CN109772346A - A kind of preparation method of composite material catalyst and its application in denitrification at low temperature - Google Patents
A kind of preparation method of composite material catalyst and its application in denitrification at low temperature Download PDFInfo
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Abstract
本发明提供了一种如式(Ⅰ)所示的以类水滑石为前驱体的复合材料催化剂，本申请还提供了所述复合材料催化剂的制备方法，包括以下步骤：A)将铈源、铜源和铝源混合后配制成水溶液；B)将所述水溶液与沉淀剂混合，得到初始沉淀液；C)将所述初始沉淀液在惰性气氛下与还原剂混合，反应，得到类水滑石前驱体；D)将类水滑石前驱体焙烧，得到复合材料催化剂。本发明提供的复合材料催化剂具有比表面大、低温活性高、不易被粉尘和SO2中毒等特点；借助该复合材料催化剂，在低温下氮氧化物的脱除率可达到98％以上；同时，该复合材料催化剂的结构稳定性高，对周围环境和生产设备无害，具有较高的应用前景。
The present invention provides a composite material catalyst with a hydrotalcite-like precursor as shown in formula (I), and the present application also provides a preparation method of the composite material catalyst, comprising the following steps: A) adding a cerium source, The copper source and the aluminum source are mixed and prepared into an aqueous solution; B) mixing the aqueous solution with a precipitant to obtain an initial precipitation solution; C) mixing the initial precipitation solution with a reducing agent under an inert atmosphere, and reacting to obtain a hydrotalcite-like precursor; D) calcining the hydrotalcite-like precursor to obtain a composite catalyst. The composite material catalyst provided by the invention has the characteristics of large specific surface, high activity at low temperature, not easy to be poisoned by dust and SO2, etc. With the aid of the composite material catalyst, the removal rate of nitrogen oxides at low temperature can reach more than 98%; at the same time, The composite material catalyst has high structural stability, is harmless to the surrounding environment and production equipment, and has high application prospects.
Description
Technical field
The present invention relates to catalyst applied technical fields more particularly to a kind of using houghite as the composite material of presoma
Catalyst, preparation method and its application.
Background technique
Civil coal is the civil coal for dispersing to use for resident's daily cooking and warming, mainly include coal briquette for civillan use and
Household coal two major classes.World Health Organization's statistical data show global annual about 3,000,000,000 populations directly utilize open fire or
The fuel such as person's stove biomass burning or coal warm oneself and cook.Every year can about 4,300,000 people die of above-mentioned fuel combustion
Caused room air pollution (Liu Haibiao, Kong Shaofei, Wang Wei etc., heavy metal in the civilian Discharged form Coal Combustion fine particle of China
Inventory, environmental science, 2016,37 (8): 2823-2834).Specific to China, about 14% town dweller and 79%
Rural resident uses always these fuel.In recent years, due to the increasing of environmentally friendly dynamics, China's civil coal dosage occurs certain
Decline, but from 2008, maintain essentially in 100,000,000 tons or so.Civil coal smoke pollution is mainly the pollution of area source dispersed, in crowd
More pollution species, nitrogen oxides (NOx) it is one of main atmosphere pollution.Studies have shown that anthracite per ton, bituminous coal, bee
Nest coal can about discharge the NO of 1.1kg, 1.6kg and 0.8kg respectivelyx, discharge can lead to acid rain, photochemical fog, greenhouse for a long time
Effect and destroy ozone layer etc. endanger (Yan Binglei, Tang Xiyuan, Lv Jialin etc., China's civil coal status and pollutant emission analysis,
Chinese coal processing and comprehensive utilization, 2017,1:1-3).
How in civil flue gas NO is effectively reducedxDischarge have become it is urgently to be resolved in China's strategy of sustainable development
The great people's livelihood and environmental problem, and the developing direction of global pollution that caused by coal burning Treatment process.Studies have shown that these nitrogen oxides
Main component is NO.Currently, the main mature technology that coal-fired flue-gas removes NO is " selective catalytic reduction ", is abbreviated as SCR.
However, the technology need to could obtain good removal effect under the action of the noble metal catalysts such as platinum group, titanium system and vanadium system.So
And above-mentioned catalyst investment is greatly, catalyst life is low；Also, the technology need to also be by NH3As reducing agent, due to NH3Have
The disadvantages of toxic, inflammable and explosive, need to inevitably establish a set of stringent transport, storage in the application process of SCR technology
It deposits, use and emergency processing and safe precaution measure；Meanwhile excessive NH3It penetrates and also will cause secondary pollution.Thus, although
SCR technology purification efficiency is high, but it is above-mentioned it is many be difficult to the shortcomings that overcoming, cause it to may not apply to civil coal denitrating flue gas
In the process.Document report, can by the NO in flue gas under the action of catalyst partial oxidation be NO2, then again by wet absorption
Agent (such as lime and NaOH) absorbs the latter, that is, oxidation-liquid absorption technology reaches removing NOxPurpose.However,
Catalyst need to just have preferable catalytic activity at 175 DEG C or more.The flue-gas temperature lower (one discharged in view of Domestic coal stove
As at 100 DEG C or so), and adsorbent adsorption capacity is limited, need to often replace, and limits oxidation-absorption skill to a certain extent
Art its civil coal denitrating flue gas application.
On the other hand, anthracite per ton, bituminous coal and honeycomb briquette burn in domestic stove can generate 69.9,140.1 respectively
With the CO of 72.8kg, far more than NOxDischarge (Yan Binglei, Tang Xiyuan, Lv Jialin etc., China's civil coal status and pollutant
Emission analysis, Chinese coal processing and comprehensive utilization, 2017,1:1-3).Thus, in the case where misoperation, easily cause
Indoor CO concentration is high, so as to cause " gas poisoning " of resident.Meanwhile CO is also a kind of typical reducing agent, is made in catalyst
It, can be with NO underXMain component NO occur as equation 1 chemical reaction:
CO+NO=N2+CO2(1)；
The implementation of the technology is converting NO to harmless N2While, the toxic CO in part is also converted into CO2, reduce
The harmfulness of CO, the prospect with large-scale promotion application.Although noble metals can be catalyzed CO's and NO including Rh, Pt and Pd etc.
Reaction, however it is expensive, is unsuitable for the large-scale application of civil denitrating flue gas.In many cheap metal denitration catalysts
In agent, Cu system oxide is had been a hot spot of research.Takashi Yamamoto et al. is prepared for Cu/Al using infusion process2O3、
Cu/ZrO2、Cu/ZSM-5、Cu/CeOx/Al2O3、Cu/ZrO2, Cu/ZnO and Cu/SiO2Equal catalyst；Wherein, Cu/Al2O3Catalysis
Activity and N2Selective highest, when reaction temperature is 500 DEG C, the conversion ratio of NO is 31%.However, at 100 DEG C, it is this
For catalyst without active, the conversion ratio of NO and CO are essentially 0 (T.Yamamoto, T.Tanaka, R.Kuma, et al.NO
reduction with CO in the presence of O2over Al2O3-supported and Cu-based
catalysts[J].Physical Chemistry Chemical Physics,2002,4:2449-2458).The benefits such as Liang Xiaojia
CuO/Al is prepared for sol-gel method2O3, when temperature is more than 400 DEG C, catalyst can just show higher denitrification ability
(Liang Xiaojia, Qi Wenyi, Zhu Jianhua, the CuO/Al for CO reduction NO2O3The preparation of catalyst and performance evaluation [J], modernization
Work, 2016,36 (2): 83-86)；B.Wen and M.He is prepared for CuO-Ce using coprecipitation2O3-MgO-Al2O3Combined oxidation
Object finds it in SO2In the presence of, can convert NO with high selectivity is N2；But reaction temperature will be up to 720 DEG C, far
Much higher than temperature (Bin Wen, Mingyuan He, the Study of the Cu-Ce synergism for of civilian burner flue gas
NO reduction with CO in the presence of O2,H2O and SO2in FCC operation,Applied
Catalysis B:Environmental,2002,37:75-82).Discoveries in 2013, Ch.Ge, L.Liu, X.Yao etc. will be by soaking
CuNi/ γ-the Al that stain method obtains2O31h is activated at 350 DEG C in (such as CO/He atmosphere) in a reducing atmosphere, could be obtained higher
Catalytic activity (Chengyan Ge, Lianjun Liu, Xiaojiang Yao, Changlin Tang, Fei Gao, Lin
Dong,Treatment induced remarkable enhancement of low-temperature activity and
selectivity of copper-based catalysts for NO reduction[J],Catalysis Science&
Technology,2013,3:1547-1557)；This undoubtedly will cause above-mentioned catalyst actual use process very big inconvenience,
The catalyst is limited in the popularization of civil flue-gas denitrification；Even across above-mentioned pretreatment, the best catalysis of the catalyst
Temperature is still at 300 DEG C or more；When temperature is 200 DEG C, the conversion ratio of NO is less than 90%, it is clear that is not met by low temperature item
The requirement of NO is removed under part.More bad, the active sites of these catalyst are at high temperature easily by SO2Institute's " poisoning " is lost
Speed living is fast.
In conclusion since civilian burner flue-gas temperature is generally lower than 150 DEG C, it is at such lower temperatures, general to be catalyzed
Agent is difficult to realize the efficient catalytic conversion of CO and NO；Also, there is also a certain amount of SO in coal-fired flue-gas2And dust, it is easy to cover
Catalyst " poisoning " is caused in lid catalyst activity position.Therefore, it is badly in need of being directed to civilian burner, develops and design and be able to achieve low temperature
Efficiently, stablize the effective catalyst for removing its flue gas nitrogen oxide.
Summary of the invention
Present invention solves the technical problem that be to provide it is a kind of using houghite as the composite catalyst of presoma and
The composite catalyst of preparation method, the application preparation can realize efficient catalytic civil at 60~120 DEG C of low temperature
CO and NO conversion in flue gas.
In view of this, this application provides one kind composite catalyst as shown in formula (I),
CuxCeyAlzOm(Ⅰ)；
Wherein, x=0.1~0.8, y=0.01~0.3, z=0.01~0.5；
M is to meet atomicity required for other three kinds of element valences.
Preferably, x=0.2~0.7, y=0.03~0.1, z=0.02~0.4.
Present invention also provides the preparation methods of the composite catalyst, comprising the following steps:
A) prepare cerium source, copper source and aluminium according to the atomicity proportion of each element in composite catalyst shown in formula (I)
Source is configured to aqueous solution after mixing cerium source, copper source and silicon source；
B) by the aqueous solution and precipitant mix, initial precipitation liquid is obtained；The precipitating reagent is sodium acetate and sodium carbonate；
C the initial precipitation liquid is mixed with reducing agent under an inert atmosphere), reacts, obtains houghite presoma；
D) houghite presoma is roasted, obtains composite catalyst.
Preferably, the reducing agent is selected from one of formaldehyde, acetaldehyde, vitamin C, glucose and hydrazine hydrate or a variety of.
Preferably, the cerium source is cerous nitrate, and copper source is copper nitrate, and source of aluminium is aluminum nitrate；Copper source with
The ratio of the molal quantity of the total molal quantity in the cerium source and the reducing agent is 1:(2~5).
6, preparation method according to claim 3, which is characterized in that the cerium source, copper source and silicon source total moles
Several ratios with the molal quantity of the sodium acetate are 1:(1.5~3), the total mole number in the cerium source, copper source and silicon source with it is described
The ratio of the molal quantity of sodium carbonate is 2:1.
Preferably, step C) specifically:
Using inert gas by the initial precipitation liquid air blow out, add reducing agent, in 60 DEG C of agings 2~
4h, decompression filter, obtained filter cake are dried in vacuo 10~12h at 80 DEG C, obtains houghite presoma.
Preferably, the temperature of the calcining is 400~800 DEG C, and the time is 4~8h.
Present invention also provides a kind of methods for removing civilian burning flue-gas nitrogen oxides, comprising:
Nitric oxide and carbon monoxide are answered prepared by the composite catalyst or the preparation method
It is reacted under the action of condensation material catalyst, obtains nitrogen and carbon dioxide.
Preferably, the temperature of the reaction is 60~120 DEG C, and the pressure of the reaction is 0.5~3MPa, air speed 1000
~8000h-1, carbon monoxide and nitric oxide production initial molar ratio are 1~5:1.
This application provides a kind of using houghite as the composite catalyst of presoma, is a kind of high activity reduction
The addition of the copper-based catalysts of state, metal Ce provides second of variable valency metal in addition to Cu, introduces in new activity
The heart, meanwhile, the meso-hole structure of composite material makes it have compared with Large ratio surface, and then is conducive to the high degree of dispersion of active component, because
This, composite catalyst provided by the present application can realize activation and the catalyzed conversion to CO and NO under cryogenic, reach
The purpose of the civilian burner flue gas of efficient removal.
Present invention also provides the preparation methods of above-mentioned composite catalyst, in houghite precursor preparation process
In, liquid phase in-situ reducing is carried out to the fresh active metal species that appraise at the current rate by reducing agent, high activity reducing condition can be obtained
Copper-based catalysts；Meanwhile in houghite presoma calcination process, decomposing the gases such as carbon dioxide and the vapor of generation has
Conducive to the formation of composite material meso-hole structure, large specific surface area is made it have, and then is conducive to the high degree of dispersion of active component,
It is final to realize the activation to CO and NO and catalyzed conversion under cryogenic, achieve the purpose that the civilian burner flue gas of efficient removal.
Detailed description of the invention
Fig. 1 is the SEM photograph of houghite presoma prepared by the embodiment of the present invention 1；
Fig. 2 be the embodiment of the present invention 1 prepare houghite presoma after calcining composite catalyst obtained
SEM photograph.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are only further explanation the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
For in the prior art, shortage is not easy to be sealed dirt and SO under the conditions of low temperature (60~120 DEG C)2It is polluted, it can
Realize the solid copper-based catalysts of CO and NO conversion in efficient catalytic civil flue gas, this application provides one kind with class neatly
Stone is the composite catalyst of presoma, shown in the composite catalyst such as formula (I),
CuxCeyAlzOm(Ⅰ)；
Wherein, x=0.1~0.8, y=0.01~0.3, z=0.01~0.5；
M is to meet oxygen atomicity required for other three kinds of element valences.
Above-mentioned composite catalyst is using stratiform hydrotalcite as the composite oxides of presoma, with good, rule
Whole thin plate crystals pattern, without agglomeration, reducing metal active sites are exposed, and are conducive to improve it as catalyst
Low-temperature catalyzed ability.
In a particular embodiment, the x=0.2~0.7, y=0.03~0.1, z=0.02 in the composite catalyst
~0.4.
Present invention also provides the preparation methods of above-mentioned composite catalyst, specifically includes the following steps:
A) prepare cerium source, copper source and aluminium according to the atomicity proportion of each element in composite catalyst shown in formula (I)
Source is configured to aqueous solution after mixing cerium source, copper source and silicon source；
B) by the aqueous solution and precipitant mix, initial precipitation liquid is obtained；The precipitating reagent is sodium acetate and sodium carbonate；
C the initial precipitation liquid is mixed with reducing agent under an inert atmosphere), reacts, obtains houghite presoma；
D) houghite presoma is roasted, obtains composite catalyst.
According to the present invention, during preparing composite catalyst, the application prepare first raw material cerium source, copper source and
Silicon source is substance well known to those skilled in the art for above-mentioned cerium source, copper source and silicon source, can be above-mentioned metallic element
Chloride, sulfate or nitrate；Exemplary, cerium source described herein is cerous nitrate, and copper source is copper nitrate, the aluminium
Source is aluminum nitrate.The adding proportion in above-mentioned cerium source, copper source and silicon source is according to each element in composite catalyst described in formula (I)
Atomicity proportion be added.Mixed aqueous solution, the concentration of the aqueous solution are hybridly prepared into water after above-mentioned raw materials mixing
For 0.2~2mol/L.
The application obtains initial precipitation liquid then by the aqueous solution and precipitant mix, in this application, the precipitating
Agent is selected from sodium acetate and sodium carbonate, and above two precipitating reagent is strong base-weak acid salt, after above-mentioned aqueous solution and precipitant mix,
Metal salt will form the precipitating of the hydroxide with houghite layer structure.In this application, the cerium source, copper source and silicon source
Total mole number and the sodium acetate molal quantity ratio be 1:(1.5~3), the cerium source, copper source and silicon source total moles
Several ratios with the molal quantity of the sodium carbonate are 2:1；The proportionate relationship of above-mentioned raw materials is to guarantee to be formed houghite layer
The hydroxide of shape structure precipitates.
Then the application mixes above-mentioned initial precipitation agent with reducing agent under an inert atmosphere, react to get class neatly is arrived
Stone presoma；In the process, the reducing agent is the reducing agent of reducing metal element, is gone back to be well known to those skilled in the art
Former agent, it is exemplary, the reducing agent be selected from one of formaldehyde, acetaldehyde, sodium borohydride, vitamin C, glucose and hydrazine hydrate or
It is a variety of.The ratio of the molal quantity of copper source and the total molal quantity in the cerium source and the reducing agent is 1:2~1:5.It is described lazy
Property atmosphere be high pure nitrogen or argon gas.After reducing agent is added, Cu2+、Ce4+The reduction of isoreactivity metal, so that part Cu2+Conversion
For Cu+Or Cu0, Ce4+It is converted into Ce3+, to make to restore species increase.Studies have shown that more Cu+Generate the suction for being conducive to CO
It is attached；CO is in Cu+Absorption lead to desorption of the NO on oxygen vacancies with O Free Radical, generate CO2With N free radical；Meanwhile
N free radical can generate N with NO or CO reaction2Perhaps NCO or two N free radical combines generation N to O2.In addition, in this process
In, Cu+Cu can be reduced into0, N2O can be reduced into N2, moreover, Cu0It is considered as N2O is reduced into N2Active sites.Thus, Cu+/Cu0The circulation of reduction pair is to realize N2O is reduced into N2Key.Under the action of this programme reducing agent, N2O can become N2With
O, O can be combined with neighbouring CO and be generated N2, complete circulation.It is not difficult to find that having enough Lacking oxygens (cave) and Cu+Ion has
NO is restored conducive to CO.Thus, the in situ of the application reducing agent is added, it can be achieved that having catalytic activity Cu+And Cu0Increase, in turn
Improve the low temperature active of catalyst.
It is to carry out in the liquid phase in the reduction reaction that above-mentioned houghite precursor preparation process can be seen that the application.
Therefore, it needs to be passed through inert gas in the reaction system before carrying out reduction reaction, to avoid other chemical reactions occur.More
For importantly, the application carries out reduction reaction in the liquid phase can avoid the pre- place of composite material use before in a reducing atmosphere
Reason；If not liquid phase in-situ reducing, after the calcining of houghite presoma, obtained active metal Cu is largely positive divalent, just
It cannot achieve above-mentioned catalytic process, it is therefore desirable in catalyst before use, by H2Or the reducing agents such as CO are right at 200~400 DEG C
It is pre-processed.Thus, this brings greatly inconvenient in domestic burners denitrogenation.Meanwhile in each family, due to safety original
Cause, it is impossible to be equipped with such reducing atmosphere condition.Thus, the liquid phase reduction in situ that the application carries out, technical operation is simple,
Time-consuming is short, temperature is low, energy consumption is few, and reducing condition is easily controllable, and security risk is not present.
The application finally roasts the class talcum presoma, to obtain composite catalyst；It is described to be roasted to ability
Technological means known to field technique personnel, herein without particularly limiting.The temperature of the roasting is 400~800 DEG C, the time
For 4~8h.
The method that the application obtains composite catalyst specifically:
1) aqueous solution by proportion by cerium source, copper source and silicon source according to metal molar than being configured to 0.2~2mol/L, together
When, sodium acetate and sodium carbonate are dissolved in deionized water and obtain precipitating reagent；
2) it by water-bath, is kept for 30~60 DEG C and is vigorously stirred down, simultaneously with precipitating reagent by mixing salt solution obtained above
It is added dropwise in 200mL deionized water dropwise, in the process 1~2h, keeping the pH of mixed system is 6~11；
3) after being added dropwise to complete, the hollow air-blowing of mixed system obtained above is gone out using high purity inert gas, is emptied, so
Afterwards, inert gas atmosphere is kept, the solution containing appropriate reducing agent is added dropwise in mixed liquor, 1~2h of time-consuming；
4) after the completion of reducing agent solution addition, 2~4h of aging is stirred at 60 DEG C, decompression filters, and deionized water is rushed repeatedly
It is washed till in filtrate and is detected without sodium ion；Filter cake is placed in baking oven again, 80 DEG C of 10~12h of vacuum drying, before obtaining houghite
Drive body；Finally, obtaining composite material in 400~800 DEG C of 4~8h of roasting in an inert atmosphere.
Present invention also provides the applications of above-mentioned composite catalyst, are applied particularly to coal-fired domestic burners low temperature conversion
In nitrogen oxides, specifically:
Nitric oxide and carbon monoxide are reacted under the action of the composite catalyst, obtain nitrogen and titanium dioxide
Carbon.
In above-mentioned reaction, the actual conditions of the reaction are as follows: reaction temperature be 60~120 DEG C, pressure be 0.5~
3MPa, air speed are 1000~8000h-1, the initial molar ratio of CO and NO are (1~5): 1.
The addition of two kinds of variable valency metals of Cu and Ce, ensure that the increase of active sites in composite catalyst of the present invention；Before
It drives body hydrotalcite-like compound and is conducive to the raising of catalyst specific surface and the dispersion of active sites.
Composite catalyst of the present invention carries out catalyst in catalyst preparation process, by liquid reducer
Liquid phase in-situ reducing realizes the modulation of active metal chemical combination valence, avoids before catalyst use in a reducing atmosphere pre-
Processing, the technical operation is simple, time-consuming is short, temperature is low, energy consumption is few, and reducing condition is easily controllable, and security risk is not present；Simultaneously
Resulting houghite presoma is co-precipitated in high-temperature burning process, can release vapor and carbon dioxide gas, thus
Make catalyst that there is regular meso-hole structure and big specific surface, conducive to the high degree of dispersion and exposure of catalyst activity position, finally
Be conducive to the activation of CO and NO under cryogenic.Catalyst provided by the invention tool is there are two types of metal active position, and active sites
High degree of dispersion, active specy ratio is high, and the NO conversion ratio more than 98% can be realized under cryogenic.Meanwhile catalyst is not
Easily by the dust and SO in flue gas2It is polluted, catalytic stability is preferable.
For a further understanding of the present invention, below with reference to embodiment to composite catalyst provided by the invention, its system
Preparation Method and its application are described in detail, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
Take 0.08mol Cu (NO3)2·3H2O、0.005mol Ce(NO3)3·6H2O and 0.04mol Al (NO3)3·9H2O
It is configured to the salting liquid (100mL) of 1.45mol/L, meanwhile, by CH3COONa·3H2O and Na2CO3It is dissolved in 100mL deionized water
In precipitating reagent, wherein CH is made3COONa·3H2The concentration of O is 2.5mol/L, Na2CO3Concentration be 0.225mol/L, use water
Bath control temperature at 50 DEG C, be vigorously stirred it is lower above two solution cocurrent is added dropwise in 100mL deionized water, keep solution
PH value is that 9,1h is added dropwise；After precipitating is complete, in a nitrogen atmosphere, fresh 100mL sodium borohydride is added dropwise
(1.7mol/L) solution, used time 1.2h；After the completion of liquid phase in-situ reducing, the lower 50 DEG C of ageings 3h of inert atmosphere is kept, is filtered by vacuum,
And rinsed with deionized water to filtrate and detected without sodium ion, filter cake is then obtained into the presoma of catalyst in 80 DEG C of drying；Most
Afterwards in N2In 500 DEG C of roasting 5h in atmosphere, obtain being made of composite oxides, in terms of metal molar, Cu0.8Ce0.05Al0.4O1.475
Catalyst.Fig. 1 is the SEM photograph of catalyst precursor manufactured in the present embodiment, and Fig. 2 is catalyst manufactured in the present embodiment
SEM photograph.
Above-mentioned catalyst NO and the experiment of CO reactivity worth carry out in the stainless steel reactor of 10mm internal diameter, evaluate item
Part is as follows: P=3.0Mpa, T=90 DEG C, GHSV=5000h-1, n (CO)/n (NO)=3.By gas chromatographic analysis product group
At gained reaction result is as shown in table 1:
The performance data table of table 1 catalyst NO and CO reaction
| NO conversion ratio (%) | N2Selectivity (%) |
| 98.7 | 99.8 |
Embodiment 2
Take 0.05mol Cu (NO3)2·3H2O、0.01mol Ce(NO3)3·6H2O and 0.02mol Al (NO3)3·9H2O
It is configured to the salting liquid (100mL) of 0.8mol/L, meanwhile, by 0.016mol CH3COONa·3H2O and 0.015mol Na2CO3
Obtained precipitating reagent is dissolved in 100mL deionized water to be vigorously stirred above two solution cocurrent being added dropwise to 100mL at 60 DEG C
In deionized water, keeping the pH value of solution is that 8,1h is added dropwise；After precipitating is complete, under an argon atmosphere, it is added dropwise fresh
100mL formaldehyde (1.8mol/L) solution, used time 1.5h；After the completion of liquid phase in-situ reducing, the lower 60 DEG C of ageings of inert atmosphere are kept
3h, vacuum filtration, and rinsed with deionized water to filtrate neutrality, filter cake is then obtained into the forerunner of catalyst in 80 DEG C of drying
Body；Finally in N2In 450 DEG C of roasting 5h in atmosphere, obtain being made of composite oxides, in terms of metal molar,
Cu0.1Ce0.01Al0.02O0.145Catalyst.
Above-mentioned catalyst NO and CO reaction carries out in the stainless steel reactor of 10mm internal diameter, and evaluation condition is as follows: P
=4.0Mpa, T=110 DEG C, GHSV=58000h-1, n (CO)/n (NO)=5.It is formed by gas chromatographic analysis product, gained
Reaction result is as shown in table 2:
The performance data table of table 2 catalyst NO and CO reaction
| NO conversion ratio (%) | N2Selectivity (%) |
| 99.4 | 99.2 |
Embodiment 3
Take 0.04mol Cu (NO3)2·3H2O、0.004mol Ce(NO3)3·6H2O and 0.01mol Al (NO3)3·9H2O
It is configured to the salting liquid (100mL) of 0.54mol/L, meanwhile, by 0.108mol CH3COONa·3H2O and 0.0025mol
Na2CO3Obtained precipitating reagent is dissolved in 100mL deionized water to be vigorously stirred at 60 DEG C and be added dropwise to above two solution cocurrent
In 100mL deionized water, keeping the pH value of solution is that 10,1h is added dropwise；Precipitating completely after, under an argon atmosphere, dropwise plus
Enter 100mL hydrazine hydrate (0.9mol/L) solution newly prepared, used time 1.5h；After the completion of liquid phase in-situ reducing, inert atmosphere is kept
Lower 40 DEG C of ageings 3h, vacuum filtration, and rinsed with deionized water to filtrate neutrality, then filter cake is catalyzed in 80 DEG C of drying
The presoma of agent；Finally in N2In 600 DEG C of roasting 5h in atmosphere, obtain being made of composite oxides, in terms of metal molar,
Cu0.1Ce0.01Al0.02O0.145Catalyst.
Above-mentioned catalyst NO and CO reaction carries out in the stainless steel reactor of 10mm internal diameter, and evaluation condition is as follows: P
=2.0Mpa, T=60 DEG C, GHSV=3000h-1, n (CO)/n (NO)=2.It is formed by gas chromatographic analysis product, gained is anti-
Answer that the results are shown in Table 3:
The performance data table of table 3 catalyst NO and CO reaction
| NO conversion ratio (%) | N2Selectivity (%) |
| 95.3 | 100 |
Embodiment 4
By 0.07mol Cu (NO3)2·3H2O、0.007mol Ce(NO3)3·6H2O and 0.03mol Al (NO3)3·9H2O
It is configured to the salting liquid (100mL) of 0.107mol/L, meanwhile, by 0.0214mol CH3COONa·3H2O and 0.007mol
Na2CO3Obtained precipitating reagent is dissolved in 100mL deionized water to be vigorously stirred at 60 DEG C and be added dropwise to above two solution cocurrent
In 100mL deionized water, keeping the pH value of solution is that 10,1h is added dropwise；Precipitating completely after, under an argon atmosphere, dropwise plus
Enter sugared (1.54mol/L) solution of the 100mL glucose newly prepared, used time 1.5h；After the completion of liquid phase in-situ reducing, inert atmosphere is kept
Lower 50 DEG C of ageings 2h, vacuum filtration, and rinsed with deionized water to filtrate neutrality, then filter cake is catalyzed in 80 DEG C of drying
The presoma of agent；Finally in N2In 400 DEG C of roasting 5h in atmosphere, obtain being made of composite oxides, in terms of metal molar,
Cu0.7Ce0.07Al0.3O1.255Catalyst.
Above-mentioned catalyst NO and CO reaction carries out in the stainless steel reactor of 10mm internal diameter, and evaluation condition is as follows: P
=4.0Mpa, T=110 DEG C, GHSV=7000h-1, n (CO)/n (NO)=4.It is formed by gas chromatographic analysis product, gained is anti-
Answer that the results are shown in Table 4:
The performance data table of table 4 catalyst NO and CO reaction
Embodiment 5
By 0.02mol Cu (NO3)2·3H2O、0.003mol Ce(NO3)3·6H2O and 0.01mol Al (NO3)3·9H2O
It is configured to the salting liquid (100mL) of 0.33mol/L, meanwhile, by 0.066mol CH3COONa·3H2O and 0.0065mol
Na2CO3Obtained precipitating reagent is dissolved in 100mL deionized water to be vigorously stirred at 60 DEG C and be added dropwise to above two solution cocurrent
In 100mL deionized water, keeping the pH value of solution is that 10,1h is added dropwise；Precipitating completely after, under an argon atmosphere, dropwise plus
Enter 100mL acetaldehyde (0.92mol/L) solution newly prepared, used time 1.5h；After the completion of liquid phase in-situ reducing, keep under inert atmosphere
50 DEG C of ageing 2h, vacuum filtration, and rinsed with deionized water to filtrate neutrality, filter cake is then obtained into catalyst in 80 DEG C of drying
Presoma；Finally in N2In 400 DEG C of roasting 5h in atmosphere, obtain being made of composite oxides, in terms of metal molar,
Cu0.2Ce0.03Al0.1O0.395Catalyst.
Above-mentioned catalyst NO and CO reaction carries out in the stainless steel reactor of 10mm internal diameter, and evaluation condition is as follows: P
=4.0Mpa, T=80 DEG C, GHSV=7000h-1, n (CO)/n (NO)=5.It is formed by gas chromatographic analysis product, gained is anti-
Answer that the results are shown in Table 5:
The performance data table of table 5 catalyst NO and CO reaction
| NO conversion ratio (%) | N2Selectivity (%) |
| 99.2 | 98.5 |
Comparative example 1
Take 0.08mol Cu (NO3)2·3H2O、0.005mol Ce(NO3)3·6H2O and 0.04mol Al (NO3)3·9H2O
It is configured to the salting liquid (100mL) of 1.45mol/L, meanwhile, by CH3COONa·3H2O and Na2CO3It is dissolved in 100mL deionized water
In precipitating reagent, wherein CH is made3COONa·3H2The concentration of O is 2.5mol/L, Na2CO3Concentration be 0.225mol/L, use water
Bath control temperature at 50 DEG C, be vigorously stirred it is lower above two solution cocurrent is added dropwise in 100mL deionized water, keep solution
PH value is that 9,1h is added dropwise, the lower 50 DEG C of ageings 3h of stirring condition, vacuum filtration, and with deionized water rinse to filtrate without sodium from
Son detection, then obtains the presoma of catalyst in 80 DEG C of drying for filter cake；Finally in N2In 500 DEG C of roasting 5h in atmosphere, obtain
It is formed to by composite oxides, in terms of metal molar, Cu0.8Ce0.05Al0.4O1.475Catalyst.
Above-mentioned catalyst NO and the experiment of CO reactivity worth carry out in the stainless steel reactor of 10mm internal diameter, evaluate item
Part is as follows: P=3.0Mpa, T=120 DEG C, GHSV=5000h-1, n (CO)/n (NO)=3.By gas chromatographic analysis product group
At gained reaction result is as shown in table 6:
The performance data table of table 6 catalyst NO and CO reaction
| NO conversion ratio (%) | N2Selectivity (%) |
| 38.7 | 87.3 |
As can be seen from Table 6, liquid phase in-situ reducing NO and CO respond low-temperature catalyzed to catalyst is weaker, illustrates low
The importance of warm liquid-phase reduction.
Comparative example 2
Take 0.08mol Cu (NO3)2·3H2O、0.005mol Ce(NO3)3·6H2O and 0.04mol Al (NO3)3·9H2O
It is configured to the salting liquid (100mL) of 1.45mol/L, meanwhile, by CH3COONa·3H2O and Na2CO3It is dissolved in 100mL deionized water
In precipitating reagent, wherein CH is made3COONa·3H2The concentration of O is 2.5mol/L, Na2CO3Concentration be 0.225mol/L, use water
Bath control temperature at 50 DEG C, be vigorously stirred it is lower above two solution cocurrent is added dropwise in 100mL deionized water, keep solution
PH value is that 9,1h is added dropwise, the lower 50 DEG C of ageings 3h of stirring condition, vacuum filtration, and with deionized water rinse to filtrate without sodium from
Son detection, then obtains the presoma of catalyst in 80 DEG C of drying for filter cake；Finally in N2In 500 DEG C of roasting 5h in atmosphere, obtain
It is formed to by composite oxides, in terms of metal molar, Cu0.8Ce0.05Al0.4O1.475Catalyst.
Before evaluating catalyst, in 400 DEG C of reductase 12 h in CO atmosphere, catalyst is activated, then in 10mm
Catalytic evaluation test is carried out to it in the stainless steel reactor of internal diameter, evaluation condition is as follows: P=3.0Mpa, T=120 DEG C, GHSV
=5000h-1, n (CO)/n (NO)=3.It is formed by gas chromatographic analysis product, gained reaction result is as shown in table 7:
The performance data table of table 7 catalyst NO and CO reaction
| NO conversion ratio (%) | N2Selectivity (%) |
| 55.6 | 90.5 |
As can be seen from Table 7, before catalyst use, high temperature reduction is carried out in CO atmosphere, although catalytic capability than
The catalytic capability for not pre-processing (table 6) improves, but compared with the result listed by the table 1, catalytic activity is low, low
The ability of warm denitrogenation is weak.Thus, again illustrate the importance of liquid phase in-situ reducing.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (10)
1. a kind of composite catalyst as shown in formula (I), which is characterized in that
CuxCeyAlzOm(Ⅰ)；
Wherein, x=0.1~0.8, y=0.01~0.3, z=0.01~0.5；
M is to meet atomicity required for other three kinds of element valences.
2. composite catalyst according to claim 1, which is characterized in that x=0.2~0.7, the y=
0.03~0.1, z=0.02~0.4.
3. the preparation method of the described in any item composite catalysts of claim 1~2, which is characterized in that including following step
It is rapid:
A) prepare cerium source, copper source and silicon source according to the atomicity proportion of each element in composite catalyst shown in formula (I), it will
Aqueous solution is configured to after cerium source, copper source and silicon source mixing；
B) by the aqueous solution and precipitant mix, initial precipitation liquid is obtained；The precipitating reagent is sodium acetate and sodium carbonate；
C the initial precipitation liquid is mixed with reducing agent under an inert atmosphere), reacts, obtains houghite presoma；
D) houghite presoma is roasted, obtains composite catalyst.
4. preparation method according to claim 3, which is characterized in that the reducing agent be selected from formaldehyde, acetaldehyde, vitamin C,
One of glucose and hydrazine hydrate are a variety of.
5. preparation method according to claim 3, which is characterized in that the cerium source is cerous nitrate, and copper source is nitric acid
Copper, source of aluminium are aluminum nitrate；The ratio of the copper source molal quantity and the molal quantity of the reducing agent total with the cerium source is
1:(2~5).
6. preparation method according to claim 3, which is characterized in that the total mole number in the cerium source, copper source and silicon source with
The ratio of the molal quantity of the sodium acetate is 1:(1.5~3), the total mole number and the carbonic acid in the cerium source, copper source and silicon source
The ratio of the molal quantity of sodium is 2:1.
7. preparation method according to claim 3, which is characterized in that step C) specifically:
The air in the initial precipitation liquid is blown out using inert gas, reducing agent is added, in 60 DEG C of 2~4h of aging, subtracts
Pressure filters, and obtained filter cake is dried in vacuo 10~12h at 80 DEG C, obtains houghite presoma.
8. preparation method according to claim 3, which is characterized in that the temperature of the calcining is 400~800 DEG C, the time
For 4~8h.
9. a kind of method for removing civilian burning flue-gas nitrogen oxides, comprising:
By nitric oxide and carbon monoxide the described in any item composite catalysts of claim 1~2 or claim 3~
It is reacted under the action of composite catalyst prepared by 8 described in any item preparation methods, obtains nitrogen and carbon dioxide.
10. according to the method described in claim 9, it is characterized in that, the temperature of the reaction be 60~120 DEG C, the reaction
Pressure be 0.5~3MPa, air speed be 1000~8000h-1, carbon monoxide and nitric oxide production initial molar ratio are 1~5:1.
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