CN104909427B - A kind of light helps the member persulfate method for treating water of porous bismuthic acid - Google Patents
A kind of light helps the member persulfate method for treating water of porous bismuthic acid Download PDFInfo
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- CN104909427B CN104909427B CN201510234345.8A CN201510234345A CN104909427B CN 104909427 B CN104909427 B CN 104909427B CN 201510234345 A CN201510234345 A CN 201510234345A CN 104909427 B CN104909427 B CN 104909427B
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Abstract
The present invention provides a kind of light help the member persulfate wastewater treatment technology of advanced oxidation of porous bismuthic acid construct and application process, belong to water technology and environment functional material field.The shape of porous bismuthic acid copper can be powder or particle, using bismuth nitrate, copper nitrate and polyvinylpyrrolidone as main material, the high porous bismuthic acid copper product of specific surface area is prepared into, is improved and persulfate is activated under the conditions of light helps is generated free radicals degradation capability to cumarin.The present invention handles the problem of poor removal effect to cumarin for existing conventional sewage, it is proposed a kind of new porous bismuthic acid copper as catalyst, and realize its successful application in persulfate system, theoretical reference is provided for the removal technology of coumarin kind compound, scientific basis and technical support are provided to ensure that water quality safety improves aquatic environment.
Description
Technical field
The present invention relates to water pollution control technology and a kind of environment functional material.
Background technology
Coumarin kind compound is the quasi-aromatic compound for being widely present in nature, is distributed in many plants and perfume (or spice)
In material, also there is presence in animal and microbial metabolic products, its parent nucleus is benzo a pyranone structures.According to benzene ring substitution group
And its difference of position, cumarin can be divided into simple cumarin, furocoumarin, pyranocoumarin and other cumarins etc., be
A kind of important flavor potentiator, is widely used in the light industries such as perfume, cosmetics, detergent.Coumarin kind compound
While there is the pharmacological actions such as anti-hypertension and anticoagulation to human body, it may have the harm to organism physiological-toxicity is made
With as part coumarin kind compound can trigger hepatic injury.With coumarin kind compound output, usage amount and discharge capacity
Constantly increase, coumarin kind compound content significantly increases in water environment, is proposed to China's sanitary sewage disposal and reuse technology
New challenge.Therefore, carry out basic theory and the application study for coumarin kind compound removal technology, ensure water quality peace
Entirely, there is highly important theoretical and realistic meaning.
High-level oxidation technology relies primarily on the extremely strong oxygen radical of activity and carrys out Recalcitrant chemicals in oxygenolysis water.Its
In, activation persulfate high-level oxidation technology is one kind developed in recent years using potentiometric titrations as main active substances
The advanced oxidation technology of degradation of contaminant.Potentiometric titrations oxidability is relatively strong, oxidation non-selectivity, its oxidation product
Sulfate radical is smaller for microorganism, Aquatic organisms in water environment.The ability of persulfate oxidation stain material itself is limited,
Reaction is slow, and under the conditions of light, heat, sound, transition metal ions and catalyst etc., persulfate can be reinforced and be decomposed into sulfate radical
Free radical, realizes efficient degradation and the detoxification of pollutant.
Bismuthic acid copper with spinel structure is as a kind of typical p-type semiconductor material, due to wider band gap
Attracted attention with good photocatalysis performance.Research finds that bismuthic acid copper is that a kind of visible ray of function admirable is urged
Change material, possess the energy gap of 1.5eV；Its magnetism, dielectric property, optical characteristics and photoelectric characteristic have been widely studied.
Bismuthic acid copper has superpower visible light-responded performance in very wide wave-length coverage, and has good heat endurance and certain journey
The luminescent properties of degree, so a kind of promising smooth co-catalyst can be used as.By introducing surface in bismuthic acid copper preparation process
Activating agent polyvinylpyrrolidone, prepares the porous bismuthic acid copper with high surface area and flourishing duct, can further strengthen
Catalytic performance of the bismuthic acid copper under the conditions of light helps.Therefore, in advanced oxidation system using porous bismuthic acid copper as catalyst,
Light activates persulfate under the conditions of helping, and photocatalysis is produced hydroxyl radical free radical produces the free base of sulfate with activation persulfate
Position coupling, realizes that the reinforcing of persistent organic pollutants removes, and helps the application of activation persulfate to provide theoretical reference for light.
The content of the invention
The present invention is for the problem that the polluted-water containing cumarin, to solve existing conventional sewage poor processing effect, wound
New property proposing a kind of light helps the member persulfate method for treating water of porous bismuthic acid, and to the system of porous bismuthic acid copper catalyst
Standby and application conditions illustrate.The porous bismuthic acid copper of catalyst prepared by the present invention, it is special using its characteristic crystal structure, dual element
The multiple feature of point, higher specific surface area and flourishing duct, persulfate is activated under the conditions of light helps and produces sulfate radical freedom
Base, realizes that the reinforcing to Recalcitrant chemicals removes.
The present invention provides a kind of light and helps the member persulfate method for treating water of porous bismuthic acid, it is characterised in that (one) utilizes
Bismuthic acid copper characteristic crystal structure and dual element feature, produce hydroxyl radical free radical by photocatalysis and produce sulfate with activation persulfate
Free radical coupling in situ, realizes that the reinforcing of persistent organic pollutants removes；By introducing surface in bismuthic acid copper preparation process
Activating agent, improves its specific surface area, expands duct, further strengthen the energy that bismuthic acid copper activates persulfate under the conditions of light helps
Power, realizes efficient mineralization and the detoxification of persistent organic pollutants；It is characterized in that (two) can complete to make by following process
It is standby：(1) prepared by precursor solution, and it is molten that the bismuth nitrate that quality is 0.01mol is dissolved in the nitric acid that 20mL concentration is 0.5mol/L
In liquid, lasting stirring is completely dissolved bismuth nitrate；The copper nitrate that quality is 0.005mol, lasting stirring are added into above-mentioned solution
It is completely dissolved bismuth nitrate；Polyvinylpyrrolidone 0.167g is added into above-mentioned solution, lasting stirring makes bismuth nitrate completely molten
Solution；(2) prepared by precipitating reagent, and the sodium hydroxide that quality is 40.0g is added in 40mL water, forms the hydrogen-oxygen that concentration is 25.0mol/L
Change sodium solution；(3) precipitate, precipitating reagent in (2) be dropwisely added in the precursor solution prepared by (1), form mixed precipitation,
Untill when pH value of solution reaches 13.45；(4) aging, precipitation of gained will be prepared in (3), be placed in room temperature place 12 it is small when；
(5) wash, using gained precipitation in deionized water and ethanol washing (4), remove wherein excessive sodium hydrate and inorganic salts.This mistake
Journey is repeated several times, untill precipitation supernatant electrical conductivity is constant；(6) dry, it is small that drying 24 at 70 DEG C will be deposited in obtained by (5)
When, obtain dried powder；(7) calcine, powder obtained by (6) is calcined in high temperature Muffle furnace, furnace temperature is risen with the speed of 1 DEG C/min
To 550 DEG C, when persistently calcining 6 is small；(8) cool down, be naturally cooling to room temperature.
The present invention provides a kind of light and helps the member persulfate method for treating water of porous bismuthic acid, it is characterised in that (three) work
Skill is realized by following technological parameter：(1) ultraviolet light 360nm needed for technique；(2) persulfate concentration needed for technique is 0
~10mmol/L；(3) porous bismuthic acid copper throwing amount is 1.0g/L needed for technique；(4) pollutant concentration is 0.08 in staying water
~0.12mmol/L；(5) time of contact is 160~200min；(6) reaction system pH scopes are 2.63~11.00.
Accompanying drawing content
Attached drawing is that the light that embodiment one obtains is helped in the member persulfate system of porous bismuthic acid to cumarin
Efficiency figure is removed, wherein the removal efficiency figure of × expression 360nm light degradation cumarins, ◆ represent 360nm UV activation over cures
The removal efficiency figure of hydrochlorate, ■ represent that light helps the removal efficiency figure of the member persulfate of bismuthic acid, ▲ represent that light helps porous bismuthic acid
The removal efficiency figure of member persulfate.It can be seen from the figure that light helps the member persulfate oxidation of porous bismuthic acid to remove
The more simple ultraviolet degradation of cumarin, UV activation persulfate, light help the member persulfate of bismuthic acid to remove cumarin
Efficiency significantly improves, and realizes the reinforcing to cumarin in water body and removes.
Embodiment
The member persulfate method for treating water of porous bismuthic acid is helped to illustrate this light, technical solution of the present invention not office
It is limited to the embodiment of act set forth below, further includes any combination between each embodiment.
Embodiment one：The preparation method of the porous bismuthic acid copper of present embodiment is：(1) prepared by precursor solution, will
The bismuth nitrate that quality is 0.01mol is dissolved in the salpeter solution that 20mL concentration is 0.5mol/L, and lasting stirring makes bismuth nitrate complete
Fully dissolved；The copper nitrate that quality is 0.005mol is added into above-mentioned solution, lasting stirring is completely dissolved bismuth nitrate；To above-mentioned
Polyvinylpyrrolidone 0.167g is added in solution, lasting stirring is completely dissolved bismuth nitrate；(2) prepared by precipitating reagent, and quality is
The sodium hydroxide of 40.0g is added in 40mL water, forms the sodium hydroxide solution that concentration is 25.0mol/L；(3) precipitate, by (2)
Precipitating reagent is dropwisely added in the precursor solution prepared by (1), is formed mixed precipitation, is when pH value of solution reaches 13.45
Only；(4) aging, precipitation of gained will be prepared in (3), be placed in room temperature place 12 it is small when；(5) wash, using deionized water and second
Gained precipitation in alcohol washing (4), removes wherein excessive sodium hydrate and inorganic salts.This process is repeated several times, until precipitating supernatant
Untill liquid electrical conductivity is constant；(6) dry, will be deposited in obtained by (5) at 70 DEG C dry 24 it is small when, obtain dried powder；(7) calcine,
Powder obtained by (6) is calcined in high temperature Muffle furnace, furnace temperature rises to 550 DEG C with the speed of 1 DEG C/min, when persistently calcining 6 is small；
(8) cool down, be naturally cooling to room temperature.
The application of porous bismuthic acid copper prepared by present embodiment in persulfate water technology is activated under the conditions of light helps
Method is：Under 360nm ultraviolet light conditions, add porous bismuthic acid copper catalyst activation persulfate and carry out oxidation processes.Light helps
Technology is decontaminated in the porous member persulfate system of bismuthic acid to realize according to following steps：(1) ultraviolet light 360nm needed for technique；
(2) persulfate concentration needed for technique is 0~10mmol/L；(3) porous bismuthic acid copper throwing amount is 1.0g/L needed for technique；(4) treat
It is 0.08~0.12mmol/L to handle pollutant concentration in water body；(5) time of contact is 160~200min；(6) reaction system pH
Scope is 2.63~11.00.
Heat treatment red mud O3 catalytic oxidation used in present embodiment remove the method for treating water of Organic substance in water with
The existing ozone oxidation system of water factory is identical, and polluted water body pretreatment and subsequent treatment process use existing process completely,
Without water treatment facilities.Present embodiment O3 catalytic oxidation reactor can be batch reactor, or continuous reaction
Device or multi-cascade reaction system.
Embodiment two：The present embodiment is different from the first embodiment in that light helps the member mistake of porous bismuthic acid
Sulfate decontaminates application process of the dyeing technique in water process：City domestic sewage passes through grid-setting pot-primary sedimentation tank-life
After changing pond-secondary settling tank processing, then carry out light and help the member persulfate processing of porous bismuthic acid, then water outlet.
Embodiment three：The present embodiment is different from the first embodiment in that light helps the member mistake of porous bismuthic acid
Sulfate decontaminates application process of the dyeing technique in water process：Industrial wastewater by grid-setting pot-primary sedimentation tank-biochemistry pool-
After secondary settling tank processing, then carry out light and help the member persulfate processing of porous bismuthic acid, then water outlet.
The porous bismuthic acid copper catalyst being prepared in present embodiment is under the conditions of light helps, by activating persulfate pair
For the removal rate of cumarin up to more than 60%, more simple ultraviolet degradation, UV activation persulfate, light help the member mistake of bismuthic acid
The efficiency that sulfate removes cumarin significantly improves, and realizes the reinforcing to cumarin in water body and removes.
Claims (1)
1. a kind of light helps the member persulfate method for treating water of porous bismuthic acid, it is characterised in that：(1) by standby in bismuthic acid copper
Surfactant is introduced in technique, its specific surface area is improved, expands duct, strengthens bismuthic acid copper and activates persulfuric acid under the conditions of light helps
The ability of salt；(2) bismuthic acid copper characteristic crystal structure and dual element feature are utilized, photocatalysis is produced into hydroxyl radical free radical and was activated
Sulfate produces potentiometric titrations coupling in situ, realizes that the reinforcing of persistent organic pollutants removes；Wherein, porous bismuthic acid copper
Complete to prepare by following process：
(1) prepared by precursor solution, and it is molten that the bismuth nitrate that quality is 0.01mol is dissolved in the nitric acid that 20mL concentration is 0.5mol/L
In liquid, lasting stirring is completely dissolved bismuth nitrate；The copper nitrate that quality is 0.005mol is added into above-mentioned solution, is persistently stirred
Mix, obtain settled solution；Polyvinylpyrrolidone 0.167g is added into above-mentioned settled solution, lasting stirring, obtains clear again
Clear solution；
(2) prepared by precipitating reagent, and the sodium hydroxide that quality is 40.0g is added in 40mL water, forms the hydrogen-oxygen that concentration is 25.0mol/L
Change sodium solution；
(3) precipitate, precipitating reagent in (2) is dropwisely added in the precursor solution prepared by (1), form mixed precipitation, until
Untill when pH value of solution reaches 13.45；
(4) aging, precipitation of gained will be prepared in (3), be placed in room temperature place 12 it is small when；
(5) wash, using gained precipitation in deionized water and ethanol washing (4), remove wherein excessive sodium hydrate and inorganic salts；
This process is repeated several times, untill precipitation supernatant electrical conductivity is constant；
(6) dry, will be deposited in obtained by (5) at 70 DEG C dry 24 it is small when, obtain dried powder；
(7) calcine, powder obtained by (6) is calcined in high temperature Muffle furnace, furnace temperature rises to 550 DEG C with the speed of 1 DEG C/min, holds
When continuous calcining 6 is small；
(8) cool down, be naturally cooling to room temperature；
Helped using the porous bismuthic acid copper of above-mentioned preparation, and applied to light in activation persulfate method for treating water, pass through following bar
Part is realized：
(1) ultraviolet light 360nm；
(2) persulfate concentration needed for technique is 0~10mmol/L；
(3) porous bismuthic acid copper throwing amount is 1.0g/L needed for technique；
(4) pollutant concentration is 0.08~0.12mmol/L in staying water；
(5) time of contact is 160~200min；
(6) reaction system pH scopes are 2.63~11.00.
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105233837B (en) * | 2015-10-29 | 2018-02-09 | 苏州耐德新明和工程技术有限公司 | A kind of modified bismuthic acid bronzing catalyst and preparation method thereof |
| CN106944043B (en) * | 2017-03-17 | 2019-07-09 | 佛山科学技术学院 | A kind of micro-nano hetero-junctions visible light composite photocatalyst and its preparation method and application |
| CN108246306B (en) * | 2018-02-08 | 2020-07-24 | 秦英皓 | One-pot synthesis of photocatalyst CuBi with visible light response2O4/Bi2WO6Nanosphere and application thereof |
| CN108928993A (en) * | 2018-06-22 | 2018-12-04 | 安徽工程大学 | A kind of removal device and method of the waste water containing bisphenol-A |
| CN111482150B (en) * | 2020-04-22 | 2022-07-19 | 上海市普陀区人民医院(上海纺织第一医院) | Visible light response all-copper-based series photoelectric catalytic device and preparation method thereof |
| CN111468138B (en) * | 2020-05-27 | 2021-11-30 | 辽宁大学 | One-dimensional rod-shaped CuBi2O4@CuBi2S4Visible light catalyst and preparation method and application thereof |
| CN112536039B (en) * | 2020-12-03 | 2021-09-17 | 浙江大学 | Preparation method of visible light catalytic material of composite oxide with hierarchical structure |
| CN113504221B (en) * | 2021-07-06 | 2023-12-08 | 中国农业科学院烟草研究所 | Application of tea extract in sulfate radical detection |
| CN113600173B (en) * | 2021-08-09 | 2022-11-01 | 中山大学 | Application of bismuth catalyst in sterilization and disinfection by activating persulfate |
| CN115779914B (en) * | 2022-12-05 | 2024-05-24 | 河南科技学院 | Copper bismuthate/calcium bismuthate composite material, preparation method and application thereof in photocatalytic plastic conversion of hydrocarbon fuel |
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