CN105800735B - A kind of method for treating water based on manganese cobalt composite oxide modified by nano particles ceramic membrane - Google Patents
A kind of method for treating water based on manganese cobalt composite oxide modified by nano particles ceramic membrane Download PDFInfo
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Abstract
The present invention relates to a kind of heterogeneous catalytic ozonation depollution water depth processing techniques, it is unfavorable for realizing the defect for separating and inactivating in water phase for conventional powders shape catalyst, proposes a kind of assemble method of novel manganese cobalt composite oxide nanoparticle catalyst load ceramic membrane.It is intended to combine multiphase ozone oxidation with ceramic membrane filter technology, utilizes the active component (MnO in ceramic membrane structure and Catalytic Layer2And Co3O4) catalysis ozone generate high oxidative capacity OH, organic matter can be by directly reacting with molecular ozone, or the OH reaction generated is decomposed with ozone to realize that drugs and the personal nursing category (PPCPs) such as ESCALOL 567 in water removal are gone in reinforcing, simultaneously ozone can in water body humic acid and other natural organic matters (NOMs) react, efficiently control the formation of fouling membrane.Manganese cobalt composite oxide nano particle is carried on ceramic membrane surface, realizes the separation of catalyst and water, for catalyst cleaning and be recycled for multiple times and provide new method.
Description
Technical field
The present invention relates to a kind of assembling of manganese cobalt composite oxide modified by nano particles catalytic ceramics film and its be catalyzed it is smelly
Application in oxygen oxidation decontamination dyeing technique.
Background technique
In recent years, the development of shield industry, drug and personal care articles (Pharmaceutical and are washed with medicine and
Personal Care Products, PPCPs) concern of people is increasingly subject to as a kind of emerging pollutant.Many PPCPs groups
Dividing has stronger bioactivity, optical activity and polarity, is mostly existed in the environment with trace concentration, content is in ng/L~μ g/
L.Veterinary preparations, agricultural medicine, the mankind take major way that medical and cosmetics uses are its importing environment.It is most of
PPCPs arranges people in the form of original or be converted and enters sewage treatment plant with sewage into sewage, wherein the PPCPs detected is represented
Substance have antimicrobial, antipyretic analgesic anti-inflammatory drug, estrogen and other drugs (such as lipid regulating agent, antiepileptic, tranquillizer,
Contrast agent etc.) and cosmetics in common fragrance.ESCALOL 567 (BP-3) is a kind of broad spectrum ultraviolet light
Absorbent, have many advantages, such as absorptivity it is high, it is nontoxic, without teratogenesis, it is good to light, thermal stability, be the main of common sun-screening agent
One of ingredient suffers from extensive use with cosmetic industry in industry.However, it is in surface water, underground water, drinking water, soil
With the appearance in sludge, it will hidden danger is brought to quality of water environment and ecology erroneous zone, due to conventional water treatment technology pair
The removal ability of hardly degraded organic substance is limited, it is therefore necessary to strengthen the removal ability to PPCPs in water by further treatment technique.
Heterogeneous catalytic ozonation technology is common water depth processing technique, it does not introduce other energy into technique
With poisonous and hazardous chemical agent, catalyst can be disposably filled in reactor, easy to operate, convenient in actual water process
It is applied in technique.Catalyst involved in heterogeneous catalytic ozonation is mainly metal oxide (Al2O3、MnO2Deng), it is negative
The metal or metal oxide (Cu/TiO being loaded on carrier2、Cu/Al2O3Deng) and Porous materials with large specific surface area.
The catalytic activity of these catalyst is mainly manifested in the catalytic decomposition to ozone and promotes the generation of hydroxyl radical free radical.However, this
The significant advantage of a little catalyst is the high catalytic activity of its powder morphology, but the separation being unfavorable in realization water phase, and due to
Multiple pollutant coexists in natural water body, the suction-operated of moieties and its intermediate oxidation product and make catalytic activity fail or
It loses.Therefore, it is necessary to which the catalyst of development of new, has easy aqueous phase separation and by-product while guaranteeing high catalytic activity
It is not easy the characteristic being adsorbed.
Membrane separation technique is new and effective isolation technics, is become with its energy saving and environmental-friendly feature and solves the whole world
One of common support of the significant problems such as the energy, environment, water resource.Wherein, at using ceramic micro filter film, ultrafiltration membrane as the water of representative
The application of science and engineering skill in practical projects has been achieved for remarkable progress.Ceramic membrane (ceramic membrane) is in inoranic membrane
One kind, mainly by Al2O3, ZrO2, TiO2And SiO2Etc. inorganic material be prepared, aperture be 1~50nm.Wastewater treatment
In ceramic filter membrane, be prepared using sol-gel method, tube wall gathers micropore.Under pressure, material liquid is in film
In pipe or flowing on the outside of film, small-molecule substance (or liquid) penetrate film, and macromolecular substances (or solid) are rejected by, to reach
The purpose of separation, concentration, purifying and environmental protection.Ceramic membrane have good separative efficiency height, effect stability, chemical stability, acid and alkali-resistance,
Organic solvent-resistant, resistance to bacterium, high temperature resistant, antipollution, high mechanical strength, regenerability is good, separation process is simple, low energy consumption, operation
Numerous advantages such as easy maintenance, long service life are widely used in engineering of water treatment field.However, being filtered in film
In the process, the particle in water, colloidal particle or solute transportation are since there are physics chemical actions or mechanism with film, and draw
Its absorption or deposition in film surface or fenestra is played, membrane aperture is caused to become smaller or block, film is caused to generate transmission flow and divide
The membrane pollution problem that can not be reduced from characteristic.Fouling membrane is considered as a major issue in ceramic membrane engineer application, it will
The stable operation of film is influenced, and determines the replacement frequency of film.Therefore, it is necessary to which suitable measure is taken to weaken or eliminate fouling membrane
Caused by adverse effect.
Compound manganese cobalt nano-particle modified ceramic film is intended to combine multiphase ozone oxidation with ceramic membrane filter technology, benefit
With the active component (MnO in ceramic membrane Catalytic Layer2And Co3O4) catalysis ozone generate high oxidative capacity hydroxyl radical free radical, it is organic
Object can decompose the OH reaction of generation by directly reacting with ozone molecule, or with ozone to realize that reinforcing ozone oxidation is difficult to degrade
Organic matter, at the same ozone can in water body humic acid and other natural organic matters (NOMs) react, prevent the shape of fouling membrane
At.More importantly compound manganese cobalt composite nanometer particulate load realizes the separation of catalyst and water in ceramic membrane surface, to urge
The cleaning and recycling of agent provide new method.In addition, China's manganese and cobalt contain it is abundant, using manganese and cobalt as material construction
Effective catalyst has relative inexpensiveness and the easily advantages such as acquisition.
Summary of the invention
1. technical scheme is as follows, MnO2-Co3O4The assemble method of modified by nano particles catalytic ceramics film can lead to
Cross following steps realization:
(1) precise 13.0973g Co (NO3)2·6H2O and 2.3706g KMnO4, it is dissolved completely in 200mL respectively
Deionized water in, be completely dissolved solute, to obtain clear solution；
(2) by Co (NO3)2Solution is added dropwise to KMnO with the speed of 2~3 drop per second4In solution, while using 5mol/L
NaOH adjusts mixed solution pH=7~8, while mixed solution is persistently stirred with 800rpm/min, obtains the suspension of homogeneous；
(3) to Co (NO3)2After solution is added dropwise, mixed liquor continues to stir 1h, to guarantee the complete progress of reaction；
(4) above-mentioned suspension is aged 12h at room temperature；
(5) it cleaned, be aged obtained solid 3~5 times with deionized water, to guarantee in filtrate without containing NO3 -；
(6) by above-mentioned filtering precipitate at 100 DEG C forced air drying 6h, obtain dried powder；
(7) taking dried powder 0.3000g to be dissolved in concentration is 0.1mmol/L, and volume is the KNO of 1L3In solution, and this is hanged
Turbid ultrasound 30min in ice water bath environment, evenly spreads to manganese cobalt composite oxide nano particle in solution, is formed suspended
Liquid；
(8) ceramic membrane is immersed in 0.2wt% diallyl dimethyl ammonium salt acid salt solution after 15min, is used
0.01mmol/L NaOH solution rinses 15s；
(9) above-mentioned ceramic membrane is continued to be immersed in 15min in manganese cobalt composite nanometer particle suspension liquid, uses 0.01mmol/L
NaOH solution rinses 15s, deposited one layer of nano particle in ceramic membrane surface in this way, repeats step (8) and (9), amounts to 80 times,
Until nano particle load capacity is met the requirements；
(10) modified ceramic membrane is placed on calcination in high temperature Muffle furnace, calcination temperature is 450 DEG C, and calcination time is
45min, the heating rate of Muffle furnace are 5 DEG C/min, later cooled to room temperature, i.e. completion manganese cobalt composite oxide nanometer
The assembling of grain Modified catalytic ceramic membrane.
MnO2-Co3O4Nano particle is to be restored using cobalt nitrate and potassium permanganate as critical active component using in-situ oxidation
Method, forms manganese cobalt composite oxide nano particle, and feature is specific surface area 90.0609m2/ g, total pore volume 0.2680m3/ g is put down
Equal aperture 16.1819nm, 7.051 ± 0.994nm of average grain diameter.
Based on the method for treating water of manganese cobalt composite oxide modified by nano particles ceramic membrane, pass through following steps reality
It is existing:
(1) manganese cobalt composite oxide nano particle diameter needed for technique is 7.051 ± 0.994nm；
(2) ozone concentration needed for technique is 0.5~2.0mg/L；
(3) ozone gas flow velocity needed for technique is 200~400mL/min；
(4) persistent organic pollutants concentration is 0.002~0.018mmol/L horizontal in staying water；
(5) staying water pH range is 6.0~8.0；
(6)MnO2-Co3O4The operating parameter of modified by nano particles ceramic membrane are as follows: regurgitant volume 3.0m3/ h, pressure 0.11Mpa,
20~30 DEG C of operation temperature.
2. protrusion effect of the invention is as follows:
Compound manganese cobalt nano-particle modified ceramic film is intended to combine multiphase ozone oxidation with ceramic membrane filter technology, benefit
With the active component (MnO in ceramic membrane Catalytic Layer2And Co3O4) catalysis ozone generate high oxidative capacity hydroxyl radical free radical, it is organic
Object can decompose the OH reaction of generation by directly reacting with ozone molecule, or with ozone to realize that reinforcing ozone oxidation is difficult to degrade
Organic matter, while preventing the formation of fouling membrane.More importantly compound manganese cobalt composite nanometer particulate load is real in ceramic membrane surface
Showed the separation of catalyst and water, for catalyst cleaning and be recycled for multiple times and provide new method.
Detailed description of the invention
Attached Fig. 1 shows the assemble methods of compound manganese cobalt nano-particle Modified catalytic ceramic membrane, and wherein expression is received in rectangle frame
The preparation flow of rice grain, metal-oxide suspension liquid.The present invention select have sequestering power high molecular polymer PDDA or
Phytic acid is adhesive, with metal cation by electrostatic adsorption in conjunction with, evenly spread to nano particle on ceramic membrane.
Attached drawing 2 is that the compound manganese cobalt nano-particle Modified catalytic ceramic membrane of different loads number imitates the removal of BP-3 in water
It can scheme, reaction condition are as follows: the initial concentration [BP-3] of ESCALOL 5670=2.0mg/L, dissolubility in water
Ozone concentration [O3]0=1.0mg/L, pH=7.13 ± 0.21.It can be seen from the figure that ozone does not change the degradation rate of BP-3
Property ceramic membrane (55%) obviously increases.And the ceramic membrane for impregnating 80 times is better than dipping 30 times to the degradation rate (77%) of BP-3
(61%), the degradation rate of 40 times (68%) and 60 times (71%).
Fig. 3 is MnO2-Co3O4Modified ceramic film scanning electron microscope diagram, it can be seen from the figure that modified ceramics
Film is obviously divided into three layers, including α-Al2O3Supporting layer, ZrO2Filter layer and compound manganese cobalt nano-particle Catalytic Layer.Wherein, it is catalyzed
Thickness degree is about 15 μm.The loading of nano particle Catalytic Layer becomes more sophisticated ceramic membrane membrane pore structure, is strengthening ozone oxidation
While, also enhance the strainability of film.
Specific embodiment
With reference to embodiment to the assemble method of manganese cobalt composite oxide modified by nano particles catalytic ceramics film
It is illustrated, to further understand invention.Technical solution of the present invention is not limited to following enumerated specific embodiment, further includes
Any combination between each specific embodiment.
Specific embodiment 1: MnO2-Co3O4The assemble method of modified by nano particles catalytic ceramics film can be by following several
A step is realized:
(1) precise 13.0973g Co (NO3)2·6H2O and 2.3706g KMnO4, it is dissolved completely in 200mL respectively
Deionized water in, be completely dissolved solute, to obtain clear solution；
(2) by Co (NO3)2Solution is added dropwise to KMnO with the speed of 2~3 drop per second4In solution, while using 5mol/L
NaOH adjusts mixed solution pH=7~8, while mixed solution is persistently stirred with 800rpm/min, obtains the suspension of homogeneous；
(3) to Co (NO3)2After solution is added dropwise, mixed liquor continues to stir 1h, to guarantee the complete progress of reaction；
(4) above-mentioned suspension is aged 12h at room temperature；
(5) it cleaned, be aged obtained solid 3~5 times with deionized water, to guarantee in filtrate without containing NO3 -；
(6) by above-mentioned filtering precipitate at 100 DEG C forced air drying 6h, obtain dried powder；
(7) taking dried powder 0.3000g to be dissolved in concentration is 0.1mmol/L, and volume is the KNO of 1L3In solution, and this is hanged
Turbid ultrasound 30min in ice water bath environment, evenly spreads to manganese cobalt composite oxide nano particle in solution, is formed suspended
Liquid；
(8) ceramic membrane is immersed in 0.2wt% diallyl dimethyl ammonium salt acid salt solution after 15min, is used
0.01mmol/L NaOH solution rinses 15s；
(9) above-mentioned ceramic membrane is continued to be immersed in 15min in manganese cobalt composite nanometer particle suspension liquid, uses 0.01mmol/L
NaOH solution rinses 15s, deposited one layer of nano particle in ceramic membrane surface in this way, repeats step (8) and (9), amounts to 80 times,
Until nano particle load capacity is met the requirements；
(10) modified ceramic membrane is placed on calcination in high temperature Muffle furnace, calcination temperature is 450 DEG C, and calcination time is
45min, the heating rate of Muffle furnace are 5 DEG C/min, later cooled to room temperature, i.e. completion manganese cobalt composite oxide nanometer
The assembling of grain Modified catalytic ceramic membrane.
The MnO assembled in present embodiment2-Co3O4Modified by nano particles catalytic ceramics film is to -4- the methoxyl group of hydroxyl containing 2-
The removal rate of the PPCPs such as benzophenone is better than existing conventional powders shape heterogeneous catalyst, significantly reduces cost of water treatment, mentions
The high depollution ability of water treatment technology, and composite oxides nano particle is carried on ceramic membrane surface, realizes simultaneously
The separation of catalyst and water.
Specific embodiment 2: the present embodiment is different from the first embodiment in that 13.0973g in step (1)
(45mmmol)Co(NO3)2·6H2O can be replaced 10.7069g CoCl2·6H2O, other steps and parameter and specific embodiment party
Formula one is identical.
Specific embodiment 3: the present embodiment is different from the first embodiment in that NaOH solution is replaced in step (2)
It is changed to KOH solution, other steps and parameter are same as the specific embodiment one.
Specific embodiment 4: the present embodiment is different from the first embodiment in that (8) 0.2wt% polydiene propyl
Dimethyl ammonium HCI solution replaces with 0.3wt% phytic acid (also referred to as phytic acid), other steps and parameter and specific real
It is identical to apply mode one.
Claims (4)
1. a kind of method for treating water based on manganese cobalt composite oxide modified by nano particles ceramic membrane, it is characterised in that: manganese cobalt is multiple
Conjunction oxide nano particles are MnO2-Co3O4Nano particle, manganese cobalt composite oxide modified by nano particles ceramic membrane is intended to will be more
Phase catalytic ozonation is combined with ceramic membrane filter technology, utilizes the active group being carried in ceramic membrane surface Catalytic Layer
Divide MnO2And Co3O4Catalysis ozone generates the hydroxyl radical free radical of high oxidative capacity, strengthens ozone oxidation hardly degraded organic substance to realize
Modification with the formation for preventing fouling membrane, manganese cobalt composite oxide nano particle can effectively solve powder nanometer catalyst and water
Separation problem, provide new method, manganese cobalt composite oxide nanometer for the cleaning and cycling and reutilization of catalyst and ceramic membrane
Granule modified ceramic membrane is realized by following steps:
(1) precise 13.0973g Co (NO3)2·6H2O and 2.3706g KMnO4, be dissolved completely in respectively 200mL go from
In sub- water, it is completely dissolved solute, to obtain clear solution；
(2) by Co (NO3)2Solution is added dropwise to KMnO with the speed of 2~3 drop per second4In solution, while using 5mol/L NaOH
Mixed solution pH=7~8 are adjusted, while persistently being stirred with 800rpm/min, the suspension of homogeneous is obtained；
(3) to Co (NO3)2After solution is added dropwise, mixed liquor continues to stir 1h, to guarantee the complete progress of reaction；
(4) above-mentioned suspension is aged 12h at room temperature；
(5) it cleaned, be aged obtained solid 3~5 times with deionized water, to guarantee in filtrate without containing NO3 -；
(6) by above-mentioned filtering precipitate at 100 DEG C forced air drying 6h, obtain dried powder；
(7) taking dried powder 0.3000g to be dissolved in concentration is 0.1mmol/L, and volume is the KNO of 1L3In solution, and by this suspension
Ultrasound 30min, evenly spreads to manganese cobalt composite oxide nano particle in solution in ice water bath environment, forms suspension；
(8) ceramic membrane is immersed in 15min in 0.2wt% diallyl dimethyl ammonium salt acid salt solution, uses 0.01mmol/L
NaOH solution rinses 15s；
(9) above-mentioned ceramic membrane is continued to be immersed in 15min in manganese cobalt composite nanometer particle suspension liquid, with 0.01mmol/L NaOH
Solution rinses 15s, deposited one layer of nano particle in ceramic membrane surface in this way, repeats step (8) and (9), amounts to 80 times, until
Until nano particle load capacity is met the requirements；
(10) modified ceramic membrane is placed on calcination in high temperature Muffle furnace, calcination temperature is 450 DEG C, and calcination time is
45min, the heating rate of Muffle furnace are 5 DEG C/min, later cooled to room temperature, i.e. completion manganese cobalt composite oxide nanometer
The assembling of grain Modified catalytic ceramic membrane.
2. according to the method described in claim 1, it is characterized in that manganese cobalt composite oxide nano particle is with cobalt nitrate and Gao Meng
Sour potassium is critical active component, using in-situ oxidation reduction method, forms manganese cobalt composite oxide nano particle, specific surface area
90.0609m2/ g, total pore volume 0.2680m3/ g, average pore size 16.1819nm, 7.051 ± 0.994nm of average grain diameter.
3. according to the method described in claim 1, it is characterized in that the ceramic membrane is used by α-Al2O3For inner standoff layer,
ZrO2For the tubular ceramic film of filter layer；Its concrete specification is length 25.0cm, port number 4~19, outer diameter 30mm, membrane area
0.12~0.20m2, fenestra size is 10.0~50.0nm.
4. according to the method described in claim 1, being realized by following steps:
(1) manganese cobalt composite oxide nano particle diameter needed for technique is 7.051 ± 0.994nm；
(2) ozone concentration needed for technique is 0.5~2.0mg/L；
(3) ozone gas flow velocity needed for technique is 200~400mL/min；
(4) persistent organic pollutants concentration is 0.002~0.018mmol/L horizontal in staying water；
(5) staying water pH range is 6.0~8.0；
(6)MnO2-Co3O4The operating parameter of modified by nano particles ceramic membrane are as follows: regurgitant volume 3.0m3/ h, pressure 0.11Mpa, operation
20~30 DEG C of temperature.
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| CN106630109B (en) * | 2016-11-03 | 2020-03-03 | 深圳市康源环境纳米科技有限公司 | Ceramic membrane and preparation method thereof, ceramic membrane module and wastewater treatment system |
| CN107376931A (en) * | 2017-03-22 | 2017-11-24 | 傅国琳 | A kind of solid catalyst and preparation method and purposes |
| CN107174955B (en) * | 2017-05-17 | 2020-07-24 | 大连理工大学 | Load nanometer MFe2O4Preparation method and application of hollow fiber composite ceramic membrane with catalytic separation function |
| CN110252331A (en) * | 2019-06-20 | 2019-09-20 | 宁波智通环保科技有限公司 | A kind of room temperature is except ozone catalyst and preparation method thereof |
| CN113929260A (en) * | 2020-06-29 | 2022-01-14 | 宝山钢铁股份有限公司 | Method and system for treating cold rolling oily wastewater |
| CN111792795A (en) * | 2020-07-28 | 2020-10-20 | 北京北宇机械设备有限公司 | Coal chemical wastewater treatment device |
| CN113526982A (en) * | 2021-07-29 | 2021-10-22 | 广东电网有限责任公司 | Method and device for manufacturing ceramic membrane, electronic equipment and storage medium |
| CN113976108B (en) * | 2021-11-23 | 2023-02-07 | 清华大学 | Ceramic catalytic membrane and preparation method and application thereof |
| CN115215492B (en) * | 2022-08-02 | 2023-07-28 | 北京林业大学 | Electric flocculation-ozone catalytic oxidation-ceramic membrane coupling water treatment technology for removing residual medicines in pharmaceutical wastewater |
| CN117772186B (en) * | 2024-02-26 | 2024-05-17 | 山东硅苑新材料科技股份有限公司 | Cerium-manganese composite catalyst supported ceramic membrane and preparation method and application thereof |
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