CN103991948B - Modified molecular screen is the method that catalyst treatment contains low-concentration perfluoro ammonium caprylate waste water - Google Patents
Modified molecular screen is the method that catalyst treatment contains low-concentration perfluoro ammonium caprylate waste water Download PDFInfo
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- CN103991948B CN103991948B CN201410206866.8A CN201410206866A CN103991948B CN 103991948 B CN103991948 B CN 103991948B CN 201410206866 A CN201410206866 A CN 201410206866A CN 103991948 B CN103991948 B CN 103991948B
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Abstract
The invention discloses a kind of modified molecular screen is the method that catalyst treatment contains low-concentration perfluoro ammonium caprylate waste water, the preparation of modified molecular screen: the mixing solutions of preparation containing cerous nitrate, lead nitrate, manganous nitrate or iron nitrate, molecular sieve be impregnated in mixing solutions, take out dry, roasting; Catalytic ozonation: by the modified molecular screen obtained and containing Perfluorocaprylic Acid ammonium concentration be 50 ~ 500mg/L, temperature is that the waste water of 20 ~ 100 DEG C is poured in container, pass into ozone, start stirring 30 ~ 120 minutes simultaneously; The recovery of modified molecular screen: obtain turbid solution through catalytic ozonation, by standing, centrifugal or filtration, separates modified molecular screen from solution, for catalytic oxidation process next time.The advantage of the method is that processing efficiency is high, easy and simple to handle, non-secondary pollution, and running cost is low.
Description
Technical field
The invention belongs to water treatment and environmental catalysis field, relate to a kind of method that modified molecular screen is catalyzer ozone oxidation degraded low-concentration perfluoro ammonium caprylate waste water.
Background technology
Along with the widespread use of organofluorine compound, ammonium perfluorocaprylate (being called for short PFOA) is as a kind of organofluoro surfactants of excellent property, normally for the production of processing aid indispensable during high-effect fluoropolymer, be widely applied in the production process of and electronic devices and components and various paint, coating etc. raw at resin, these high-effect fluoropolymers can be widely used in science and technology of aviation, transport, electron trade, and the people's livelihood articles for use such as kitchen tools.Such as to add a certain amount of dispersion agent ammonium perfluorocaprylate when dispersion method produces teflon resin, the last waste water produced in these production processes contains low dense Perfluorocaprylic Acid radical ion, usually only has about 0.1%, even lower, recovery value is low, process relative difficulty.Ammonium perfluorocaprylate is a kind of expensive efficient tensio-active agent, and physicochemical property is stablized, difficult for biological degradation, can discharge in the environment, enter human body accumulation, cause great murder by poisoning to human body with after the ammonium perfluorocaprylate decomposition of discharge of wastewater.Less to the treatment research of low-concentration perfluoro ammonium caprylate waste water both at home and abroad, the traditional separation method of main employing is as precipitation, vacuum distilling, anionresin etc., because the concentration of ammonium perfluorocaprylate in waste water is often very low, if adopted, exist and recycle difficulty, high, the facility investment of consuming energy is large and there is secondary pollution problem, if directly processed the carrying out of ammonium perfluorocaprylate waste water, the problems such as there is complex process again, recovery utilization rate is not high, industrialization difficulty.Therefore, it is very necessary for developing for carrying out advanced treatment process containing low-concentration perfluoro ammonium caprylate waste water, and existing considerable economic benefit, has again important Significance for Environment.
Summary of the invention
The present invention is directed to the deficiency that existing low-concentration perfluoro ammonium caprylate wastewater processing technology exists, mainly utilize modified molecular screen for catalyzer, by the ammonium perfluorocaprylate in catalytic ozonation degrading waste water.
Modified molecular screen is the method that catalyst treatment contains low-concentration perfluoro ammonium caprylate waste water, it is characterized in that, comprises following technical process:
(1) preparation of modified molecular screen: the mixing solutions of preparation containing cerous nitrate, lead nitrate, manganous nitrate or iron nitrate, 20 ~ 40 dried order molecular sieves to be impregnated in mixing solutions 3 ~ 6 hours, take out and to put at baking oven 60 ~ 120 DEG C of temperature dry 2 ~ 5 hours.Then retort furnace 450 ~ 600 DEG C of roastings 2 ~ 4 hours are placed in;
(2) catalytic ozonation: by the modified molecular screen obtained in step (1) and containing Perfluorocaprylic Acid ammonium concentration be 50 ~ 500mg/L, temperature is that the waste water of 20 ~ 100 DEG C is poured in container, pass into ozone, start stirring 30 ~ 120 minutes simultaneously;
(3) recovery of modified molecular screen: obtain turbid solution through catalytic ozonation, by standing, centrifugal or filtration, separates modified molecular screen from solution, for catalytic oxidation process next time.
Described molecular sieve is 13X molecular sieve, through modified molecular sieve component and mass percent is: the molecular sieve of 96 ~ 98%, the plumbous oxide of 1 ~ 3%, the cerium oxide of 1 ~ 3% and the manganese oxide of 0 ~ 3% or ferric oxide.
The advantage of the method is that special efficacy type is strong, technique is simple, with low cost, non-secondary pollution etc.
Embodiment
Below case study on implementation of the present invention is elaborated: the present embodiment is implemented under premised on technical solution of the present invention, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1:
(1) 5g cerous nitrate is taken and 4g lead nitrate adds in the deionized water of 100mL, stir and be mixed with nitrate mixed solution, 100g20 ~ 40 order molecular sieve to be impregnated in this solution 4 hours, taking-up to be put at baking oven 100 DEG C of temperature dry 6 hours, then retort furnace 600 DEG C of roastings 2 hours are placed in, obtain required modified molecular screen, wherein CeO
22% and 1% is respectively with the mass percentage content of PdO.
(2) by the modified molecular screen obtained in step (1) and containing Perfluorocaprylic Acid ammonium concentration be 300mg/L, temperature is that the 1000mL waste water of 40 DEG C is poured in container, pass into ozone, start stirring 60 minutes simultaneously, filter and modified molecular screen is separated from solution, in waste water after process, Perfluorocaprylic Acid ammonium concentration is 49mg/L, and clearance is 83.7%.
Embodiment 2:
(1) 5g cerous nitrate is taken and 6g lead nitrate adds in the deionized water of 100mL, stir and be mixed with nitrate mixed solution, 100g20 ~ 40 order molecular sieve to be impregnated in this solution 5 hours, taking-up to be put at baking oven 80 DEG C of temperature dry 4 hours, then retort furnace 400 DEG C of roastings 4 hours are placed in, obtain required modified molecular screen, wherein CeO
22% and 1.5% is respectively with the mass percentage content of PdO.
(2) by the modified molecular screen obtained in step (1) and containing Perfluorocaprylic Acid ammonium concentration be 500mg/L, temperature is that the 1000mL waste water of 40 DEG C is poured in container, pass into ozone, start stirring 80 minutes simultaneously, filter and modified molecular screen is separated from solution, in waste water after process, Perfluorocaprylic Acid ammonium concentration is 76mg/L, and clearance is 84.8%.
Embodiment 3:
(1) 3.78g cerous nitrate is taken and 4g lead nitrate adds in the deionized water of 100mL, stir and be mixed with nitrate mixed solution, 100g20 ~ 40 order molecular sieve to be impregnated in this solution 3 hours, taking-up to be put at baking oven 60 DEG C of temperature dry 5 hours, then retort furnace 500 DEG C of roastings 3 hours are placed in, obtain required modified molecular screen, wherein CeO
22% and 1.5% is respectively with the mass percentage content of PdO.
(2) by the modified molecular screen obtained in step (1) and containing Perfluorocaprylic Acid ammonium concentration be 200mg/L, temperature is that the 1000mL waste water of 30 DEG C is poured in container, pass into ozone, start stirring 50 minutes simultaneously, filter and modified molecular screen is separated from solution, in waste water after process, Perfluorocaprylic Acid ammonium concentration is 35mg/L, and clearance is 82.5%.
Embodiment 4:
(1) taking 5g cerous nitrate and 4g lead nitrate and 10.12g iron nitrate adds in the deionized water of 100mL, stir and be mixed with nitrate mixed solution, 100g20 ~ 40 order molecular sieve to be impregnated in this solution 4 hours, taking-up to be put at baking oven 100 DEG C of temperature dry 6 hours, then retort furnace 600 DEG C of roastings 2 hours are placed in, obtain required modified molecular screen, wherein CeO
2, PdO and Fe
2o
3mass percentage content be respectively 2%, 1% and 2%.
(2) by the modified molecular screen obtained in step (1) and containing Perfluorocaprylic Acid ammonium concentration be 300mg/L, temperature is that the 1000mL waste water of 40 DEG C is poured in container, pass into ozone, start stirring 60 minutes simultaneously, filter and modified molecular screen is separated from solution, in waste water after process, Perfluorocaprylic Acid ammonium concentration is 55mg/L, and clearance is 81.7%.
Embodiment 5:
(1) taking 5g cerous nitrate and 2.87g lead nitrate and 5.04g manganous nitrate adds in the deionized water of 100mL, stir and be mixed with nitrate mixed solution, 100g20 ~ 40 order molecular sieve to be impregnated in this solution 5 hours, taking-up to be put at baking oven 80 DEG C of temperature dry 4 hours, then retort furnace 400 DEG C of roastings 4 hours are placed in, obtain required modified molecular screen, wherein CeO
2, PdO and Fe
2o
3mass percentage content be respectively 2% and 1.5% and 2%.
(2) by the modified molecular screen obtained in step (1) and containing Perfluorocaprylic Acid ammonium concentration be 500mg/L, temperature is that the 1000mL waste water of 40 DEG C is poured in container, pass into ozone, start stirring 80 minutes simultaneously, filter and modified molecular screen is separated from solution, in waste water after process, Perfluorocaprylic Acid ammonium concentration is 62mg/L, and clearance is 87.6%.
Embodiment 6:
(1) taking 2.5g cerous nitrate, 1.26g lead nitrate and 10.1g manganous nitrate adds in the deionized water of 100mL, stir and be mixed with nitrate mixed solution, 100g20 ~ 40 order molecular sieve to be impregnated in this solution 3 hours, taking-up to be put at baking oven 60 DEG C of temperature dry 5 hours, then retort furnace 500 DEG C of roastings 3 hours are placed in, obtain required modified molecular screen, wherein CeO
2, PdO and MnO mass percentage content be respectively 2%, 1.5% and 4%.
(2) by the modified molecular screen obtained in step (1) and containing Perfluorocaprylic Acid ammonium concentration be 200mg/L, temperature is that the 1000mL waste water of 30 DEG C is poured in container, pass into ozone, start stirring 50 minutes simultaneously, filter and modified molecular screen is separated from solution, in waste water after process, Perfluorocaprylic Acid ammonium concentration is 26mg/L, and clearance is 87%.
Claims (2)
1. modified molecular screen is the method that catalyst treatment contains low-concentration perfluoro ammonium caprylate waste water, it is characterized in that, comprises following technical process:
(1) preparation of modified molecular screen: preparation contains the mixing solutions of cerous nitrate and lead nitrate, described mixing solutions is also containing manganous nitrate or iron nitrate, 20 ~ 40 dried order molecular sieves to be impregnated in mixing solutions 3 ~ 6 hours, take out and to put at baking oven 60 ~ 120 DEG C of temperature dry 2 ~ 5 hours;
Then retort furnace 450 ~ 600 DEG C of roastings 2 ~ 4 hours are placed in;
(2) catalytic ozonation: by the modified molecular screen obtained in step (1) and containing Perfluorocaprylic Acid ammonium concentration be 50 ~ 500mg/L, temperature is that the waste water of 20 ~ 100 DEG C is poured in container, pass into ozone, start stirring 30 ~ 120 minutes simultaneously;
(3) recovery of modified molecular screen: obtain turbid solution through catalytic ozonation, by standing, centrifugal or filtration, separates modified molecular screen from solution, for catalytic oxidation process next time.
2. modified molecular screen is the method that catalyst treatment contains low-concentration perfluoro ammonium caprylate waste water according to claim 1, it is characterized in that, described molecular sieve is 13X molecular sieve, through modified molecular sieve component and mass percent is: the molecular sieve of 96 ~ 98%, the plumbous oxide of 1 ~ 3%, the cerium oxide of 1 ~ 3% and the manganese oxide of 0 ~ 3% or ferric oxide.
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| EP3646946A1 (en) * | 2018-10-30 | 2020-05-06 | Helmholtz-Zentrum für Umweltforschung GmbH-UFZ | Method for the removal of polyfluorinated organic compounds from water by means of an adsorbent and regeneration thereof |
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| CN104289216B (en) * | 2014-09-09 | 2016-06-15 | 上海纳米技术及应用国家工程研究中心有限公司 | For the ozone catalyst of Surfactant-Catalyzed of degrading and preparation thereof and application |
| CN107876062A (en) * | 2017-11-06 | 2018-04-06 | 上海纳米技术及应用国家工程研究中心有限公司 | Ozone catalyst preparation method and products thereof and application |
| CN111185151B (en) * | 2020-01-20 | 2022-08-02 | 哈尔滨工业大学 | Heterogeneous ozone catalyst for efficiently treating acidic industrial wastewater and preparation method thereof |
| CN113842942B (en) * | 2021-11-01 | 2023-12-15 | 北京工业大学 | Preparation and application of Fe-Ce-LDH/13X particle type catalyst for heterogeneous electro-Fenton system |
| CN115121215B (en) * | 2022-07-11 | 2023-09-22 | 中山大学 | Preparation of cerium doped high-crystallization carbon nitride adsorbent and application thereof in adsorption of emerging pollutants |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1835794A (en) * | 2003-06-20 | 2006-09-20 | 大金工业株式会社 | Process for the recovery of surfactants |
| CN101460527A (en) * | 2006-04-11 | 2009-06-17 | 索维索莱克西斯公开有限公司 | Fluoropolymer dispersion purification |
| CN102276040A (en) * | 2004-02-05 | 2011-12-14 | 3M创新有限公司 | Removal of fluorinated surfactants from waste water |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1835794A (en) * | 2003-06-20 | 2006-09-20 | 大金工业株式会社 | Process for the recovery of surfactants |
| CN102276040A (en) * | 2004-02-05 | 2011-12-14 | 3M创新有限公司 | Removal of fluorinated surfactants from waste water |
| CN101460527A (en) * | 2006-04-11 | 2009-06-17 | 索维索莱克西斯公开有限公司 | Fluoropolymer dispersion purification |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3646946A1 (en) * | 2018-10-30 | 2020-05-06 | Helmholtz-Zentrum für Umweltforschung GmbH-UFZ | Method for the removal of polyfluorinated organic compounds from water by means of an adsorbent and regeneration thereof |
| WO2020089192A1 (en) * | 2018-10-30 | 2020-05-07 | Helmholtz-Zentrum Für Umweltforschung Gmbh - Ufz | Method for removing polyfluorinated organic compounds from water by means of an adsorbent and regeneration of the latter |
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