyst, is doped into Ce, and Zr oxide component passes through different preparation methods and synthesizes a system
Cu-Ce-Zr ternary oxide composite catalyst is arranged, as a result, it has been found that three-way catalyst can effectively promote the catalytic activity of CuO,
230 DEG C can by ammonia complete oxidation, and guarantee 90% N2Selectivity (Catal.Sci.&Technol.2016,6:4491-
4502).But the research of current CuO catalyst concentrates on loaded catalyst or multiplex catalyst, and complicated system can produce
Raw cumbersome preparation step and the waste for causing resource, and the conversion temperature of catalyst still needs to further decrease, to match reality
Application demand.
In Cu oxide research, cuprous oxide (Cu2O) material is easy into due to the unstability in oxidizing atmosphere
For ignored object.However, with Cu2The extensive research of O material, more and more researchs, which are conceived to, passes through exploitation
Its unique physico-chemical property having, and applied in every field.Up to the present, cuprous oxide material is extensive
Ground is applied to electrochemical sensor, electrode material of lithium battery, photocatalytic degradation, in modified catalyst and organic synthesis.
Cu2The pattern effect and Surface Layer Atomic Structure of O material are the key that influence catalytic effect, in oxidation reaction process, Cu2O catalysis
Agent surface can occur surface atom and retake row, to influence catalytic activity.For Cu2O nano material and its restructuring procedure are ground
It is extremely important for studying carefully.However there is presently no Cu2O is in NH3In-SCO application and subsequent control restructuring procedure is adjusted
The research of catalyst activity.
Summary of the invention
The technology of the present invention solves the problems, such as: overcoming existing catalyst system complicated, is unfavorable for synthesizing, and reaction temperature is higher not
Foot place provides a kind of one pack system double activated position Cu for ammonia catalytic reaction2O-CuO nanometers of mixed phase structure Cu oxides
Catalyst realizes the control to cuprous particle surface restructuring procedure, by adjusting catalyst pretreatment condition to reach regulation table
Face copper oxide outer wall forms purpose.It finally obtains with Cu2O nano particle is core, the Cu of outside package CuO shell2O-CuO nanometers
Mixed phase structural composite material.The catalyst has outstanding ammoxidation activity and N2Selectivity and good reaction stability.
Technical solution of the present invention:
A kind of one pack system double activated position Cu2O-CuO nanometers of mixed phase structure copper oxide catalysts, with Cu2O nano particle is
Core, the Cu of outside package CuO shell2O-CuO nanometers of mixed phase structural composite materials.
One pack system double activated position Cu2The partial size of O-CuO nanometers of mixed phase structure copper oxide catalysts is 100-
400nm。
Described CuO layers with a thickness of 10nm.
A kind of one pack system double activated position Cu2The preparation method of O-CuO nanometers of mixed phase structure copper oxide catalysts, step is such as
Under:
(1) dissolution of copper presoma is configured to the solution a that concentration is 0.01mol/L in deionized water, then to described
Citric acid is added in solution a, 0.5-1h is stirred at room temperature, obtains solution b；Wherein, the mass ratio of copper presoma and citric acid
For 1:(15~20)；
(2) pH that alkaline solution is added to solution in Xiang Suoshu solution b is 11, is added after 20-30min is stirred at room temperature
Ascorbic acid solution obtains solution c, and by solution c after 40 DEG C of stirring 3h, centrifugation, washing, vacuum drying obtain Cu2O；It is described
The concentration of ascorbic acid solution is 0.6mol/L；The volume of the ascorbic acid solution and the volume ratio of solution b are 1:10；
(3) Cu for preparing step (2)2O is in NH3、O2With calcining pretreatment is carried out in the mixed gas of He；Mixed gas
Total flow is 100ml/min；NH3Concentration is 0-5000ppm, O2Concentration is 10vol%, pretreatment time 1h；Treatment temperature is
225-275℃。
The copper presoma is copper nitrate, copper sulphate or copper chloride.
Step (2) the neutral and alkali solution is sodium hydroxide or potassium hydroxide, concentration 2.0mol/L.
Pretreatment mixed gas concentration is 1000ppm NH3；Pretreatment temperature is 250 DEG C.
One pack system double activated position Cu2What O-CuO nanometers of mixed phase structure copper oxide catalysts were reacted as ammonia catalytic
Catalyst, air speed 50000h-1, reacting gas concentration 1000ppm NH3, 10vol%O2, He balance.
Beneficial effects of the present invention: the present invention has as follows compared with existing CuO is system supported or compound system catalyst
Advantage: since the catalyst is that have single Cu oxide component, double activated position Cu2O-CuO nanometers of mixed structures, catalyst are available
It is reacted in ammine selective catalytic oxidation.By adjusting catalyst pretreatment condition, realize to cuprous particle surface restructuring procedure
Control, to reach the regulation purpose of copper oxide surface outer wall formation.It finally obtains with Cu2O nano particle is core, outside package
The Cu of CuO shell2O-CuO nanometers of mixed phase structural composite materials.This catalyst shows good ammoxidation activity and high N2Choosing
Selecting property, stability.The catalyst can convert completely ammonia at 210 DEG C, and have the N greater than 90%2Selectivity.
Preparation process is simple, easy to operate, can be mass-produced.
Catalyst system is single, is conducive to save the cost.
By the way that citric acid is added, the settling velocity of Kocide SD is controlled, to control Cu2The size of O particle.
By controlling pretreatment condition, the formation of outer layer CuO can control；Cu is formed under given conditions2O-CuO mixed phase
Structure nano catalyst, catalytic performance are excellent.
Detailed description of the invention
Fig. 1 is the Cu of 1,2 gained sample of embodiment2Catalyst prepared by O-CuO mixed phase structure catalyst and comparative example 1,2
(a) NH3Catalytic activity and (b) N2Selective figure.
Fig. 2 is the resulting Cu of embodiment 12The stability of O-CuO-A sample.
Fig. 3 is the Cu of 1,2 gained sample of embodiment2Catalyst prepared by O-CuO mixed phase structure catalyst and comparative example 1,2
XRD diffraction pattern.
Fig. 4 is the resulting Cu of embodiment 12The scanning of catalyst prepared by O-CuO mixed phase structure catalyst and comparative example 1,2
Electronic Speculum characterizes (SEM) comparison diagram；Wherein (a) Cu2O, (b) Cu2O-CuO-A, (c) CuO.
Specific embodiment
Below by embodiment, the present invention will be further described in detail, but scope of the presently claimed invention is not
It is limited to these embodiments.Meanwhile embodiment has been merely given as reaching the partial condition of this purpose, is not meant to expire
This purpose just may be implemented in these conditions of foot.
Embodiment 1
Liquid phase reduction prepares cubic structure Cu2O particle:
(1) copper nitrate is dissolved in 900ml deionized water first and is configured to solution, concentration 0.01mol/L simultaneously will
The lemon granulates of 0.09g are added in solution, and 0.5h is stirred at room temperature.Then by the sodium hydroxide solution of 2.0mol/L by
Step is added dropwise in mixed solution, until pH=11.After being stirred for 0.5h at room temperature, the ascorbic acid solution of 0.6mol/L is added
Enter into solution, 40 DEG C will be mixed and heated at this time and remain constant, continues to stir 3h.The Cu obtained by centrifugation2O sample,
It is cleaned with deionized water and alcohol.Last catalyst dry 12h in vacuum environment.The scanning electron microscope of sample obtained is such as
Fig. 1, the results showed that catalyst shows typical Cu2O cubic crystal structure and surface is smooth, grain edges are having a size of 100
To 400nm.
Cu2The preparation of O-CuO mixed phase nanocatalyst:
Cu prepared by step (1)2O is in NH3, O2With calcining pretreatment is carried out in the mixed gas of He；Mixed gas always flows
Amount is 100ml/min；NH3Concentration is 1000ppm, O2Concentration is 10vol%, pretreatment time 1h；Pretreatment temperature is 250
DEG C, obtain catalyst Cu2O-CuO-A。
Embodiment 2
Pretreatment temperature is changed to 225 DEG C and 275 DEG C, other steps obtain catalyst Cu with embodiment 12O-CuO-B and
Cu2O-CuO-C, catalyst are still Cu2O-CuO mixed structure.
Comparative example 1
Calcining pretreatment step in example 1 is cancelled, other steps obtain catalyst Cu with comparative example 12O。
Comparative example 2
Calcining pretreatment temperature in example 1 is changed to 300 DEG C, other steps obtain catalyst CuO with comparative example 1.
Embodiment 3
Catalyst prepared by embodiment 1,2 and comparative example 1,2 is to NH3Catalytic oxidation performance test is in fixed bed reaction
Continuous operation carries out on device, and He does Balance Air, using NH3Gaseous material after analyzer and gas chromatograph on-line analysis reaction
NH3Molecule and product N2Molecule.Reaction condition specifically: 1000ppm NH3, 10vol%O2, for He as Balance Air, reaction is empty
Speed is 50000h-1, catalyst quality 0.15g.Ammonia conversion ratio is as shown in Figure 1a, Cu2The catalytic activity of O-CuO-A is best,
Reach 100%NH at 210 DEG C3Conversion ratio, while such as Fig. 1 b, N2Selectivity reaches 90% or more in reaction temperature section.
Embodiment 4
Cu prepared by embodiment 12O-CuO mixed phase nanocatalyst, investigates the stability of the catalyst, is keeping implementing
1800min stability experiment is carried out under 3 reaction condition of example, then tests Cu in 210 DEG C of continuous operations2O-CuO-A catalyst
Stability, stability is as shown in Fig. 2, ammonia conversion ratio maintains essentially in 100%.
Embodiment 5
It carries out XRD test to catalyst prepared by embodiment 1,2 and comparative example 1,2 to characterize, crystal form evolution process, such as
Shown in Fig. 3.Cu2O catalyst exists with the cuprous crystal form of typical cuprite, and the cuprous oxide structure initially synthesized possesses good crystalline substance
Type structure and stronger lattice energy.Work as Cu2For O in 225-275 DEG C of progress calcination processing, main crystalline structure is from Cu2O gradually mistake
It crosses to CuO.Catalyst Cu2There is Cu in O-CuO- (A~C)2O-CuO mixed phase structure.When calcination temperature is increased to 300 DEG C, belong to
Cu2The diffraction maximum of O crystal phase almost disappears, and only exists CuO phase.
Embodiment 6
Electronic Speculum characterization carried out to nanocatalyst prepared by embodiment 1 and comparative example 1,2, Evolution of Morphology, such as
Shown in Fig. 4 a.Cu2O shows typical cubic crystal structure and surface is smooth, and grain edges arrive 400nm having a size of 100.?
After 250 DEG C of pretreatments, such as Fig. 4 b, catalyst Cu2The size of O-CuO-A particle is almost unchanged, and still maintains cube
Body structure.But particle starts to become coarse, surface forms the circular granular for being less than 50nm.When calcination temperature is promoted to 300 DEG C
When, such as Fig. 4 c, it can be seen that CuO shell constantly thickens, but still has cube pattern.
It should be noted that those skilled in the art are that this hair may be implemented completely according to the various embodiments described above of the present invention
Bright independent claims and the full scope of appurtenance, realize process and the same the various embodiments described above of method；And the present invention is not
It elaborates and partly belongs to techniques well known.
Above embodiments are provided just for the sake of the description purpose of the present invention, and are not intended to limit the scope of the invention.This
The range of invention is defined by the following claims.The various equivalent replacements for not departing from Spirit Essence and principle of the invention and making
And modification, it should all cover within the scope of the present invention.
Claims (7)
1. a kind of one pack system double activated position Cu2O-CuO nanometers of mixed phase structure copper oxide catalysts, which is characterized in that the list
Component double activated position Cu2O-CuO nanometers of mixed phase structure copper oxide catalysts are with Cu2O nano particle is core, and outside is wrapped up outside CuO
The Cu of shell2O-CuO nanometers of mixed phase structural composite materials；One pack system double activated position Cu2O-CuO nanometers of mixed phase structure copper oxidations
The partial size of object catalyst is 100-400nm；Described CuO layers with a thickness of 10nm.
2. a kind of one pack system double activated position Cu2The preparation method of O-CuO nanometers of mixed phase structure copper oxide catalysts, feature exist
In steps are as follows:
(1) dissolution of copper presoma is configured to the solution a that concentration is 0.01mol/L in deionized water, then to the solution a
Middle addition citric acid, is stirred at room temperature 0.5-1h, obtains solution b；Wherein, the mass ratio of copper presoma and citric acid is 1:
(15~20)；
(2) pH that alkaline solution is added to solution in Xiang Suoshu solution b is 11, be stirred at room temperature after 20-30min be added it is anti-bad
Hematic acid solution obtains solution c, and by solution c after 40 DEG C of stirring 3h, centrifugation, washing, vacuum drying obtain Cu2O；It is described anti-bad
The concentration of hematic acid solution is 0.6mol/L；The volume of the ascorbic acid solution and the volume ratio of solution b are 1:10；
(3) Cu for preparing step (2)2O is in NH3、O2With calcining pretreatment is carried out in the mixed gas of He；Mixed gas always flows
Amount is 100ml/min；NH3Concentration is 0-5000ppm, O2Concentration is 10vol%, pretreatment time 1h；Treatment temperature is 225-
275℃。
3. preparation method according to claim 2, which is characterized in that the copper presoma is copper nitrate, copper sulphate or chlorine
Change copper.
4. preparation method according to claim 2 or 3, which is characterized in that step (2) the neutral and alkali solution is hydroxide
Sodium or potassium hydroxide, concentration 2.0mol/L.
5. preparation method according to claim 2 or 3, which is characterized in that pretreatment mixed gas concentration is 1000ppm
NH3；Pretreatment temperature is 250 DEG C.
6. the preparation method according to claim 4, which is characterized in that pretreatment mixed gas concentration is 1000ppm NH3；
Pretreatment temperature is 250 DEG C.
7. one pack system double activated described in claim 1 position Cu2O-CuO nanometers of mixed phase structure copper oxide catalysts are urged as ammonia
The catalyst of oxidation, air speed 50000h-1, reacting gas concentration 1000ppm NH3, 10vol%O2, He balance.
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