[go: up one dir, main page]

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 PDF

Info

Publication number
CN105800735B
CN105800735B CN201510658188.3A CN201510658188A CN105800735B CN 105800735 B CN105800735 B CN 105800735B CN 201510658188 A CN201510658188 A CN 201510658188A CN 105800735 B CN105800735 B CN 105800735B
Authority
CN
China
Prior art keywords
ceramic membrane
cobalt composite
composite oxide
manganese
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201510658188.3A
Other languages
Chinese (zh)
Other versions
CN105800735A (en
Inventor
齐飞
郭杨
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing Forestry University
Original Assignee
Beijing Forestry University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing Forestry University filed Critical Beijing Forestry University
Priority to CN201510658188.3A priority Critical patent/CN105800735B/en
Publication of CN105800735A publication Critical patent/CN105800735A/en
Application granted granted Critical
Publication of CN105800735B publication Critical patent/CN105800735B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Catalysts (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

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

A kind of method for treating water based on manganese cobalt composite oxide modified by nano particles ceramic membrane
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)

1.一种基于锰钴复合氧化物纳米颗粒改性陶瓷膜的水处理方法，其特征在于：锰钴复合氧化物纳米颗粒为MnO2-Co3O4纳米颗粒，锰钴复合氧化物纳米颗粒改性陶瓷膜旨在将多相催化臭氧氧化技术与陶瓷膜过滤技术相结合，利用负载于陶瓷膜表面催化层上的活性组分MnO2和Co3O4催化臭氧产生高氧化能力的羟基自由基，以实现强化臭氧氧化难降解有机物和防止膜污染的形成，锰钴复合氧化物纳米颗粒的改性可以有效解决粉末纳米催化剂与水的分离问题，为催化剂和陶瓷膜的清洗与循环再利用提供了新方法，锰钴复合氧化物纳米颗粒改性陶瓷膜通过以下几个步骤实现：1. a water treatment method based on manganese-cobalt composite oxide nanoparticles modified ceramic membrane, it is characterized in that: manganese-cobalt composite oxide nanoparticles are MnO 2 -Co 3 O 4 nanoparticles, manganese-cobalt composite oxide nanoparticles The modified ceramic membrane is designed to combine the heterogeneous catalytic ozone oxidation technology with the ceramic membrane filtration technology, using the active components MnO2 and Co3O4 supported on the surface catalytic layer of the ceramic membrane to catalyze ozone to generate hydroxyl free radicals with high oxidation ability The modification of manganese-cobalt composite oxide nanoparticles can effectively solve the problem of separation of powder nano-catalysts and water, which can be used for the cleaning and recycling of catalysts and ceramic membranes. A new method is provided, and the modified ceramic film of manganese-cobalt composite oxide nanoparticles is realized by the following steps: (1)准确称量13.0973g Co(NO3)2·6H2O和2.3706g KMnO4，分别完全溶解于200mL的去离子水中，使溶质完全溶解，以得到澄清溶液；(1) Accurately weigh 13.0973g Co(NO 3 ) 2 ·6H 2 O and 2.3706g KMnO 4 , and dissolve them in 200 mL of deionized water respectively to completely dissolve the solute to obtain a clear solution; (2)将Co(NO3)2溶液以每秒2～3滴的速度逐滴加到KMnO4溶液中，同时使用5mol/L NaOH调节混合溶液pH＝7～8，同时以800rpm/min持续搅拌，获得均质的悬浊液；(2) Add the Co(NO 3 ) 2 solution to the KMnO 4 solution dropwise at a rate of 2 to 3 drops per second, while using 5mol/L NaOH to adjust the pH of the mixed solution to 7 to 8, while continuing at 800 rpm/min Stir to obtain a homogeneous suspension; (3)待Co(NO3)2溶液滴加完毕后，混合液继续搅拌1h，以保证反应的完全进行；(3) After the dropwise addition of the Co(NO 3 ) 2 solution is completed, the mixed solution is continuously stirred for 1 h to ensure the complete reaction of the reaction; (4)将上述悬浊液在室温条件下陈化12h；(4) ageing the above suspension for 12h at room temperature; (5)用去离子水清洗、陈化所得固体3～5次，以保证滤液中不含有NO3 -；(5) wash and age the obtained solids with deionized water 3 to 5 times to ensure that the filtrate does not contain NO 3 − ; (6)将上述过滤沉淀物在100℃下鼓风干燥6h，获得干燥粉末；(6) drying the above-mentioned filtered precipitate at 100° C. for 6 h to obtain dry powder; (7)取干燥粉末0.3000g溶于浓度为0.1mmol/L，体积为1L的KNO3溶液中，并将此悬浊液在冰水浴环境中超声30min，使锰钴复合氧化物纳米颗粒均匀分散到溶液中，形成悬浊液；(7) Dissolve 0.3000 g of dry powder in a KNO solution with a concentration of 0.1 mmol/L and a volume of 1 L, and sonicate the suspension in an ice-water bath for 30 min to uniformly disperse the manganese-cobalt composite oxide nanoparticles into the solution to form a suspension; (8)将陶瓷膜浸泡在0.2wt％聚二烯丙基二甲基铵盐酸盐溶液中15min，用0.01mmol/LNaOH溶液漂洗15s；(8) Soak the ceramic membrane in 0.2wt% polydiallyldimethylammonium hydrochloride solution for 15min, and rinse with 0.01mmol/L NaOH solution for 15s; (9)将上述陶瓷膜继续浸泡在锰钴复合纳米颗粒悬浮液中15min，用0.01mmol/L NaOH溶液漂洗15s，这样在陶瓷膜表面沉积了一层纳米颗粒，重复步骤(8)和(9)，共计80次，直至纳米颗粒负载量满足要求为止；(9) Continue to immerse the above-mentioned ceramic membrane in the manganese-cobalt composite nanoparticle suspension for 15min, rinse with 0.01mmol/L NaOH solution for 15s, so that a layer of nanoparticles is deposited on the surface of the ceramic membrane, repeat steps (8) and (9) ), a total of 80 times, until the nanoparticle loading meets the requirements; (10)将改性后的陶瓷膜放置在高温马弗炉中灼烧，灼烧温度为450℃，灼烧时间为45min，马弗炉的升温速度为5℃/min，之后自然冷却至室温，即完成锰钴复合氧化物纳米颗粒改性催化陶瓷膜的组装。(10) The modified ceramic membrane is placed in a high temperature muffle furnace for burning, the burning temperature is 450 ° C, the burning time is 45 min, the heating rate of the muffle furnace is 5 ° C/min, and then naturally cooled to room temperature , that is, the assembly of manganese-cobalt composite oxide nanoparticles modified catalytic ceramic membrane is completed. 2.根据权利要求1所述的方法，其特征在于锰钴复合氧化物纳米颗粒以硝酸钴和高锰酸钾为关键活性组分，利用原位氧化还原法，形成锰钴复合氧化物纳米颗粒，比表面积90.0609m2/g，总孔容0.2680m3/g，平均孔径16.1819nm，平均粒径7.051±0.994nm。2. method according to claim 1, it is characterized in that manganese cobalt composite oxide nano-particles are key active components with cobalt nitrate and potassium permanganate, utilize in-situ redox method, form manganese-cobalt composite oxide nano-particles , the specific surface area is 90.0609m 2 /g, the total pore volume is 0.2680m 3 /g, the average pore diameter is 16.1819nm, and the average particle size is 7.051±0.994nm. 3.根据权利要求1所述的方法，其特征在于所述的陶瓷膜采用由α-Al2O3为内部支撑层、ZrO2为过滤层的管状陶瓷膜；其具体规格为长度25.0cm，通道数4～19，外径30mm，膜面积0.12～0.20m2，膜孔大小为10.0～50.0nm。3. method according to claim 1, is characterized in that described ceramic membrane adopts by α-Al 2 O 3 is inner support layer, ZrO 2 is the tubular ceramic membrane of filter layer; Its specific specification is length 25.0cm, The number of channels is 4-19, the outer diameter is 30 mm, the membrane area is 0.12-0.20 m 2 , and the membrane pore size is 10.0-50.0 nm. 4.根据权利要求1所述的方法，通过以下几个步骤实现：4. method according to claim 1, realizes by following several steps: (1)工艺所需锰钴复合氧化物纳米颗粒粒径为7.051±0.994nm；(1) The particle size of the manganese-cobalt composite oxide nanoparticles required by the process is 7.051±0.994nm; (2)工艺所需臭氧浓度为0.5～2.0mg/L；(2) The ozone concentration required by the process is 0.5 to 2.0 mg/L; (3)工艺所需臭氧气体流速为200～400mL/min；(3) The flow rate of ozone gas required by the process is 200 to 400 mL/min; (4)待处理水体中难降解有机污染物浓度为0.002～0.018mmol/L水平；(4) The concentration of refractory organic pollutants in the water to be treated is 0.002 to 0.018 mmol/L; (5)待处理水体pH范围为6.0～8.0；(5) The pH range of the water to be treated is 6.0 to 8.0; (6)MnO2-Co3O4纳米颗粒改性陶瓷膜的运行参数为：回流量3.0m3/h,压力0.11Mpa，操作温度20～30℃。(6) The operating parameters of the MnO 2 -Co 3 O 4 nanoparticle-modified ceramic membrane are: reflux 3.0 m 3 /h, pressure 0.11 Mpa, and operating temperature 20-30 °C.
CN201510658188.3A 2015-10-14 2015-10-14 A kind of method for treating water based on manganese cobalt composite oxide modified by nano particles ceramic membrane Active CN105800735B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510658188.3A CN105800735B (en) 2015-10-14 2015-10-14 A kind of method for treating water based on manganese cobalt composite oxide modified by nano particles ceramic membrane

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510658188.3A CN105800735B (en) 2015-10-14 2015-10-14 A kind of method for treating water based on manganese cobalt composite oxide modified by nano particles ceramic membrane

Publications (2)

Publication Number Publication Date
CN105800735A CN105800735A (en) 2016-07-27
CN105800735B true CN105800735B (en) 2019-03-19

Family

ID=56465605

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510658188.3A Active CN105800735B (en) 2015-10-14 2015-10-14 A kind of method for treating water based on manganese cobalt composite oxide modified by nano particles ceramic membrane

Country Status (1)

Country Link
CN (1) CN105800735B (en)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 A kind of preparation method and application of hollow fiber composite ceramic membrane loaded with nanometer MFe2O4 for 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 A 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

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102897895A (en) * 2012-11-06 2013-01-30 浙江省农业科学院 Method for degrading humus organic pollutants in water by catalytic ozonation
CN103331170A (en) * 2013-06-28 2013-10-02 华南理工大学 Ceramsite catalyst containing metallic oxide particles as well as preparation method and application thereof
CN103951028A (en) * 2014-04-10 2014-07-30 北京林业大学 Water treatment method for catalytic ozonation of refractory organics in water by ceramic membrane

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2780053B1 (en) * 1998-06-18 2000-08-11 Degremont PROCESS FOR THE MINERALIZATION OF ORGANIC POLLUTANTS OF WATER BY CATALYTIC OZONATION
CN102600861B (en) * 2012-03-26 2016-03-16 中国科学院生态环境研究中心 For the manganese base composite oxidate Catalysts and its preparation method of catalytic decomposition ozone
CN104841292B (en) * 2015-05-25 2017-02-01 哈尔滨工业大学 Ozone-catalytic functional ceramic membrane, preparation method thereof and circulating coating device

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102897895A (en) * 2012-11-06 2013-01-30 浙江省农业科学院 Method for degrading humus organic pollutants in water by catalytic ozonation
CN103331170A (en) * 2013-06-28 2013-10-02 华南理工大学 Ceramsite catalyst containing metallic oxide particles as well as preparation method and application thereof
CN103951028A (en) * 2014-04-10 2014-07-30 北京林业大学 Water treatment method for catalytic ozonation of refractory organics in water by ceramic membrane

Also Published As

Publication number Publication date
CN105800735A (en) 2016-07-27

Similar Documents

Publication Publication Date Title
CN105800735B (en) A kind of method for treating water based on manganese cobalt composite oxide modified by nano particles ceramic membrane
Wang et al. Bioinspired synthesis of photocatalytic nanocomposite membranes based on synergy of Au-TiO2 and polydopamine for degradation of tetracycline under visible light
Mohd Kaus et al. Effective strategies, mechanisms, and photocatalytic efficiency of semiconductor nanomaterials incorporating rGO for environmental contaminant degradation
Molinari et al. Overview of photocatalytic membrane reactors in organic synthesis, energy storage and environmental applications
Rahimi et al. Visible light photocatalytic disinfection of E. coli with TiO2–graphene nanocomposite sensitized with tetrakis (4-carboxyphenyl) porphyrin
Dunkle et al. BiVO4 as a visible-light photocatalyst prepared by ultrasonic spray pyrolysis
CN105800767B (en) The structure of a kind of nanometer of mangaic acid copper spinelle catalytic film reactor and its application process in water process
CN102423611B (en) Method for removing VOCs by UV light catalytic oxidation cooperating with biofiltration
Faraji et al. Enhanced photocatalytic activity by synergic action of ZIF-8 and NiFe2O4 under visible light irradiation
Li et al. Carboxylated Nanodiamond-enhanced photocatalytic membranes with improved antifouling and self-cleaning properties
CN103741263B (en) A kind of high-ratio surface porous TiO 2the preparation method of nanofiber
CN107617447A (en) A kind of Ag@MOFs/TiO2The preparation method of photochemical catalyst and application
CN105582916B (en) A kind of titanium dioxide is sequentially depositing the preparation method of the photochemical catalyst of nanogold and rhodium
CN101015790A (en) Titanium dioxide microsphere photocatalyst capable of degrading organic pollutant and its prodn. method
Kumar Metal Oxides‐Based Nano/Microstructures for Photodegradation of Microplastics
Roy et al. Recent advances in Cu-BTC MOF-based engineered materials for the photocatalytic treatment of pharmaceutical wastewater towards environmental remediation
CN111632625A (en) A kind of preparation method and application of Prussian blue quantum dot titanium carbide composite catalyst
Gao et al. Engineered inverse opal structured semiconductors for solar light-driven environmental catalysis
Li et al. N-doped TiO2 coupled with manganese-substituted phosphomolybdic acid composites as efficient photocatalysis-fenton catalysts for the degradation of Rhodamine B
CN104147924A (en) Novel photo-catalyst air purifying agent and preparation method
Yang et al. 3D-printed N-doped porous carbon aerogels for efficient flow-through degradation and disinfection of wastewater
Ghasemzadeh et al. Heterostructured Ag@ MOF-801/MIL-88A (Fe) nanocomposite as a biocompatible photocatalyst for degradation of reactive black 5 under visible light
Zhao Research progress of semiconductor photocatalysis applied to environmental governance
Jiang et al. PVDF-based nanofiber membrane decorated with Z-scheme TiO2/MIL-100 (Fe) heterojunction for efficient oil/water emulsion separation and dye photocatalytic degradation
Shaheen et al. RETRACTED ARTICLE: Investigation on the role of graphene-based composites for in photocatalytic degradation of phenol-based compounds in wastewater: a review

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant