CN109718827A - Cu0.2Ni0.8O/SBA-15, preparation method and the method for being combined degradation sulfanilamide (SN) solution with persulfate - Google Patents
Cu0.2Ni0.8O/SBA-15, preparation method and the method for being combined degradation sulfanilamide (SN) solution with persulfate Download PDFInfo
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Abstract
The present invention provides a kind of Cu0.2Ni0.8O/SBA-15 preparation method and the method for being combined degradation sulfanilamide (SN) solution with persulfate.In the present invention, Cu0.2Ni0.8O/SBA-15 catalyst and persulfate can effectively improve the utilization rate of catalyst when being combined, greatly improve degradation efficiency.Cu0.2Ni0.8Wide pH range, various pollutants concentration, various environmental wastewater processing can be used in O/SBA-15 catalyst activity with higher and stability, and it may be reused under certain number, keep higher degradation rate.Cu in the application0.2Ni0.8O/SBA-15 catalyst can also degrade with ultrasound, electrochemical method combination, greatly improve catalytic degradation efficiency, more illustrate that the sphere of action of this catalyst is wide, the height of degradation rate compares other catalyst, a variety of application methods can be more provided, it is widened significantly and use field.
Description
Technical field
This disclosure relates to technical field of waste water processing more particularly to a kind of Cu0.2Ni0.8O/SBA-15, preparation method and with
The method of persulfate combination degradation sulfanilamide (SN) solution.
Background technique
With the progress of social science and technology, our living environment problem is also got more and more attention, although passing through energy-saving and emission-reduction
With the implementation of the policies such as the adjustment of the industrial structure, the environment in China has very big improvement, but the environmental quality in China is still in tight
Heavily contaminated.The sulfanilamide (SN) such as sulfapryidine, cistosulfa substance is largely used in drug and livestock aquaculture, deposits in the environment
Sufficiently stable, it is not easy nature and degrades.Currently, the processing method of sulfanilamide (SN) substance mainly passes through light degradation method, i.e., it is sharp
Use UV/H2O2Catalysis generates free radicals (HO, O2And HO2) degrade to sulfanilamide (SN) substance.
But light degradation method needs to provide external light energy and generates free radicals to excite, and its drop to sulfanilamide (SN) substance
It solves inefficient.In addition, with the continuous development of industry, huge and ever-increasing organic pollutant leads to photodegradative speed
The appearance speed of pollutant is lagged significantly behind, and measuring usually requires high expenditure and expensive equipment.Thus, it is desirable to provide
A kind of new catalyst, with sulfanilamide (SN) substance of degrading.
Summary of the invention
The present invention provides a kind of Cu0.2Ni0.8O/SBA-15, preparation method and degradation sulfanilamide (SN) solution is combined with persulfate
Method, to solve the problems, such as sulfamido mass degradation low efficiency in the prior art and need by external energy.
The present invention provides a kind of Cu0.2Ni0.8The preparation method of O/SBA-15 catalyst, the catalyst includes the following steps:
S01: by Ni (NO3)2·6H2O and Cu (NO3)2·3H2The mixture of O is added ultrasonic dissolution in distilled water, then to its
Middle addition SBA-15 molecular sieve ultrasonic dissolution, obtains mixed liquor.
Copper, nickel are chemical element common in nature, and cost is relatively low.Copper, nickel nitrate be easy to be fired into bimetallic
Compound, and the bimetallic compound stability with higher being fired into.The application uses the nitrate system of copper, nickel as a result,
Standby Cu0.2Ni0.8O/SBA-15 catalyst.
Specifically, by Ni (NO3)2·6H2O (six water nickel nitrates) and Cu (NO3)2·3H2The mixture of O (nitrate trihydrate copper)
It is added in distilled water and carries out ultrasonic dissolution.Wherein, Ni (NO3)2·6H2O and Cu (NO3)2·3H2The ratio between molar fraction of O is
(1.1-1.2): 1, distilled water is the triple distillation water obtained after 0.45 μm of micropore filtering film filters.Ni(NO3)2·6H2O and
Cu(NO3)2·3H2After the mixture ultrasonic dissolution of O, SBA-15 molecular sieve ultrasonic dissolution 30min is added into mixture, obtains
Mixed liquor.
S02: the mixed liquor that S01 is obtained is stirred, and until heating evaporation to paste.
The mixed liquor that S01 is obtained, which is placed in magnetic stirring apparatus, to be stirred, and until heating evaporation to paste, is pasted
Shape object.More preferably, the whipping temp of magnetic stirring apparatus is 50 DEG C.
S03: the paste that S02 is obtained is 12-16 hours dry at 80-100 DEG C, obtains molecular sieve mixture.
The paste that S02 is obtained is 12-16 hours dry at 80-100 DEG C, obtains molecular sieve mixture.More preferably
Ground, drying temperature are 100 DEG C, drying time 12h.
S04: molecular sieve mixture made from S03 is subjected to high-temperature calcination.
Molecular sieve mixture made from S03 is placed in the calcining of Muffle furnace high temperature.Wherein, calcination temperature is 500-600 DEG C,
Heating rate is 2 °/min, and calcination time is 6-8 hours.
S05: calcined molecular sieve mixture is ground, Cu is obtained0.2Ni0.8O/SBA-15 catalyst.
The present invention also provides a kind of Cu0.2Ni0.8The method of O/SBA-15 and persulfate combination degradation sulfanilamide (SN) solution, should
Method includes the following steps:
S11: Cu is added in sulfanilamide (SN) solution0.2Ni0.890min is stirred in O/SBA-15 catalyst.
Cu is added in sulfanilamide (SN) solution0.2Ni0.890min is stirred in O/SBA-15 catalyst.Wherein, the sulfasolucin in the application
Liquid is sulfapryidine solution or cistosulfa solution.Cu0.2Ni0.8The additional amount of O/SBA-15 catalyst is 1~1.5g/L, sulphur
The concentration of amine aqueous solution is 50 μm of ol/L.
S12: being added persulfate in the mixed liquor that S11 is obtained, and stirs 90 minutes.
Persulfate is added in the mixed liquor that S11 is obtained, stirs 90 minutes.Wherein, in sulfanilamide (SN) solution sulfanilamide (SN) substance with
The molar ratio of persulfate is 1:(10~30), the concentration of persulfate is 1mmol/L.Persulfate in the application included
Potassium acid sulfate complex salt (chemical formula: 2KHSO5·KHSO4·K2SO4), peroxy-monosulfate (SO5 -, PMS), peroxydisulfate
(S2O8 2-, PS) etc. can generate the sulfate of potentiometric titrations.More preferably, the persulfate in the application was selected
Potassium acid sulfate complex salt.
Further, get started and clock after persulfate being added in mixed liquor, and respectively timing 0min, 5min,
It is sampled when 10min, 20min, 30min, 60min and 90min.After samples taken filtering, 1mL filtered fluid is added to sample bottle
In.In addition, needing to be added the thio sulphur that volume is 0.2mL, concentration is 20mmol/L before filtered fluid is added into sample bottle
Sour sodium is as inactivator.After filtered fluid is mixed with sodium thiosulfate, mixed liquor is measured in high performance liquid chromatograph point
Analysis, to measure analysis Cu0.2Ni0.8To the degradation effect of sulfanilamide (SN) solution after O/SBA-15 catalyst and persulfate combination.Work as sulphur
When amine aqueous solution selects sulfapryidine solution, the chromatographic condition of high performance liquid chromatograph are as follows: C18 chromatographic column, mobile phase ratio are as follows: first
Alcohol: water=30:70；Detection wavelength is 254nm；Column temperature is 30 DEG C；Flow velocity is 0.3ml/min；Detection time is 5min.Work as sulfanilamide (SN)
When solution selects cistosulfa solution, the chromatographic condition of high performance liquid chromatograph are as follows: C18 chromatographic column, mobile phase ratio are as follows: first
Alcohol: water=35:65, the another concentration that is added is 0.1% formic acid；Detection wavelength is 270nm；Column temperature is 30 DEG C；Flow velocity is 0.3ml/
min；Detection time is 8min.
The application's has the beneficial effect that:
1, in the present invention, potentiometric titrations (SO4) there is high oxidation-reduction potential (2.5-3.1V), and energy
It is reacted with most of organic matters closely to spread the speed of speed control and oxidation reaction occurs, it could be theoretically argued that can be big with oxidative degradation
Partial organic matter.Meanwhile persulfate is mostly solid-state, easily stored and transport, it is relatively stable in the environment, it is water-soluble compared with
It is good, therefore, in practical applications, there is apparent advantage relative to other oxidants.
Molecular sieve SBA-15 load is the porous material with high-specific surface area, there is preferable dispersion to make transition metal
With making Cu0.2Ni0.8O/SBA-15 and CuO is uniformly adhered in the duct SBA-15 or surface, thermal stability with higher,
The stabilization of catalyst in the reaction system, while its site for improving PMS and catalyst reaction in experiment can effectively be enhanced, and
The high-specific surface area of SBA-15 effectively improves the rate of activation potentiometric titrations, carries out reaction more quickly, effectively
The utilization rate for improving catalyst, greatly improves degradation efficiency.
2, Cu is prepared in the application0.2Ni0.8The method of O/SBA-15 catalyst is simple, the ultrasonic cleaning used
Device, magnetic stirring apparatus, Muffle furnace all act on metal ion and are scattered in molecule consent road or are attached to molecule plug table
It on face, and is the common instrument in laboratory, therefore catalyst can be mass produced, it is more simple that mode is put in storage, only
It need to be sealed using drying basin, and the degradation rate that catalyst will not follow storage time to increase reduces, its is kept stable to urge
Change activity.
3, the Cu in the application0.2Ni0.8O/SBA-15 catalyst activity with higher and stability can be used relatively wide
General pH range, various pollutants concentration, various environmental wastewaters processing, and it may be reused under certain number, keep
Higher degradation rate.
4, the Cu in the application0.2Ni0.8O/SBA-15 catalyst action range is wider, generates potentiometric titrations to sulfanilamide (SN)
Not there is a kind of substance and degrade in the degradation of substance selectivity all with higher, suitable for degradation, there are various sulfanilamide (SN)
The complicated water body of class pollution.
5, the Cu in the application0.2Ni0.8O/SBA-15 catalyst efficiency is higher, and sulfapryidine, cistosulfa are in 90min
Interior degradation rate respectively reaches 96.52%, 99.27%, and the degradation rate that PMS-65% is more only added increases significantly, right
Than SBA-15 catalyst is only added, degradation rate improves 70%, therefore obtains Cu0.2Ni0.8O/SBA-15 has higher catalytic activity, is
A kind of superior catalytic having good development prospect.
6. the Cu in the application0.2Ni0.8O/SBA-15 catalyst aequum is less, and degradation effect is preferable, ion leaching
Extracting rate is lower, is a kind of novel green catalyst, extraneous offer energy is not needed during catalytic degradation, under field conditions (factors)
It can react, catalyst recycle can be recycled from water body by centrifuge separation means after reaction, and can prevent from urging
Pollution of the agent to water body.Cu in the application0.2Ni0.8O/SBA-15 catalyst can be also combined with ultrasound, electrochemical method into
Row degradation, greatly improves catalytic degradation efficiency, thus more illustrates that the sphere of action of this catalyst is wide, the height of degradation rate, phase
Compared with other catalyst, a variety of application methods can be more provided, it is widened significantly and uses field.
Detailed description of the invention
The drawings herein are incorporated into the specification and forms part of this specification, and shows and meets implementation of the invention
Example, and be used to explain the principle of the present invention together with specification.
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, for those of ordinary skill in the art
Speech, without any creative labor, is also possible to obtain other drawings based on these drawings.
Fig. 1 is Cu provided by the embodiments of the present application0.2Ni0.8The flow diagram of the preparation method of O/SBA-15 catalyst；
Fig. 2 is Cu provided by the embodiments of the present application0.2Ni0.8The side of O/SBA-15 and persulfate combination degradation sulfanilamide (SN) solution
Method flow diagram；
Fig. 3 is the Cu that the embodiment of the present application 4 provides0.2Ni0.8The XRD wide-angle figure of O/SBA-15 catalyst；
Fig. 4 is the Cu that the embodiment of the present application 4 provides0.2Ni0.8The XRD low-angle figure of O/SBA-15 catalyst；
Fig. 5 is the Cu that the embodiment of the present application 4 provides0.2Ni0.8The TEM of O/SBA-15 catalyst schemes；
Fig. 6 is the Cu that the embodiment of the present application 4 provides0.2Ni0.8The SEM of O/SBA-15 catalyst schemes；
Fig. 7 is the Cu that the embodiment of the present application 4 provides0.2Ni0.8The EDS of O/SBA-15 catalyst schemes；
Fig. 8 is difference Cu provided by the embodiments of the present application0.2Ni0.8Drop of the additive amount of O/SBA-15 to sulfapryidine solution
Solve Kinetics Rate Constants By Using curve graph；
Fig. 9 provides different Cu for the embodiment of the present application0.2Ni0.8Drop of the additive amount of O/SBA-15 to cistosulfa solution
Solve Kinetics Rate Constants By Using curve graph；
Figure 10 is difference Cu provided by the embodiments of the present application0.2Ni0.8O/SBA-15 and sulfamido material mol ratio and power
Learn the graph of relation of rate constant；
Figure 11 provides degradation kinetics speed of the concentration to sulfapryidine solution of different persulfates for the embodiment of the present application
Rate constant curve graph；
Figure 12 is degradation power of the concentration to cistosulfa solution of different persulfates provided by the embodiments of the present application
Learn rate constant curve graph；
Figure 13 is the different concentration of persulfate provided by the embodiments of the present application and the relation curve of Kinetics Rate Constants By Using
Figure；
Figure 14 is the degradation of dehydrated alcohol provided by the embodiments of the present application and tert-butyl alcohol different multiples to sulfapryidine solution
Kinetics Rate Constants By Using curve graph；
Figure 15 is the drop of dehydrated alcohol provided by the embodiments of the present application and tert-butyl alcohol different multiples to cistosulfa solution
Solve Kinetics Rate Constants By Using curve graph；
Degradation power of the sulfapryidine solution to sulfapryidine solution that Figure 16 is difference pH provided by the embodiments of the present application
Learn rate constant curve graph；
Figure 17 is degradation of the cistosulfa solution of difference pH provided by the embodiments of the present application to cistosulfa solution
Kinetics Rate Constants By Using curve graph；
The relationship of sulfapryidine solution and Kinetics Rate Constants By Using that Figure 18 is difference pH provided by the embodiments of the present application is bent
Line chart；
Figure 19 is the difference cistosulfa solution of pH provided by the embodiments of the present application and the relationship of Kinetics Rate Constants By Using
Curve graph；
Figure 20 be it is provided by the embodiments of the present application under ultrasonic conditions, Cu0.2Ni0.8O/SBA-15 catalyst and persulfuric acid
Salt is combined the degradation test chart to sulfanilamide (SN) substance；
Figure 21 is time speed figure of the different electric currents provided by the embodiments of the present application to sulfapryidine solution degradation；
Figure 22 is time speed figure of the different electric currents provided by the embodiments of the present application to cistosulfa solution degradation；
Figure 23 be various concentration provided by the embodiments of the present application sulfapryidine solution to sulfapryidine solution degradation when
Between rate diagram；
Figure 24 is the cistosulfa solution of various concentration provided by the embodiments of the present application to cistosulfa solution degradation
Time speed figure；
Figure 25 is same Cu provided by the embodiments of the present application0.2Ni0.8O/SBA-15 catalyst five times to sulfapryidine solution
Degradation test chart；
Figure 26 is same Cu provided by the embodiments of the present application0.2Ni0.8O/SBA-15 catalyst five times molten to cistosulfa
The degradation test chart of liquid；
Figure 27 is comparative example 1-4 under different time provided by the embodiments of the present application, embodiment 4 to the drop of sulfapryidine solution
Solve result figure；
Figure 28 is comparative example 1-4, embodiment 4 under different time provided by the embodiments of the present application to cistosulfa solution
Degradation results figure.
Specific embodiment
Technical solution in order to enable those skilled in the art to better understand the present invention, below in conjunction with of the invention real
The attached drawing in example is applied, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work, all should belong to protection of the present invention
Range.
Attached drawing 1,2 is please referred to, attached drawing 1 shows Cu provided by the embodiments of the present application0.2Ni0.8The system of O/SBA-15 catalyst
The flow diagram of Preparation Method；Attached drawing 2 shows Cu provided by the embodiments of the present application0.2Ni0.8O/SBA-15 and persulfate join
With the method flow schematic diagram of degradation sulfanilamide (SN) solution.The description of following specific embodiments is based on attached drawing 1,2.
Embodiment 1
The embodiment of the present application provides a kind of Cu0.2Ni0.8O/SBA-15 catalyst, the catalyst the preparation method comprises the following steps:
S101: the Ni (NO for being 1.1:1 by the ratio between molar fraction3)2·6H2O and Cu (NO3)2·3H2The mixture of O is added
Ultrasonic dissolution in distilled water, then SBA-15 molecular sieve ultrasonic dissolution is added thereto, obtain mixed liquor；
S102: above-mentioned mixed liquor is stirred, and until heating evaporation to paste；
S103: above-mentioned paste is 16 hours dry at 80 DEG C, obtain molecular sieve mixture；
S104: above-mentioned molecular sieve mixture is subjected to high-temperature calcination；High-temperature calcination condition are as follows: calcination temperature is 600 DEG C, is risen
Warm speed is 2 °/min, and calcination time is 6 hours；
S105: calcined molecular sieve mixture is ground, Cu is obtained0.2Ni0.8O/SBA-15 catalyst.
The embodiment of the present application also provides a kind of Cu0.2Ni0.8The side of O/SBA-15 and persulfate combination degradation sulfanilamide (SN) solution
Method, this method comprises:
S111: the sulfanilamide (SN) solution that concentration is 50 μm of ol/L is added to Cu0.2Ni0.8It is stirred in O/SBA-15 catalyst
90min；Wherein, Cu0.2Ni0.8The additional amount of O/SBA-15 catalyst is 1.5g/L；
S112: being added persulfate in above-mentioned mixed liquor, stirs 90 minutes, wherein in sulfanilamide (SN) solution sulfanilamide (SN) substance with
The molar ratio of persulfate is 1:10.
Embodiment 2
The embodiment of the present application provides a kind of Cu0.2Ni0.8O/SBA-15 catalyst, the catalyst the preparation method comprises the following steps:
S201: the Ni (NO for being 1.2:1 by the ratio between molar fraction3)2·6H2O and Cu (NO3)2·3H2The mixture of O is added
Ultrasonic dissolution in distilled water, then SBA-15 molecular sieve ultrasonic dissolution is added thereto, obtain mixed liquor；
S202: above-mentioned mixed liquor is stirred, and until heating evaporation to paste；
S203: above-mentioned paste is 14 hours dry at 90 DEG C, obtain molecular sieve mixture；
S204: above-mentioned molecular sieve mixture is subjected to high-temperature calcination；High-temperature calcination condition are as follows: calcination temperature is 500 DEG C, is risen
Warm speed is 2 °/min, and calcination time is 8 hours；
S205: calcined molecular sieve mixture is ground, Cu is obtained0.2Ni0.8O/SBA-15 catalyst.
The embodiment of the present application also provides a kind of Cu0.2Ni0.8The side of O/SBA-15 and persulfate combination degradation sulfanilamide (SN) solution
Method, this method comprises:
S211: the sulfanilamide (SN) solution that concentration is 50 μm of ol/L is added to Cu0.2Ni0.8It is stirred in O/SBA-15 catalyst
90min；Wherein, Cu0.2Ni0.8The additional amount of O/SBA-15 catalyst is 1.1g/L；
S212: being added persulfate in above-mentioned mixed liquor, stirs 90 minutes, wherein in sulfanilamide (SN) solution sulfanilamide (SN) substance with
The molar ratio of persulfate is 1:30.
Embodiment 3
The embodiment of the present application provides a kind of Cu0.2Ni0.8O/SBA-15 catalyst, the catalyst the preparation method comprises the following steps:
S301: the Ni (NO for being 1.15:1 by the ratio between molar fraction3)2·6H2O and Cu (NO3)2·3H2The mixture of O is added
Ultrasonic dissolution in distilled water, then SBA-15 molecular sieve ultrasonic dissolution is added thereto, obtain mixed liquor；
S302: above-mentioned mixed liquor is stirred, and until heating evaporation to paste；
S303: above-mentioned paste is 15 hours dry at 85 DEG C, obtain molecular sieve mixture；
S304: above-mentioned molecular sieve mixture is subjected to high-temperature calcination；High-temperature calcination condition are as follows: calcination temperature is 510 DEG C, is risen
Warm speed is 2 °/min, and calcination time is 7.5 hours；
S305: calcined molecular sieve mixture is ground, Cu is obtained0.2Ni0.8O/SBA-15 catalyst.
The embodiment of the present application also provides a kind of Cu0.2Ni0.8The side of O/SBA-15 and persulfate combination degradation sulfanilamide (SN) solution
Method, this method comprises:
S311: the sulfanilamide (SN) solution that concentration is 50 μm of ol/L is added to Cu0.2Ni0.8It is stirred in O/SBA-15 catalyst
90min；Wherein, Cu0.2Ni0.8The additional amount of O/SBA-15 catalyst is 1.4g/L；
S312: being added persulfate in above-mentioned mixed liquor, stirs 90 minutes, wherein in sulfanilamide (SN) solution sulfanilamide (SN) substance with
The molar ratio of persulfate is 1:28.
Embodiment 4
The embodiment of the present application provides a kind of Cu0.2Ni0.8O/SBA-15 catalyst, the catalyst the preparation method comprises the following steps:
S401: the Ni (NO for being 1.2:1 by the ratio between molar fraction3)2·6H2O and Cu (NO3)2·3H2The mixture of O is added
Ultrasonic dissolution in 30ml distilled water, then 1.0000gSBA-15 molecular sieve ultrasonic dissolution 30min is added thereto, obtain mixed liquor；
Wherein, above-mentioned distilled water is the triple distillation water obtained after 0.45 μm of micropore filtering film filters.
S402: above-mentioned mixed liquor is placed in magnetic stirring apparatus and is stirred, and until heating evaporation to paste；Wherein,
The whipping temp of magnetic stirring apparatus is 50 DEG C；
S403: above-mentioned paste is 12 hours dry at 100 DEG C, obtain molecular sieve mixture；
S404: above-mentioned molecular sieve mixture is subjected to high-temperature calcination；High-temperature calcination condition are as follows: calcination temperature is 550 DEG C, is risen
Warm speed is 2 °/min, and calcination time is 8 hours；
S405: calcined molecular sieve mixture is ground, Cu is obtained0.2Ni0.8O/SBA-15 catalyst.
The embodiment of the present application also provides a kind of Cu0.2Ni0.8The side of O/SBA-15 and persulfate combination degradation sulfanilamide (SN) solution
Method, this method comprises:
S411: the sulfanilamide (SN) solution that by volume be 50ml, concentration is 50 μm of ol/L is added to Cu0.2Ni0.8O/SBA-15 catalysis
90min is stirred in agent；Wherein, Cu0.2Ni0.8The additional amount of O/SBA-15 catalyst is 1g/L；
S412: being added persulfate in above-mentioned mixed liquor, stirs 90 minutes, wherein in sulfanilamide (SN) solution sulfanilamide (SN) substance with
The molar ratio of persulfate is 1:20.
In above-described embodiment 1-4, sulfapryidine solution or cistosulfa solution is respectively adopted in sulfanilamide (SN) solution.The application with
Cu has been carried out for embodiment 40.2Ni0.8XRD (X-ray diffraction, X-ray diffraction) big angle of O/SBA-15 catalyst
(Transmission electron microscope, transmitted electron are aobvious by degree (10-80 °) and (0-4 °) of low-angle characterization, TEM
Micro mirror) characterization, SEM (scanning electron microscope, scanning electron microscope) characterization and EDS (Energy
Dispersive Spectroscopy, dispersion spectrum) characterization, characterization result difference is as shown in figs. 3-7.
By attached drawing 3,4 as it can be seen that by XRD wide-angle map it can be seen that with Ni (NO3)2·6H2O and Cu (NO3)2·3H2O
As nickel source and copper source, Cu is ultimately formed0.2Ni0.8Alloy and CuO, wherein Cu0.2Ni0.8The diffraction maximum of alloy is main peak, is
Mainly generate product；The diffraction maximum of CuO is the side peak on both sides, is by-product.SBA-15 and Cu as shown in Figure 40.2Ni0.8O/
The XRD low-angle scanning figure of SBA-15, two kinds of samples have its distinctive diffraction maximum under 0.7,1.4,1.6 angle of diffraction.
Thus illustrate, the material of this embodiment of the present application synthesis has the hexagonal symmetry structure of high-sequential, it means that has good
Good pore structure uniformity.In Ni metal0.2Ni0.8After O load, the case where intensity at three apparent peaks reduces,
The mesoporous channel of order reduces, and the absorption property of material weakens, to can more illustrate the embodiment of the present application preparation
Cu0.2Ni0.8O/SBA-15 catalyst degradation sulfanilamide (SN) substance is in such a way that degradation progress is adsorbed absolutely not.
By attached drawing 5-7 as it can be seen that SEM image finds that the bimetallic formed is with evenly sized particulate load in SBA- in the middle
15 surface, and the surface area of catalyst is increased, this is conducive to improve the time that solution is contacted with catalyst, increases reaction
Active site, to accelerate the progress of reaction.Find that part metals particle has entered molecule plug Jie of SBA-15 in TEM
In the track of hole, so that the mesoporosity decline of SBA-15, but ordered arrangement is still remain, it is such to be scanned with XRD low-angle
The result obtained matches, and a large amount of orderly loads, wherein the bimetallic that the light and shade region occurred is different dispersion degrees aoxidizes
Object.Middle Cu and Ni always occurs in pairs in EDS energy spectrum diagram, illustrates that two kinds of metals are to form stable bimetallic oxidation
Object is on a small quantity single metal oxides, so as to cause it can be concluded that Ni is finally formd with Cu in material prepared by embodiment 4
Cu0.2Ni0.8O/SBA-15 rather than NiO or CuO.
The embodiment of the present application is also to Cu0.2Ni0.8O/SBA-15 and persulfate combination degradation sulfanilamide (SN) solution dynamics into
Research of having gone is verified, such as Cu0.2Ni0.8Influence of the additive amount of O/SBA-15 to degradation effect, persulfate concentration to degradation
Influence of the influence, different activities oxide of effect to degradation effect, influence of the sulfanilamide (SN) substance to degradation effect of difference pH,
Influence to degradation effect of influence of influence, electric current of the ultrasonic wave to degradation effect to degradation effect, different sulfanilamide (SN) solution concentrations,
Cu0.2Ni0.8The recycling of O/SBA-15 and persulfate and Cu0.2Ni0.8Whether O/SBA-15 generates pollution to water body, under
It states and is specifically described respectively.
1、Cu0.2Ni0.8Influence of the additive amount of O/SBA-15 to degradation effect
In Cu0.2Ni0.8In the heterogeneous catalytic reaction system of O/SBA-15, persulfate, sulfanilamide (SN) substance,
Cu0.2Ni0.8O/SBA-15, persulfate are used to activate persulfate oxidation agent as catalyst and generate active sulfate radical freedom
Base, the target compound that sulfanilamide (SN) substance is attacked as free radical.The potentiometric titrations generated by catalyst and oxidant
It is important in the degradation of sulfanilamide (SN) substance, it is therefore desirable to study Cu0.2Ni0.8Shadow of the O/SBA-15 dosage to degradation kinetics
It rings.Specifically, selecting addition concentration respectively is the Cu of 0.25g/L, 0.5g/L, 1.0g/L, 1.5g/L and 2.0g/L0.2Ni0.8O/
SBA-15 and persulfate combination degradation sulfanilamide (SN) substance, wherein persulfate is the permonosulphuric acid potassium that concentration is 1Mmol/L,
Sulfamido material concentration is 50 μm of ol/L.When test, test condition is all identical, test result respectively as table 1 and attached drawing 8,9,
Shown in 10, wherein table 1 shows different Cu0.2Ni0.8Degradation of the additive amount of O/SBA-15 when degradation time reaches 90min
Efficiencies, attached drawing 8 show different Cu0.2Ni0.8Degradation kinetics speed of the additive amount of O/SBA-15 to sulfapryidine solution
Rate constant curve graph；Attached drawing 9 shows different Cu0.2Ni0.8The additive amount of O/SBA-15 is dynamic to the degradation of cistosulfa solution
Mechanics rate constant curve graph；Attached drawing 10 shows different Cu0.2Ni0.8O/SBA-15 and sulfamido material mol ratio and dynamics
The graph of relation of rate constant.
Table 1: different Cu0.2Ni0.8Degradation efficiency result of the additive amount of O/SBA-15 when degradation time reaches 90min
From table 1 it follows that difference Cu0.2Ni0.8Effect of the additive amount of O/SBA-15 to different sulfanilamide (SN) mass degradations
Difference, in certain catalyst amount, with the increase of catalytic amount, degradation rate is higher and higher, reaches certain when the time
When, sulfanilamide (SN) substance all can be degradable.It is analyzed according to sample time, in first 20 minutes, sulfamido mass degradation
Rate rapid increase, this illustrates that catalyst plays an important role.
From attached drawing 8,9,10 as it can be seen that the degradation of sulfanilamide (SN) substance meets First order dynamic model ln (C/C0)=- k1T, C and
C0 respectively indicates sulfanilamide (SN) substance in time t and time t0When concentration.Cu0.2Ni0.8The dosage of O/SBA-15 catalyst from
When 0.5g/L increases to 1.0g/L, the rate constants k of sulfapryidine1From 0.0165min-1Rapidly rise to 0.0345min-1, sulphur
The rate constants k of amine chlorine pyridazine1From 0.0165min-1Rise to 0.0557min-1.And continuing growing Cu0.2Ni0.8O/SBA-15
When the dosage of catalyst, the degradation rate constant increase of two kinds of sulfanilamide (SN) substances obviously slows down.Thus illustrate, in Cu0.2Ni0.8O/
In the optimization process of SBA-15 catalyst, the catalyst amount effect of 1.0g/L is the most obvious.Meanwhile high Cu0.2Ni0.8O/
SBA-15 catalytic amount increases the number of adsorption site and provides the activation that more permonosulphuric acid potassium generate potentiometric titrations
Site, therefore lead to the increase of rates of oxidative degradation.In addition, in experiment before, only individual permonosulphuric acid potassium and sulphur
The molar ratio of amine substance is in the system of 20:1, and the reduction amount of sulfamido material concentration is about when 90min
46.50%, illustrate Cu0.2Ni0.8O/SBA-15 plays key effect in the degradation of sulfanilamide (SN) substance.
2, influence of the concentration of persulfate to degradation effect
Selecting addition concentration respectively is the mistake of 0.25mol/L, 0.5mol/L, 1.0mol/L, 1.5mol/L and 2.0mol/L
Sulfate and Cu0.2Ni0.8O/SBA-15 catalyst combination degradation sulfanilamide (SN) substance, wherein Cu0.2Ni0.8O/SBA-15 catalyst
Additive amount be 1.0g/L, sulfamido material concentration be 50 μm of ol/L, persulfate be permonosulphuric acid potassium.When test, test-strips
Part is all identical, and test result is respectively as shown in attached drawing 11,12,13, wherein attached drawing 11 shows the concentration of different persulfates
To the degradation kinetics rate constant curve graph of sulfapryidine solution；Attached drawing 12 shows the concentration of different persulfates to sulfanilamide (SN)
The degradation kinetics rate constant curve graph of chlorine pyridazine solution；Attached drawing 13 shows the concentration and dynamics speed of different persulfates
The graph of relation of rate constant.
By attached drawing 11-13 as it can be seen that when the concentration 0.5mol/L for having served as a potassium sulfate increases to 1.0mol/L, two kinds of sulfanilamide (SN) objects
The degradation rate of matter has apparent increase, this is primarily due to the increase of permonosulphuric acid potassium concn, it is meant that more oxidants
It can be by Cu0.2Ni0.8O/SBA-15 activation of catalyst and generate potentiometric titrations, thus improve two kinds of sulfanilamide (SN) substances degradation
Effect, and sulfuric acid potassium concn continuation has been served as when progressively increasing to 2.0mol/L from 1.0mol/L, the degradation rate of sulfanilamide (SN) substance increases
It is not very big for adding, this may be because total catalytic amount is constant in the case where, it is opposite to urge as the amount of permonosulphuric acid potassium increases
Be for the amount of agent it is excessive, will not influence the concentration of potentiometric titrations in system.Furthermore also some researches show that excessive
Permonosulphuric acid root generates quenching effect to potentiometric titrations, and therefore, in the embodiment of the present application, the concentration of persulfate is
1mol/L。
In addition, sulfamido mass degradation meets First order dynamic model.The initial concentration of permonosulphuric acid potassium is from very low
0.5mol/L to 2.5mol/L, therefore, sulfanilamide (SN) mass degradation rate are related with the instantaneous concentration of permonosulphuric acid potassium, and degradation speed
Rate is restricted one of factor.Upper figure shows that Kinetics Rate Constants By Using increases with the increase of permonosulphuric acid potassium dosage, is crossing one
When the molar ratio of potassium sulfate and sulfapryidine, cistosulfa is 50:1, k1Respectively equal to 0.0496min-1、0.0805min-1。
From attached drawing 13 as can be seen that permonosulphuric acid potassium and sulfanilamide (SN) substance ratio are before 20:1, the efficiency that sulfanilamide (SN) substance is degraded more is increased
Effect, this is because permonosulphuric acid potassium is the starting point of potentiometric titrations reaction, the increase of permonosulphuric acid potassium dosage promotes sulfate radical
The generation of free radical.
3, influence of the different activities oxide to degradation effect
According to the literature, alcohol and hydroxyl or potentiometric titrations reaction rate with higher containing α hydrogen atom, such as second
The reaction rate constant of alcohol and hydroxyl radical free radical is about 50 times of potentiometric titrations, and is free of the tert-butyl alcohol and hydroxyl of α hydrogen
The reaction rate constant of free radical is about its 1000 times with potentiometric titrations reaction rate.In comparison, hydroxyl or sulphur
Acid group free radical is approximately 3 × 10 compared with the bimolecular reaction rate constant of sulfanilamide (SN) substance9M-1s-1.Therefore, more than being based on
Reaction rate constant considers that the ethyl alcohol containing α hydrogen can distinguish that over cure acid group is quenched with what hydroxyl or potentiometric titrations were contributed
Agent, and influence of the tert-butyl alcohol to sulfamido mass degradation effect can be used to distinguish potentiometric titrations and hydroxyl radical free radical is contributed
Size.In addition, experiment shows not react between over cure acid group and object, so the different activities such as Alcohols
Influence of the oxide to sulfamido mass degradation is particularly significant.
In the embodiment of the present application, dehydrated alcohol (EtOH) and the tert-butyl alcohol (TBA) is selected to degrade as activating oxide
The research of effect is tested, and the concentration of EtOH and TBA are respectively 1M and 5M.When test, test condition is all identical, test result point
Not as shown in attached drawing 14,15, wherein attached drawing 14 shows dehydrated alcohol and tert-butyl alcohol different multiples to the drop of sulfapryidine solution
Solve Kinetics Rate Constants By Using curve graph；Attached drawing 15 shows dehydrated alcohol and tert-butyl alcohol different multiples to cistosulfa solution
Degradation kinetics rate constant curve graph.
By attached drawing 14,15 as it can be seen that the experimental result of display is inconsistent with our hypothesis, this sufficiently shows hydroxyl radical free radical
It is not main active specy during sulfanilamide (SN) mass degradation, it is right when continuing the concentration of the quencher tert-butyl alcohol being increased to 5M
Potentiometric titrations quenching effects can reach 5%, at this point, the degradation effect of sulfanilamide (SN) substance organizes experiment earlier above certain drop
It is low, further illustrate hydroxyl radical free radical not and be the chief active species in sulfanilamide (SN) substance.In experimental system plus 1M
When ethyl alcohol, about 90% hydroxyl radical free radical can be quenched, about 20% potentiometric titrations, the degradation of sulfanilamide (SN) substance can be quenched
Effect is substantially reduced.And when continuing quencher concentration of alcohol being increased to 5M, 99% hydroxyl radical free radical can be quenched substantially,
And about 70%. can be improved at this point, sulfamido mass degradation effect is greatly reduced to the quenching effects of potentiometric titrations, 1.5
Hour when sulfamido mass degradation rate low 80%, this sufficiently shows that potentiometric titrations are main in the degradation of sulfanilamide (SN) substance
Lead effect.
4, influence of the sulfanilamide (SN) substance of difference pH to degradation effect
Selecting additive amount is the Cu of 1.0g/L0.2Ni0.8The permonosulphuric acid potassium that O/SBA-15 catalyst and concentration are 1mol/L
Combination, the sulfanilamide (SN) substance for being respectively 3,5,7,9 and 11 to pH value carry out degradation test, wherein sulfamido material concentration is 50 μ
mol/L.When test, test condition is all identical, and test result is respectively as shown in attached drawing 16-19, wherein attached drawing 16 is shown not
Sulfapryidine solution with pH is to the degradation kinetics rate constant curve graph of sulfapryidine solution；It is attached that Figure 17 shows different pH
Cistosulfa solution to the degradation kinetics rate constant curve graph of cistosulfa solution；Attached drawing 18 shows different pH
Sulfapryidine solution and Kinetics Rate Constants By Using graph of relation；Attached drawing 19 shows the cistosulfa solution of different pH
With the graph of relation of Kinetics Rate Constants By Using.
By attached drawing 16-19 it is found that his degradation efficiency of the pH value of different solutions is different, but in neutral conditions
Their degradation efficiency is best.When pH is in 6-7, degradation rate number persistently rises.When pH reaches 7, degradation rate constant reaches
To maximum value.When pH is more than 7, rate constant just persistently reduces.Thus illustrate, in neutral conditions, the drop of sulfanilamide (SN) substance
Rate is solved relative to being appropriate under other conditions.Pass through this description of test Cu0.2Ni0.8O/SBA-15 can be used as catalyst and go
Excitation oxidant quickly generates sulfate ion, and has preferable activity in neutral conditions, this Fenton than traditional classical
Reaction has the wider pH scope of application.
5, influence of the ultrasonic wave to degradation effect
Cu provided by the embodiments of the present application0.2Ni0.8O/SBA-15 catalyst and persulfate combination are applicable not only to general
Catalytic degradation, can be also used for and ultrasonic wave combination carry out catalytic degradation.It is in ultrasonic wave due to there was only seldom hydroxyl
It is formed in the case where individualism.By quenching experiments obtain degradation be by potentiometric titrations carry out simultaneously non-hydroxyl from
By base, so chemical reaction rate is relatively slow, therefore the concentration of sulfamido material concentration is not substantially reduced.It is super in order to study
Influence of the sound wave to sulfamido mass degradation, the embodiment of the present application test Cu under identical ultrasound condition0.2Ni0.8O/SBA-
15 catalyst and persulfate are combined the degradation effect to sulfanilamide (SN) substance.Wherein, attached drawing 20 is shown under ultrasonic conditions,
Cu0.2Ni0.8O/SBA-15 catalyst and persulfate are combined the degradation test chart to sulfanilamide (SN) substance.By attached drawing 20 it is found that
Under Ultrasonic Conditions, isomerization reaction is enhanced, and degradation efficiency increases.But in ultrasound, Cu0.2Ni0.8O/SBA-15 catalysis
In the presence of agent, persulfate, sulfanilamide (SN) substance is degradable complete in 10min.This is because ultrasound wave irradiation can form miniflow, knot
Fruit is to promote the mixing of metal-liquid surface and Cu0.2Ni0.8The continuous wash on the surface O/SBA-15, so that
Cu0.2Ni0.8The time of O/SBA-15 catalyst contact persulfate increases, and further enhances the reaction of its surface.Further, since empty
Change turbulent flow and miniflow caused by bubble avalanche, the time with ultrasound increases, and mixing intensity will increase.With reaction position
Point increases, and generates a large amount of potentiometric titrations for degrading.
6, influence of the electric current to degradation effect
In order to evaluate size of current for sulfamido mass degradation rate and degradation rate, the present invention is selected in degradation system
The different size of current for being passed through 0.1-0.9mA are tested, and test result is respectively as shown in attached drawing 21,22, wherein attached drawing 21
Different electric currents are shown to the time speed figure of sulfapryidine solution degradation；Attached drawing 22 shows different electric currents to cistosulfa
The time speed figure of solution degradation.
It is interior in 5min by attached drawing 21,22 as it can be seen that when electric current slowly improves, the system for not being passed through electric current is compared, is degraded
Rate is significantly improved, and in the experiment of high current, electrolysis rate can also be improved the anode table that reason is electrode
Face has the development formation of hydroxyl and metal forms low price with the continuous circulation of high price to promote a large amount of sulfate radical certainly
It is formed by base, but during electric current increases, degradation rate can't change, and it is secondary anti-to be that the increase of electric current is conducive to
The hydrogen of the formation answered, especially cathode development.The result of this experiment is that will not shift to an earlier date sulfamido object in the system for being passed through electric current
Matter is degraded the complete time, but its degradation rate is improved within the of short duration time.
7, influence of the different sulfanilamide (SN) solution concentrations to degradation effect
Selecting additive amount is the Cu of 1.0g/L0.2Ni0.8The permonosulphuric acid potassium that O/SBA-15 catalyst and concentration are 1mol/L
Combination is the sulfamido object of 50umol/L, 100umol/L, 150umol/L, 200umol/L and 250umol/L to concentration respectively
Matter carries out degradation test.When test, test condition is all identical, and test result is respectively as shown in attached drawing 23,24, wherein attached drawing
23 show time speed figure of the sulfapryidine solution to sulfapryidine solution degradation of various concentration；Attached drawing 24 shows difference
Time speed figure of the cistosulfa solution of concentration to cistosulfa solution degradation.
By attached drawing 23,24 it is found that with sulfamido concentration continuous growth, degradation rate constantly reducing, and reason is just
The increase of beginning permonosulphuric acid potassium and sulfamido material concentration causes to generate when sulfanilamide (SN) substance is in degradation a large amount of intermediate
Body and carbonaceous deposits attachment in the catalyst, so that the area of reaction contact constantly reduces, inactivate so as to cause activation site.
Therefore after suitable dilution should being carried out to high concentration sulfanilamide (SN) substance in practical degradation process, after reducing its concentration again into
Row degradation, can just be such that degradation rate is improved.
8、Cu0.2Ni0.8The recycling of O/SBA-15 and persulfate
Before each degradation, it is attached to avoid previous remaining sulfanilamide (SN) substance and persulfate from remaining
Cu0.2Ni0.8On O/SBA-15 catalyst, use triple distillation water cleaning three times, washes of absolute alcohol three times, to avoid remaining
Ethyl alcohol exist to the persulfate that is added next time and be quenched, reuse the cleaning of triple distillation water three times, and every time after cleaning
It is centrifuged 3min under conditions of 4400 (r/min) using centrifuge, pours out supernatant, it is cooling then again after 100 DEG C of baking oven drying
Carry out degradation test again afterwards.When test, test condition is all identical, test result respectively as shown in table 2 and attached drawing 25,26,
Wherein, table 2 shows same Cu0.2Ni0.8O/SBA-15 catalyst is in five degradations test, when degradation time reaches 90min
When, the degradation efficiency of sulfanilamide (SN) substance；Attached drawing 25 shows same Cu0.2Ni0.8O/SBA-15 catalyst five times to sulfapryidine
The degradation test chart of solution；Attached drawing 26 shows same Cu0.2Ni0.8O/SBA-15 catalyst five times to cistosulfa solution
Degradation test chart.
Table 2: same Cu0.2Ni0.8O/SBA-15 catalyst is in five degradations test, when degradation time reaches 90min,
The degradation efficiency of sulfanilamide (SN) substance
By 25,26 as it can be seen that Cu of table 2 and attached drawing0.2Ni0.8O/SBA-15 catalyst is under conditions of being used for multiple times, 90min
Interior degradation effect can still reach 50%, and gradually tend towards stability.Meanwhile Cu2+\Ni2+Ion leaching rate is compared with other catalyst
Possess lower leaching rate, this shows that sulfanilamide (SN) substance and persulfate cannot effectively destroy the table of catalyst in degradation process
Face structure and its active site, this again shows that SBA-15 can be with steady load bind metal ion.By experiment it can be proved that
Cu0.2Ni0.8O/SBA-15 can continuous several times catalytic degradation sulfanilamide (SN) substance, and continue keep efficient catalytic, stability.
In addition, since metallic nickel and metallic copper are all heavy metal, to can have serious pollution in water body, but from attached drawing
25, degradation rate of the 26 visible Cu ions in water body is lower than 4mg/L, and Ni ion is lower than 1mg/L, compares the maximum emission of Cu ion
Concentration is 5mg/L, and the maximum emission standard of Ni ion is 1.0mg/L.It follows that provided by the embodiments of the present application
Cu0.2Ni0.8O/SBA-15 catalyst will not generate pollution to our water body.Meanwhile it is provided by the embodiments of the present application
Cu0.2Ni0.8O/SBA-15 catalyst by centrifugation and water body according to ingredient from, will not polluted-water because in molecule institute beyond the Great Wall
Formed hexa-atomic symmetrical crystal structure stability with higher, thus by molecular sieve carried raising catalyst stability come
Overcome the problems, such as secondary pollution in the prior art.
To verify Cu0.2Ni0.8The degradation effect of O/SBA-15 catalyst and persulfate combination degradation sulfanilamide (SN) solution, with reality
It applies and carries out high performance liquid chromatography detection for example 4.Detection process specifically: get started note after persulfate is added in mixed liquor
When, and sampled respectively in timing 0min, 5min, 10min, 20min, 30min, 60min and 90min.After samples taken filtering,
1mL filtered fluid is added in sample bottle.In addition, into sample bottle be added filtered fluid before need to be added volume be 0.2mL,
Concentration is the sodium thiosulfate of 20mmol/L as inactivator.After filtered fluid is mixed with sodium thiosulfate, by mixed liquor efficient
Analysis is measured in liquid chromatograph, to measure analysis Cu0.2Ni0.8To sulphur after O/SBA-15 catalyst and persulfate combination
The degradation effect of amine aqueous solution.When sulfanilamide (SN) solution selects sulfapryidine solution, the chromatographic condition of high performance liquid chromatograph are as follows: C18
Chromatographic column, mobile phase ratio are as follows: methanol: water=30:70；Detection wavelength is 254nm；Column temperature is 30 DEG C；Flow velocity is 0.3ml/
min；Detection time is 5min.When sulfanilamide (SN) solution selects cistosulfa solution, the chromatographic condition of high performance liquid chromatograph are as follows:
C18 chromatographic column, mobile phase ratio are as follows: methanol: water=35:65, the another concentration that is added is 0.1% formic acid；Detection wavelength is 270nm；
Column temperature is 30 DEG C；Flow velocity is 0.3ml/min；Detection time is 8min.
It further, is Cu prepared by contrast verification the embodiment of the present application 40.2Ni0.8O/SBA-15 and persulfate are combined
The degradation effect of degradation sulfanilamide (SN) solution, the application is respectively with Cu0.2Ni0.8O/SBA-15 catalyst individually degrade sulfanilamide (SN) solution be pair
Ratio 1 is individually degraded sulfanilamide (SN) solution as comparative example 2 using SBA-15 molecular sieve, is dropped with SBA-15 molecular sieve and persulfate combination
Sulfanilamide (SN) solutions Comparative Examples 3 are solved, sulfanilamide (SN) solution of individually degrading using persulfate compares test as comparative example 4, wherein comparative example
The mixing condition of 1-4 and sulfanilamide (SN) solution, the chromatographic condition of high performance liquid chromatograph are identical with embodiment 4.Test result is such as
Shown in attached drawing 27,28, wherein attached drawing 27 is comparative example 1-4 under different time, embodiment 4 to the degradation knot of sulfapryidine solution
Fruit figure, attached drawing 28 are comparative example 1-4 under different time, embodiment 4 to the degradation results figure of cistosulfa solution.Attached drawing 27,
In 28, broken line is followed successively by comparative example 1, comparative example 2, comparative example 3, comparative example 4 and embodiments herein 4 from top to bottom.
Comparative example 1-4, embodiment 4 are to sulfapryidine solution or cistosulfa solution it can be seen from attached drawing 27,28
Interior with degradation effect, but at the same time, the degradation efficiency of comparative example 1-4 is far below the embodiment of the present application 4 to sulfanilamide (SN) pyrrole
The degradation efficiency of pyridine solution or cistosulfa solution.Thus illustrate, the Cu that the embodiment of the present application 4 provides0.2Ni0.8O/SBA-15
Can significantly degrade sulfanilamide (SN) solution, i.e. Cu are combined with persulfate0.2Ni0.8The sulfuric acid generated after O/SBA-15 activation persulfate
Root free radical can degrade the sulfanilamide (SN) substance in aqueous solution.
All the embodiments in this specification are described in a progressive manner, same and similar portion between each embodiment
Dividing may refer to each other, and each embodiment focuses on the differences from other embodiments.Especially for device or
For system embodiment, since it is substantially similar to the method embodiment, so describing fairly simple, related place is referring to method
The part of embodiment illustrates.Apparatus and system embodiment described above is only schematical, wherein as separation
The unit of part description may or may not be physically separated, component shown as a unit can be or
It can not be physical unit, it can it is in one place, or may be distributed over multiple network units.It can be according to reality
Border needs to select some or all of the modules therein to achieve the purpose of the solution of this embodiment.Those of ordinary skill in the art
It can understand and implement without creative efforts.
The above is only a specific embodiment of the invention, it is noted that those skilled in the art are come
It says, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should be regarded as
Protection scope of the present invention.
Claims (10)
1. a kind of Cu0.2Ni0.8The preparation method of O/SBA-15 catalyst, which is characterized in that described method includes following steps:
Step 1: by Ni (NO3)2·6H2O and Cu (NO3)2·3H2Ultrasonic dissolution in distilled water is added in the mixture of O, then thereto
SBA-15 molecular sieve ultrasonic dissolution is added, obtains mixed liquor；
Step 2: the mixed liquor that step 1 is obtained is stirred, and until heating evaporation to paste；
Step 3: the paste that step 2 is obtained is 12-16 hours dry at 80-100 DEG C, obtains molecular sieve mixture；
Step 4: molecular sieve mixture made from step 3 is subjected to high-temperature calcination；
Step 5: calcined molecular sieve mixture being ground, Cu is obtained0.2Ni0.8O/SBA-15 catalyst.
2. the method according to claim 1, wherein Ni (NO in step 13)2·6H2O and Cu (NO3)2·3H2O
The ratio between molar fraction be (1.1-1.2): 1.
3. the method according to claim 1, wherein in step 4 calcination temperature be 500-600 DEG C, heating rate
For 2 °/min, calcination time is 6-8 hours.
4. the method according to claim 1, wherein distilled water described in step 1 is through 0.45 μm of micropore mistake
The triple distillation water that filter membrane obtains after filtering.
5. a kind of Cu0.2Ni0.8O/SBA-15 catalyst, which is characterized in that the Cu0.2Ni0.8O/SBA-15 catalyst is by right
It is required that method described in 1-3 any one is made.
6. a kind of Cu0.2Ni0.8The method of O/SBA-15 and persulfate combination degradation sulfanilamide (SN) solution, which is characterized in that the side
Method includes the following steps:
Step 1: Cu is added in sulfanilamide (SN) solution0.2Ni0.890min is stirred in O/SBA-15 catalyst；
Step 2: persulfate being added in the mixed liquor that step 1 obtains, stirs 90min.
7. according to the method described in claim 6, it is characterized in that, Cu in step 10.2Ni0.8The addition of O/SBA-15 catalyst
Amount is 1~1.5g/L.
8. according to the method described in claim 6, it is characterized in that, in sulfanilamide (SN) solution sulfanilamide (SN) substance and persulfate molar ratio
For 1:(10~30).
9. according to the method described in claim 6, it is characterized in that, sulfanilamide (SN) solution is sulfapryidine solution or sulfanilamide (SN) in step 1
Chlorine pyridazine solution.
10. according to the method described in claim 9, it is characterized in that, the concentration of the sulfanilamide (SN) solution is 50 μm of ol/L.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111167506A (en) * | 2020-03-13 | 2020-05-19 | 重庆文理学院 | Sr2FeO4/SBA-15 composite catalyst material and preparation method thereof |
| CN111359654A (en) * | 2020-03-13 | 2020-07-03 | 重庆文理学院 | Mesoporous supported catalyst material and preparation method thereof |
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2018
- 2018-12-28 CN CN201811622621.8A patent/CN109718827A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111167506A (en) * | 2020-03-13 | 2020-05-19 | 重庆文理学院 | Sr2FeO4/SBA-15 composite catalyst material and preparation method thereof |
| CN111359654A (en) * | 2020-03-13 | 2020-07-03 | 重庆文理学院 | Mesoporous supported catalyst material and preparation method thereof |
| CN111359654B (en) * | 2020-03-13 | 2021-02-02 | 重庆文理学院 | Mesoporous supported catalyst material and preparation method thereof |
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Application publication date: 20190507 |