CN108906066B - Wastewater degradation catalysis material and preparation method thereof and purposes - Google Patents
Wastewater degradation catalysis material and preparation method thereof and purposes Download PDFInfo
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- CN108906066B CN108906066B CN201810803158.0A CN201810803158A CN108906066B CN 108906066 B CN108906066 B CN 108906066B CN 201810803158 A CN201810803158 A CN 201810803158A CN 108906066 B CN108906066 B CN 108906066B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The present invention provides a kind of wastewater degradation catalysis material, belongs to technical field of waste water processing.The catalysis material includes carrier and the active component that is carried on carrier, and above-mentioned carrier is active carbon, active component Co3O4, which further includes catalyst aid cerium zirconium sosoloid.On the one hand, Recalcitrant chemicals toxic in waste water can be adsorbed onto around catalysis material by active carbon in catalysis material of the invention, and further pass through active component Co3O4By pollutant efficiently catalyzing and oxidizing；On the other hand, catalysis material of the invention further includes catalyst aid cerium zirconium sosoloid, and cerium zirconium sosoloid can generate more Lacking oxygen, and can timely and effectively store oxygen, is conducive to active component Co3O4High-valence state is maintained, while can also improve catalyst activity component Co3O4Stability.
Description
Technical field
The invention belongs to field of waste water treatment, and in particular to a kind of wastewater degradation catalysis material and preparation method thereof with
On the way.
Background technique
Water pollution problems has become the problem of increasingly serious harm human health and natural environment.Waste water main source
In the discharge of chemical plant, pharmaceutical factory or printing and dyeing mill and pesticide residue etc., these wastewater toxicities are big, complex in composition and be difficult to drop
Solution, these waste water can not only break the beauty of fast water body, influence the visual experience of people, can also reduce the intake of sunlight, interfere water
The photosynthesis of plant causes toxic action to aquatiles such as fish and algae, or even can form virtue under anaerobic environment
The carcinogenic compounds such as fragrant amine cause to seriously endanger to human health.Therefore, how the pollution toxic, difficult to degrade in degrading waste water
Object reduces the toxicity of waste water, and the biodegradability for improving waste water causes vast concern.
Currently, the method for the treatment of Organic Wastewater containing phenyl amines mainly has ozone oxidation, persulfate oxidation, Fenton oxygen
The high-level oxidation technologies such as change, photochemical oxidation and electrochemical oxidation.And the key of high-level oxidation technology is waste water catalysis material,
Waste water catalysis material can be catalyzed the oxidants such as hydrogen peroxide, persulfate, ozone and resolve into the higher active oxygen of oxidizing potential,
And the higher active oxygen of these oxidizing potentials can be non-selective Decomposition Wastewater in toxic, Recalcitrant chemicals, to reach
To wastewater toxicity is reduced, the purpose of the biodegradability of waste water is improved.Currently, common wastewater treatment catalysis material is predominantly homogeneous
Catalysis material and heterogeneous catalysis material, homogeneous catalysis material are using deliquescent metal salt as catalyst, and there are catalyst
It is not easily recycled and there are problems that heavy metal secondary pollution；Heterogeneous catalysis material be using solid metal oxide as catalyst,
It has the advantage for easily recycling and avoiding heavy metal secondary pollution, therefore is the hot spot researched and developed now.
However, the solid metal oxide in existing heterogeneous catalysis material is unstable, lead to its degradation to waste water
Effect is undesirable.Therefore, a kind of heterogeneous catalysis material is researched and developed with the toxic dirt difficult to degrade in organic wastewater containing phenyl amines of degrading
Object is contaminated, the toxicity of waste water is reduced, improves the biodegradability of waste water, this is one urgently to be resolved to those skilled in the art
Technical problem.
Summary of the invention
The present invention provides a kind of wastewater degradation catalysis material, which can degrade containing having in amino benzene analog waste water
Poison, Recalcitrant chemicals, reduce the toxicity of waste water, improve the biodegradability of waste water.Furthermore the present invention further provides its preparations
Method and purposes.
The present invention solves the technical solution that above-mentioned technical problem uses are as follows:
The first aspect of the present invention provides a kind of wastewater degradation catalysis material, including carrier, is carried on the carrier
Active component and catalyst aid cerium zirconium sosoloid, wherein the carrier is active carbon, and the active component is Co3O4。
In above-mentioned wastewater degradation catalysis material, it is preferable that the general formula of the cerium zirconium sosoloid is CexZr1~xO2, 0.3 in formula
≤ x≤0.8, preferably 0.5≤x≤0.6.
In above-mentioned wastewater degradation catalysis material, it is preferable that the carrier, the active component and the cerium zirconium sosoloid
Mass ratio is 100:(0.1~3.0): (2~10).
The second aspect of the present invention provides the preparation method of above-mentioned wastewater degradation catalysis material comprising following steps:
(1) Vehicle element
Active carbon is put into nitric acid solution and is impregnated, is then taken out, until being washed with distilled water to washing solution as neutrality,
Drying, obtains pretreated active carbon；
(2) load of the active component on carrier
By Co (NO3)2·6H2O and NaNO3Addition is stirred into n-hexyl alcohol, and system in the step (1) is then added
The pretreated active carbon obtained impregnates, and then oil bath is heated at reflux, after reaction natural cooling, and obtaining the load has work
Property component carrier, the carrier of the active component of the load is taken out, wash with distilled water, dehydrated alcohol, drying；
(3) load of the catalyst aid on carrier
By the molar ratio of cerium, zirconium in catalyst aid, weighs cerium salt, zirconates and urea and be dissolved in wiring solution-forming A in deionized water；
The carrier of the active component of load is added and is ground into deionized water, obtains average particle size less than 15
The suspension B of the support type carrier of micron；
Solution A is mixed to suspension B and is carried out hydro-thermal reaction, then collects solid phase, the solid phase is washed, it is dry,
Roasting, obtains the wastewater degradation catalysis material.
Above-mentioned preparation method, it is preferable that in step (1), the concentration of the nitric acid solution is 2.5~3.5mol/L, preferably
For 2.8~3.0mol/L, soaking time is 20~26h, preferably 22~25h, and drying temperature is 100~110 DEG C, preferably 101
~108 DEG C, the time is 10~12h, preferably 11~11.5h.
In step (2), the Co (NO3)2·6H2The O and NaNO3Mass ratio be (1~4): (0.5~0.8)；Institute
State Co (NO3)2·6H2The ratio between the mass parts of O and the parts by volume of the n-hexyl alcohol are (0.1~0.4): 200, preferably (0.1~
0.3):200；Co (the NO3)2·6H2The mass ratio of O and the pretreated active carbon is (1~4): 0.1, preferably (1~
3):0.1；The mass parts and the parts by volume relationship are g/mL.
The temperature of the oil bath heating is 140~160 DEG C, preferably 150~160 DEG C, time of oil bath heating is 10~
16h, preferably 11~15h；
The drying temperature is 100~110 DEG C, and preferably 102~108 DEG C, the time is 10~12h, preferably 11~11.5h.
In step (3), the cerium salt is cerous nitrate or ammonium ceric nitrate；The zirconates is zirconyl nitrate；The cerium salt and institute
The molar ratio for stating urea is 1:(1.5~2), preferred 1:(1.6~1.8)；The hydro-thermal reaction is carried out in hydrothermal reaction kettle
, the hydrothermal temperature is 75~95 DEG C, and preferably 78~90 DEG C, the time is 1~2h, preferably 1.4~1.6h；The drying
Temperature is 90~100 DEG C, and preferably 95~98 DEG C, the time is 6~12h, and preferably 7~10h, maturing temperature is 300~650 DEG C, excellent
350~600 DEG C are selected, the time is 1.5~2.5h, preferably 1.6~2.0h.
The third aspect of the present invention provides a kind of wastewater degradation catalysis material prepared by the preparation method.
The fourth aspect of the present invention provides above-mentioned wastewater degradation catalysis material or waste water that above-mentioned preparation method is prepared
Purposes of the degradation catalysis material in wastewater degradation.
Above-mentioned technical proposal of the invention has the advantages that
(1) wastewater degradation catalysis material of the present invention, including carrier and the active component being carried on carrier, wherein
Above-mentioned carrier is active carbon, active component Co3O4, which further includes catalyst aid cerium zirconium sosoloid.One
Aspect, active carbon is cheap in catalysis material of the invention, is easy recycling, easily reuses, and active carbon can will be in waste water
Toxic Recalcitrant chemicals are adsorbed onto catalysis material surface, and further pass through active component Co3O4By pollutant efficient catalytic oxygen
Change；On the other hand, catalysis material of the invention further includes catalyst aid cerium zirconium sosoloid, and cerium zirconium sosoloid can generate more oxygen
Vacancy, and oxygen can be timely and effectively stored, be conducive to active component Co3O4High-valence state is maintained, while it is living also to improve catalyst
Property component Co3O4Stability, to improve wastewater degradation catalysis material of the invention to the degradation effect of waste water；In addition, living
Mutually disperse and contact between property component, cerium zirconium sosoloid and carrier, plays mutual barrier action, improve active component
Dispersion degree and stability.
(2) preparation method of wastewater degradation catalysis material of the present invention, first pre-processes carrier, then will
Active component Co3O4It is loaded on carrier after the pre-treatment, finally catalyst aid is loaded on carrier, specifically, by urging
The molar ratio for changing cerium, zirconium in auxiliary agent, weighs cerium salt, zirconates and urea and is dissolved in wiring solution-forming A in deionized water；The load is had
The carrier and anti-settling agent of active component are added to be ground into deionized water, obtains suspension of the average particle size less than 15 microns
B；Solution A is mixed to suspension B and carried out hydro-thermal reaction, then collects solid phase, the solid phase is washed, dry, roasting, i.e.,
The wastewater degradation catalysis material is made, by the way that catalyst aid cerium zirconium sosoloid to be loaded on carrier, is conducive to active component
Co3O4High-valence state is maintained, while can also improve catalyst activity component Co3O4Stability, to improve produced by the present invention
Degradation effect of the wastewater degradation catalysis material to waste water.
Specific embodiment
Technical solution of the present invention will be clearly and completely described below, it is clear that described embodiment is this hair
Bright a part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not having
Every other embodiment obtained under the premise of creative work is made, shall fall within the protection scope of the present invention.In addition, below
Technical characteristic involved in described different embodiments of the present invention as long as they do not conflict with each other can be mutual
In conjunction with.
In the present invention, the waste water is the waste water of the type organic containing aniline.
Embodiment 1
The preparation method of wastewater degradation catalysis material provided in this embodiment includes the following steps:
(1) Vehicle element
20g active carbon is put into 3mol/L nitric acid solution and impregnates 22h, then takes out active carbon, is washed with distilled water to
Until solution is washed as neutrality, then carrier is placed in baking oven in 105 DEG C of drying 11h, obtains pretreated active carbon；
(2) load of the active component on carrier
By 30gCo (NO3)2·6H2O and 6gNaNO3Be added into 20L n-hexyl alcohol, stirring to being uniformly mixed, and it is backward just
Pretreated active carbon obtained in 1g step (1) is added in hexanol, impregnates 5h, oil bath heating is then carried out at 150 DEG C
Reflux, heating time 14h, natural cooling, obtains the carrier of the active component of load, by the load after reaction
The carrier of active component takes out, and is washed with distilled water, dehydrated alcohol, then places in baking oven and dries 11h at 105 DEG C；
(3) load of the catalyst aid on carrier
The urea of 8g ammonium ceric nitrate, 7.8g zirconyl nitrate and 1.3g is taken to be dissolved in wiring solution-forming A in 300mL deionized water；
By the active component Co of load obtained in step (2)3O4Carrier be added into 300mL deionized water and ground
Mill, obtains the suspension B of support type carrier of the average particle size less than 15 microns；
Solution A is mixed with suspension B and carries out hydro-thermal reaction 1.5h in hydrothermal reaction kettle at 90 DEG C, is then collected solid
Phase, the solid phase is washed, 95 DEG C of dry 8h, 600 DEG C of roasting 2h, obtains wastewater degradation catalysis material A.
In the present embodiment, the carrier in wastewater degradation catalysis material obtained, active component Co3O4With cerium zirconium sosoloid
Mass ratio be 100:2:5.
Embodiment 2
The preparation method of wastewater degradation catalysis material provided in this embodiment includes the following steps:
(1) Vehicle element
20g active carbon is put into 2.5mol/L nitric acid solution and impregnates 26h, active carbon is then taken out and is washed with distilled water to
Until solution is washed as neutrality, then carrier is placed in baking oven in 100 DEG C of drying 12h, obtains pretreated active carbon；
(2) load of the active component on carrier
By 10gCo (NO3)2·6H2O and 8gNaNO3Be added into 20L n-hexyl alcohol, stirring to being uniformly mixed, and it is backward just
Pretreated active carbon obtained in 1g step (1) is added in hexanol, impregnates 6h, oil bath heating is then carried out at 160 DEG C
Reflux, heating time 10h, natural cooling, obtains the carrier of the active component of load, by the load after reaction
The carrier of active component takes out, and is washed with distilled water, dehydrated alcohol, then places in baking oven and dries 10h at 110 DEG C；
(3) load of the catalyst aid on carrier
The urea of 8g cerous nitrate, 1.07g zirconyl nitrate and 2.2g is taken to be dissolved in wiring solution-forming A in 300mL deionized water；
By the active component Co of load obtained in step (2)3O4Carrier be added into 300mL deionized water and ground
Mill, obtains the suspension B of support type carrier of the average particle size less than 15 microns；
Solution A is mixed with suspension B and carries out hydro-thermal reaction 2h in hydrothermal reaction kettle at 75 DEG C, then collects solid phase,
The solid phase is washed, 90 DEG C of dry 12h, 300 DEG C of roasting 1.5h, obtains wastewater degradation catalysis material B.
In the present embodiment, the carrier in wastewater degradation catalysis material obtained, active component Co3O4With cerium zirconium sosoloid
Mass ratio be 100:0.1:10.
Embodiment 3
The preparation method of wastewater degradation catalysis material provided in this embodiment includes the following steps:
(1) Vehicle element
20g active carbon is put into 3.5mol/L nitric acid solution and impregnates 20h, active carbon is then taken out and is washed with distilled water to
Until solution is washed as neutrality, then carrier is placed in baking oven in 110 DEG C of drying 10h, obtains pretreated active carbon；
(2) load of the active component on carrier
By 40gCo (NO3)2·6H2O and 5gNaNO3Be added into 20L n-hexyl alcohol, stirring to being uniformly mixed, and it is backward just
Pretreated active carbon obtained in 1g step (1) is added in hexanol, impregnates 5h, oil bath heating is then carried out at 140 DEG C
Reflux, heating time 16h, natural cooling, obtains the carrier of the active component of load, by the load after reaction
The carrier of active component takes out, and is washed with distilled water, dehydrated alcohol, then places in baking oven and dries 12h at 100 DEG C；
(3) load of the catalyst aid on carrier
The urea of 8g ammonium ceric nitrate, 3.37g zirconyl nitrate and 1.65g is taken to be dissolved in wiring solution-forming A in 300mL deionized water；
By the active component Co of load obtained in step (2)3O4Carrier be added into 300mL deionized water and ground
Mill, obtains the suspension B of support type carrier of the average particle size less than 15 microns；
Solution A is mixed with suspension B and carries out hydro-thermal reaction 1.0h in hydrothermal reaction kettle at 95 DEG C, is then collected solid
Phase, the solid phase is washed, 100 DEG C of dry 6h, 650 DEG C of roasting 2.5h, obtains wastewater degradation catalysis material C.
In the present embodiment, the carrier in wastewater degradation catalysis material obtained, active component Co3O4With cerium zirconium sosoloid
Mass ratio be 100:3:2.
Embodiment 4
The preparation method of wastewater degradation catalysis material provided in this embodiment includes the following steps:
(1) Vehicle element
20g active carbon is put into 3.2mol/L nitric acid solution and impregnates 25h, active carbon is then taken out and is washed with distilled water to
Until solution is washed as neutrality, then carrier is placed in baking oven in 108 DEG C of drying 11h, obtains pretreated active carbon；
(2) load of the active component on carrier
By 20gCo (NO3)2·6H2O and 7gNaNO3Be added into 20L n-hexyl alcohol, stirring to being uniformly mixed, and it is backward just
Pretreated active carbon obtained in 1g step (1) is added in hexanol, impregnates 5h, oil bath reflux is then carried out at 155 DEG C
Heating, being heated at reflux the time is 11h, after reaction natural cooling, obtains the carrier of the active component of load, will be described
The carrier for loading active component takes out, and is washed with distilled water, dehydrated alcohol, then places and dries at 105 DEG C in baking oven
11h；
(3) load of the catalyst aid on carrier
The urea of 8g ammonium ceric nitrate, 7.8g zirconyl nitrate and 1.91g is taken to be dissolved in wiring solution-forming A in 300mL deionized water；
By the active component Co of load obtained in step (2)3O4Carrier be added into 300mL deionized water and ground
Mill, obtains the suspension B of support type carrier of the average particle size less than 15 microns；
Solution A is mixed with suspension B and carries out hydro-thermal reaction 1.2h in hydrothermal reaction kettle at 88 DEG C, is then collected solid
Phase, the solid phase is washed, 97 DEG C of dry 9.5h, 450 DEG C of roasting 2.2h, obtains wastewater degradation catalysis material D.
In the present embodiment, the carrier in wastewater degradation catalysis material obtained, active component Co3O4With cerium zirconium sosoloid
Mass ratio be 100:0.5:3.
Embodiment 5
The preparation method of wastewater degradation catalysis material provided in this embodiment includes the following steps:
(1) Vehicle element
20g active carbon is put into 2.8mol/L nitric acid solution and impregnates 21h, active carbon is then taken out and is washed with distilled water to
Until solution is washed as neutrality, then carrier is placed in baking oven in 101 DEG C of drying 11.5h, obtains pretreated activity
Charcoal；
(2) load of the active component on carrier
By 20gCo (NO3)2·6H2O and 7.5gNaNO3It is added into 20L n-hexyl alcohol, stirring is and backward to being uniformly mixed
Pretreated active carbon obtained in 1g step (1) is added in n-hexyl alcohol, impregnates 5h, then carries out oil bath at 145 DEG C and returns
Stream heating, being heated at reflux the time is 13h, after reaction natural cooling, the carrier of the active component of load is obtained, by institute
The carrier taking-up for loading active component is stated, is washed with distilled water, dehydrated alcohol, is then placed and dried at 100 DEG C in baking oven
12h；
(3) load of the catalyst aid on carrier
The urea of 8g ammonium ceric nitrate, 7.8g zirconyl nitrate and 1.55g is taken to be dissolved in wiring solution-forming A in 300mL deionized water；
By the active component Co of load obtained in step (2)3O4Carrier be added into 300mL deionized water and ground
Mill, obtains the suspension B of support type carrier of the average particle size less than 15 microns；
Solution A is mixed with suspension B and carries out hydro-thermal reaction 1.4h in hydrothermal reaction kettle at 91 DEG C, is then collected solid
Phase, the solid phase is washed, 90 DEG C of dry 6h, 650 DEG C of roasting 2.5h, obtains wastewater degradation catalysis material E.
In the present embodiment, the carrier in wastewater degradation catalysis material obtained, active component Co3O4With cerium zirconium sosoloid
Mass ratio be 100:2.5:6.
Comparative example 1
The activated carbon fiber-loaded Co that Chinese patent literature CN108176403 A is prepared3O4Catalysis material, it is specific
The preparation method is as follows:
(1) activated carbon fibre pre-processes: weighing 20g activated carbon fibre, puts it into nitric acid solution (concentration 3M), room
Temperature is lower to impregnate for 24 hours, takes out ACF and is washed with distilled water for several times, until being neutrality with pH test paper measurement washing solution, is put into 105 DEG C
It is dried in drying box；
(2) 0.04g Co (NO is weighed3)2·6H2O and 0.05g NaNO3It is added in 200mL n-hexyl alcohol beaker, in room temperature
Lower magnetic agitation 2h is transferred in round-bottomed flask to being uniformly mixed, pretreated activated carbon fibre is added into round-bottomed flask
0.6g impregnates 10h, and then oil bath is heated at reflux, and heating temperature is 140 DEG C, and being heated at reflux the time is 12h, after reaction certainly
It is so cooling, ACF distilled water, dehydrated alcohol supersound washing 4 times are taken out, product is finally dried into 10h in 105 DEG C of drying boxes,
Up to activated carbon fiber-loaded Co3O4Catalysis material.
Experimental example 1
To wastewater degradation catalysis material A~E made from Examples 1 to 5 with it is activated carbon fiber-loaded made from comparative example 1
Co3O4Catalysis material carries out the catalytic performance assessment of containing benezene organic wastewater
By Examples 1 to 5 preparation wastewater degradation catalysis material A~E with it is activated carbon fiber-loaded made from comparative example 1
Co3O4PH=9.0 is added according to the dosage of 10g/L respectively in catalysis material, and concentration is the trifluoro-methoxyaniline of 500mg/L
It in indoxacarb waste water solution, is aerated according to the ozonation aerated amount of 300mL/min, control ozone concentration is 64mg/L, processing
Time is 20min, and after treatment detects water quality, detects the degradation rate of trifluoro-methoxyaniline, as a result as shown in table 1 below.
Table 1 is to COD removal rate in trifluoro-methoxyaniline aqueous solution
As shown in Table 1, the catalytic degradation effect for the wastewater degradation catalysis material that the present invention is prepared is preferable.
Experimental example 2
Service life Performance Evaluation is carried out to wastewater degradation catalysis material A made from embodiment 1
5 times of wastewater degradation catalysis material A continuous processing trifluoro-methoxyaniline aqueous solution prepared by embodiment 1, often
It is secondary handled after the trifluoro-methoxyaniline aqueous solution that all more renews, but use identical wastewater degradation catalysis material, locate every time
Reason operation is equal are as follows: pH=9.0 is added according to the dosage of 10g/L, concentration is the aqueous solution of the trifluoro-methoxyaniline of 500mg/L
In, it is aerated according to the ozonation aerated amount of 300mL/min, control ozone concentration is 64mg/L, and the processing time is 20min.5 times
After continuous processing, water quality is detected respectively.The results are shown in Table 2.
Trifluoro-methoxyaniline degradation rate after 2 continuous processing of table 5 times
As shown in Table 2, wastewater degradation catalysis material produced by the present invention has longer service life.
Experimental example 3
The catalytic degradation Performance Evaluation of different substrates is carried out to wastewater degradation catalysis material A made from embodiment 1
Each 1L of aniline, m-toluidine, parachloroanilinum for taking 1mol/L respectively is then respectively adding 10g present invention implementation
Wastewater degradation catalysis material A is made in example 1, is aerated according to the ozonation aerated amount of 300mL/min, and control ozone concentration is
64mg/L, processing time are 20min, and after treatment detects water quality, as a result as shown in table 3 below.
The catalytic degradation performance of the different substrates of table 3
| Aniline | M-toluidine | Parachloroanilinum | |
| Degradation of substrates rate (%) | 84 | 80 | 82 |
As shown in Table 3, wastewater degradation catalysis material produced by the present invention all has preferable catalysis drop to different substrates
Solve performance.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (9)
1. a method of prepare wastewater degradation catalysis material, which is characterized in that the wastewater degradation catalysis material include carrier,
The active component and catalyst aid cerium zirconium sosoloid being carried on the carrier；Wherein, the carrier is active carbon, the activity
Group is divided into Co3O4；
Described method includes following steps:
(1) Vehicle element
Active carbon is put into nitric acid solution and is impregnated, is then taken out, until being washed with distilled water to washing solution as neutrality, is dried
It is dry, obtain pretreated active carbon；
(2) load of the active component on carrier
By Co (NO3)2·6H2O and NaNO3Addition is stirred into n-hexyl alcohol, is then added obtained pre- in the step (1)
Treated, and active carbon impregnates, and then oil bath heating flows back, and natural cooling, obtains the load for loading active component after reaction
The carrier for loading active component is taken out, is washed with distilled water, dehydrated alcohol, dried by body；
(3) load of the catalyst aid on carrier
By the molar ratio of cerium, zirconium in catalyst aid, weighs cerium salt, zirconates and urea and be dissolved in wiring solution-forming A in deionized water；
The carrier for loading active component is added and is ground into deionized water, it is negative less than 15 microns to obtain average particle size
The suspension B of load type carrier；
Solution A is mixed to suspension B and carried out hydro-thermal reaction, then collects solid phase, the solid phase is washed, dry, roasting,
Obtain the wastewater degradation catalysis material.
2. preparation method according to claim 1, which is characterized in that in the step (1), the concentration of the nitric acid solution
For 2.5~3.5mol/L, soaking time is 20~26h, and drying temperature is 100~110 DEG C, and drying time is 10~12h.
3. preparation method according to claim 1 or 2, which is characterized in that in the step (2),
Co (the NO3)2·6H2The O and NaNO3Mass ratio be (1~4): (0.5~0.8)；
Co (the NO3)2·6H2The ratio between the mass parts of O and the parts by volume of the n-hexyl alcohol are (0.1~0.4): 200；
Co (the NO3)2·6H2The mass ratio of O and the pretreated active carbon is (1~4): 0.1；
The mass parts and the parts by volume relationship are g/mL.
4. preparation method according to claim 1, which is characterized in that in the step (2),
The temperature of the oil bath heating is 140~160 DEG C, and the time of the oil bath heating is 10~16h；
The drying temperature is 100~110 DEG C, and the drying time is 10~12h.
5. preparation method according to claim 1, which is characterized in that in the step (3),
The cerium salt is cerous nitrate or ammonium ceric nitrate；The zirconates is zirconyl nitrate；The molar ratio of the cerium salt and the urea
For 1:(1.5~2)；The hydro-thermal reaction carries out in hydrothermal reaction kettle, and the hydrothermal temperature is 75~95 DEG C, when reaction
Between be 1~2h；The drying temperature is 90~100 DEG C, and drying time is 6~12h, and maturing temperature is 300~650 DEG C, roasting
Time is 1.5~2.5h.
6. a kind of wastewater degradation catalysis material being prepared by the described in any item preparation methods of Claims 1 to 5.
7. wastewater degradation catalysis material according to claim 6, wherein the cerium zirconium sosoloid general formula is CexZr1-xO2,
0.3≤x≤0.8 in formula.
8. wastewater degradation catalysis material according to claim 6, which is characterized in that the carrier, the active component with
The mass ratio of the cerium zirconium sosoloid is 100:(0.1~3.0): (2~10).
9. purposes of the wastewater degradation catalysis material according to claim 6 in wastewater degradation.
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