CN104492455B - Copper-ferromanganese-iron-cerium quaternary composite oxide catalyst as well as preparation method and application thereof - Google Patents
Copper-ferromanganese-iron-cerium quaternary composite oxide catalyst as well as preparation method and application thereof Download PDFInfo
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- CN104492455B CN104492455B CN201410830590.0A CN201410830590A CN104492455B CN 104492455 B CN104492455 B CN 104492455B CN 201410830590 A CN201410830590 A CN 201410830590A CN 104492455 B CN104492455 B CN 104492455B
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- copper
- ferromanganese
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- iron
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Abstract
The invention discloses a copper-ferromanganese-iron-cerium quaternary composite oxide catalyst as well as a preparation method and application thereof. The copper-ferromanganese-iron-cerium quaternary composite oxide catalyst is prepared by dissolving metal salts of copper, ferromanganese, iron and cerium elements in water, adding an alkali solution for coprecipitation reaction, after the reaction is completed, drying and calcining the obtained precipitate, and naturally cooling to the room temperature, thereby obtaining a copper-ferromanganese-iron-cerium composite oxide, wherein the mole ratio of the copper, ferromanganese, iron and cerium elements is 1:1:1:7. The catalyst disclosed by the invention is high in active component content, high in inactivation resistance, low in raw material price, relatively good in mechanical strength and good in stability and activity in ultrasonic water treatment, and under certain reaction conditions, the removal rate can be up to 87.2% within 30 minutes when the catalyst is adopted to catalyze ultrasonic degradation reaction of diclofenac sodium.
Description
Technical field
The invention belongs to catalyst field, is related to a kind of copper ferromanganese cerium quaternary composite oxide catalysts and preparation method thereof
With application.
Background technology
With economic fast development, the effective process of China's industrial wastewater especially high-concentration hardly-degradable waste water becomes water
The key issue of process.This kind of waste strength is high, toxicity is big, and common process is difficult to qualified discharge, and water environment is caused
Serious pollution.High-level oxidation technology has obtained extensive concern and research as the new and effective wastewater processing technology of a class.
Ultrasonic irradiation technology is one kind of high-level oxidation technology, with wide spectrum oxidisability, cleans non-secondary pollution, therefore with very high
Application potential, but exist the not high defect of degradation efficiency be used alone, thus limit its extensive application in water process.
Heterogeneous catalysis ultrasound water technology is that catalyst is introduced in ultrasonic water treatment system, can improve the degraded effect of organic matter
Rate, shortens the reaction time, reducing energy consumption so that the technology has more practical application.Thus, preparing the catalyst of efficient stable is
Improve the key of ultrasonic water technology degradation efficiency.
Study at present more catalyst be mainly transition-metals and their oxides, rare-earth oxide, noble metal, point
Sub- sieve, heteropoly acid etc., wherein, transition metal and rare earth metal are due to aboundresources, cheap, active higher and become research
Focus.The d electronic shell of transition-metal cation is easier to lose or capture electronics, with stronger redox property, and mistake
Cross metal oxide heat-resisting strong with resistance to poison, with photosensitive, temperature-sensitive and impurity sensitiveness, therefore be more beneficial for catalyst property
Modulation.Rare-earth oxide because rich reserves, and with stronger oxygen storage capacity and redox property, while also having
The ability of good chemical stability and the quick Lacking oxygen diffusion of high temperature, thus is widely studied.Frequently as catalyst system
The metal of standby material has Ti, V, Mn, Fe, Ni, Cu, Zn, Ce, La etc..Transient metal Mn, Fe, Cu and its oxide are in catalysis oxygen
There is significant catalysis activity, rare earth metal Ce and its oxide not only have catalysis activity but also often make in water chemical treatment technology
Use for carrier.Due to transition metal ions and the difference of rare earth ion radius, when both form composite oxides, meeting
The more Lacking oxygen of generation and high hole mobility, can improve the mechanical strength of catalyst, and can significantly strengthen lattice
Defect, increases the Electronic activity of catalyst, increases substantially catalysis activity.Catalysis is applied to regard to binary metal composite oxides
The report of oxidation water process is more, but preparation method is complex, and flow process is loaded down with trivial details, organic reagent using more, using when repeat
Usability is low, and the reaction time is long.At present, the quaternary composite oxides of transient metal Mn, Fe, Cu and rare earth metal Ce be there is no
Prepare and application report.
The content of the invention
It is an object of the invention to provide a kind of copper ferromanganese cerium quaternary composite oxide catalysts and preparation method and application.
The method for preparing copper ferromanganese cerium composite oxides that the present invention is provided, comprises the steps:
The slaine of copper, manganese, iron and Ce elements is dissolved in after water, adding the aqueous solution of alkali carries out coprecipitation reaction, reacts
Finish and again calcine gained precipitation drying, naturally cool to room temperature and obtain the copper ferromanganese cerium composite oxides;
The mol ratio of the copper, manganese, iron and Ce elements is 1:1:1:7.
In said method, the aqueous solution of alkali is the aqueous solution of NaOH or the aqueous solution of potassium hydroxide;
The concentration of the aqueous solution of the alkali is 1~3mol/L, specially 2mol/L;
The slaine is nitrate;
The copper is 0.001~0.15 with the mol ratio of alkali:0.002~0.3, specially 0.005:0.01.
In the coprecipitation reaction step, the pH value of reaction system is 9~11, specially 9-10;Time be 1.5h~
2.5h, specially 2h;Temperature is 20~30 DEG C, specially 25 DEG C;
In the drying steps, temperature is 100~120 DEG C, and specially 110 DEG C, the time is 10h~14h, specially 12h;
In the calcining step, temperature is 400~600 DEG C, and concretely 450 DEG C, the time is 3h~5h, concretely
4h。
Said method may also include the steps of:After the reaction is finished, before drying steps, by gained reactant
System's centrifugation, the pH value for washing gained precipitation with water is neutrality.
In addition, the copper ferromanganese cerium composite oxides for preparing according to the method described above and the copper ferromanganese cerium composite oxides exist
Application in wastewater treatment, falls within protection scope of the present invention.Wherein, the wastewater treatment specifically may include following steps:
The copper ferromanganese cerium composite oxides are placed in waste water carries out ultrasound;
The waste water concretely aqueous solution containing C14H10Cl2NNaO2.
The pH value of the waste water concretely 3~8, more specifically can be 5;Concentration tool of the C14H10Cl2NNaO2 in the waste water
Body can be 20mg/L;
The amount ratio of the copper ferromanganese cerium composite oxides and waste water concretely 1g~10g:1L;
In the ultrasonic step, ultrasound power be 65W~650W, specially 130W, ultrasound frequency be 20~
25KHz, concretely 24KHz, ultrasonic time is 10min~60min, concretely 30min.
Instant invention overcomes deficiency of the prior art, it is proposed that a kind of to prepare that simple, raw material is cheap, catalysis activity is high
Copper ferromanganese cerium quaternary composite oxide catalysts and preparation method, the catalyst can significantly improve ultrasonotomography C14H10Cl2NNaO2
Reaction efficiency.
The invention has the beneficial effects as follows:
(1) preparation method of copper ferromanganese cerium quaternary composite oxides is simple, and raw material is cheap and easy to get, building-up process cycle is short,
Nontoxic pollution-free, there is certain industrial value.
(2) copper ferromanganese cerium quaternary composite oxides have preferable mechanical strength, have in the ultrasonic water treatment system of catalysis
There is good stability and activity, be conducive to it to carry out practical application.
Description of the drawings
Fig. 1 is the SEM photograph of the products obtained therefrom of embodiment 1.
Specific embodiment
With reference to specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Institute
State method and be conventional method if no special instructions.The raw material can be obtained if no special instructions from open commercial sources.
Ultrasonically catalyzing reactor used is the new sesame JY92-IIN type ultrasonic cell disruptors in Ningbo in following embodiments, is surpassed
Acoustic frequency is 24KHz.
The specification of various raw materials used of the invention and the information of manufacturer are as shown in table 1.
The raw materials used specification of table 1, embodiment and the information of manufacturer
In following embodiments, the catalytically active assessment test of copper ferromanganese cerium composite oxides is carried out in accordance with the following steps:
Simulated wastewater is constituted:Running water 100mL and C14H10Cl2NNaO2 2mg.
Activity rating method:Copper ferromanganese cerium composite oxides 0.5g is added in simulated wastewater, initial pH value 5 is adjusted, is surpassed
Acoustical power is 130W, and supersonic frequency is 24KHz, after ultrasonic 30min, will solution centrifugal after reaction using 3000 turns of centrifuge
5min, Jing after 0.22 micron of organic system filter membrane vacuum ultrafiltration, collects filtrate and uses high-performance liquid chromatogram determination C14H10Cl2NNaO2
Concentration simultaneously calculates clearance.
High performance liquid chromatography detection condition:Using U.S.'s Waters e2695 high performance liquid chromatography, be equipped with 250mm ×
The C18 reversed-phase columns of 4.6mm and UV-detector.Ultraviolet detection wavelength is 275nm;Elution requirement:Mobile phase is by concentration
The glacial acetic acid aqueous solution of 0.05mol/L and acetonitrile are constituted, and volume ratio is 30%:70%, flow velocity is 1ml/min, and sample size is 10 μ
L, column temperature is 30 DEG C.
The computing formula of C14H10Cl2NNaO2 clearance:The concentration of C14H10Cl2NNaO2 is detected using high performance liquid chromatography,
Under the UV absorption wavelength of 275nm, appearance time is 3.157min, and the dense of C14H10Cl2NNaO2 is calculated by going out integrating peak areas
Degree, and calculate the clearance={ 1- (C/C of C14H10Cl2NNaO20) * 100%
Wherein, C0For the initial concentration value of C14H10Cl2NNaO2, C is the concentration for reacting the C14H10Cl2NNaO2 detected after 30min
Value.
Embodiment 1
(1) 1.22g (0.005mol) Cu (NO are weighed3)2·3H2O、1.16mL(0.005mol)Mn(NO3)2、2.06g
(0.005mol)Fe(NO3)3·9H2O、15.36g(0.035mol)Ce(NO3)3·6H2O is dissolved in 160mL ultra-pure waters, gained
In solution, the mol ratio of copper, manganese, iron and Ce elements is 1:1:1:7.
(2) the 20gNaOH aqueous solution for being settled to prepared 2mol/L NaOH in 250mL ultra-pure waters soluble in water is weighed.Constantly
The mol ratio that the aqueous solution to copper and alkali of 2mol/L NaOH is slowly added dropwise under stirring is 0.005:0.01, the pH value of system
For 9~10, continuing stirring carries out coprecipitation reaction 2h.
(3) by above-mentioned solution centrifugal, it is neutrality that gained sediment is washed to pH, and in an oven 110 DEG C are dried 12h.
(4) will dried sediment agate mortar grind after be put in covered crucible, be placed in Muffle furnace 450 DEG C and forge
4h is burnt, the copper ferromanganese cerium composite oxides of present invention offer are provided after natural cooling.
The SEM photograph of the copper ferromanganese cerium composite oxides is shown in Fig. 1, and as seen from the figure, copper ferromanganese cerium composite oxides are prepared into
Work(, said composition is a kind of composite oxides, and active ingredient copper ferromanganese is all carried on the surface of cerium oxide, is conducive to anti-
Mass transfer during answering.
The Activity evaluation of catalyst is shown in Table 1.
In the catalytically active assessment test of the embodiment gained copper ferromanganese cerium composite oxides, in the UV absorption of 275nm
Under wavelength, appearance time is 3.157min, and the concentration of C14H10Cl2NNaO2, initial concentration value C are calculated by going out integrating peak areas0
For 41.33mg/L, detectable concentration value C is 5.42mg/L after reaction 30min.
The clearance of C14H10Cl2NNaO2={ 1- (C/C0) * 100%={ 1- (5.42/42.33) } * 100%=
87.20%.
Comparative example 1
(1) 21.92g Ce (NO are weighed3)3·6H2O is dissolved in 160mL ultra-pure waters.
(2) identical with step (2)~(4) in embodiment 1, gained single metal oxides are designated as CeO2.The activity of catalyst
Evaluation result is shown in Table 1.
Comparative example 2
(1) 12.20g Cu (NO are weighed3)2·3H2O is dissolved in 160mL ultra-pure waters.
(2) identical with step (2)~(4) in embodiment 1, gained single metal oxides are designated as CuO.The activity of catalyst is commented
Valency the results are shown in Table 1.
Comparative example 3
(1) 11.62mL Mn (NO are weighed3)2In being dissolved in 160mL ultra-pure waters.
(2) identical with step (2)~(4) in embodiment 1, gained single metal oxides are designated as MnO2.The activity of catalyst
Evaluation result is shown in Table 1.
Comparative example 4
(1) 20.50g Fe (NO are weighed3)3·9H2O is dissolved in 160mL ultra-pure waters.
(2) identical with step (2)~(4) in embodiment 1, gained single metal oxides are designated as Fe2O3.The activity of catalyst
Evaluation result is shown in Table 1.
Comparative example 5
(1) 12.20g Cu (NO are weighed3)2·3H2O and 15.36g Ce (NO3)3·6H2O is dissolved in 160mL ultra-pure waters.
(2) identical with step (2)~(4) in embodiment 1, products therefrom is copper cerium binary composite oxides.Catalyst
Activity evaluation is shown in Table 1.
Comparative example 6
(1) 3.48mL Mn (NO are weighed3)2With 15.36g Ce (NO3)3·6H2O is dissolved in 160mL ultra-pure waters.
(2) identical with step (2)~(4) in embodiment 1, products therefrom is manganese cerium binary composite oxides.Catalyst
Activity evaluation is shown in Table 1.
Comparative example 7
(1) 6.16g Fe (NO are weighed3)3·9H2O and 15.36g Ce (NO3)3·6H2O is dissolved in 160mL ultra-pure waters.
(2) identical with step (2)~(4) in embodiment 1, products therefrom is iron cerium binary composite oxides.Catalyst
Activity evaluation is shown in Table 1.
Comparative example 8
(1) 1.83g Cu (NO are weighed3)2·3H2O、1.74mL Mn(NO3)2With 15.36g Ce (NO3)3·6H2O is dissolved in
In 160mL ultra-pure waters.
(2) identical with step (2)~(4) in embodiment 1, products therefrom is copper manganese cerium ternary compound oxides.Catalyst
Activity evaluation be shown in Table 1.
Comparative example 9
(1) 1.83g Cu (NO are weighed3)2·3H2O、3.08g Fe(NO3)3·9H2O and 15.36g Ce (NO3)3·6H2O
In being dissolved in 160mL ultra-pure waters.
(2) identical with step (2)~(4) in embodiment 1, products therefrom is copper and iron cerium ternary compound oxides.Catalyst
Activity evaluation be shown in Table 1.
Comparative example 10
(1) 1.74mL Mn (NO are weighed3)2、3.08g Fe(NO3)3·9H2O and 15.36g Ce (NO3)3·6H2O is dissolved in
In 160mL ultra-pure waters.
(2) identical with step (2)~(4) in embodiment 1, products therefrom is ferromanganese cerium ternary compound oxides.
Above-described embodiment 1 and comparative example 1-10 gained oxide or composite oxides catalyst activity in the treatment of waste water
Evaluation result is shown in Table 1.
Table 1, catalyst activity evaluation result
As can be seen from the above table, the present invention provide copper ferromanganese cerium composite oxides, compared to single metal oxides, two
Unit, ternary compound oxides have higher catalysis activity.Meanwhile, the catalysis of the copper ferromanganese cerium composite oxides that the present invention is provided
The clearance of ultrasonotomography C14H10Cl2NNaO2 is up to 87.2%.Also, the system of the copper ferromanganese cerium composite oxides that the present invention is provided
Standby process is simple, it is easy to operate.
Claims (7)
1. a kind of method for preparing copper ferromanganese cerium composite oxides, comprises the steps:
The slaine of copper, manganese, iron and Ce elements is dissolved in after water, adding the aqueous solution of alkali carries out coprecipitation reaction, and reaction is finished
Gained precipitation drying is calcined again, room temperature is naturally cooled to and is obtained the copper ferromanganese cerium composite oxides;
The mol ratio of the copper, manganese, iron and Ce elements is 1:1:1:7.
2. method according to claim 1, it is characterised in that:The aqueous solution of the alkali is the aqueous solution or hydrogen of NaOH
The aqueous solution of potassium oxide;
In the aqueous solution of the alkali, the concentration of alkali is 1~3mol/L;
The slaine is nitrate;
The copper is 0.001~0.15 with the mol ratio of alkali:0.002~0.3.
3. method according to claim 1 and 2, it is characterised in that:In the coprecipitation reaction step, the pH of reaction system
It is worth for 9~11;Time is 1.5h~2.5h;Temperature is 20~30 DEG C;
In the drying steps, temperature is 100~120 DEG C, and the time is 10h~14h;
In the calcining step, temperature is 400~600 DEG C, and the time is 3h~5h.
4. the copper ferromanganese cerium composite oxides that the arbitrary methods described of claim 1-3 is obtained.
5. copper ferromanganese cerium composite oxides application in the treatment of waste water described in claim 4.
6. application according to claim 5, it is characterised in that:The wastewater treatment comprises the steps:By the copper manganese
Iron cerium composite oxides are placed in waste water carries out ultrasound.
7. application according to claim 6, it is characterised in that:The pH value of the waste water is 3~8;
The copper ferromanganese cerium composite oxides are 1g~10g with the amount ratio of waste water:1L;
In the ultrasonic step, the power of ultrasound is 65~650W, and the frequency of ultrasound is 20~25KHz, and ultrasonic time is 10min
~60min.
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CN112495386A (en) * | 2020-12-07 | 2021-03-16 | 山东公用同太环保科技有限公司 | Cerium-copper-iron ternary composite oxide catalyst, and preparation method and application thereof |
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