CN107973366A - One kind utilizes persulfuric acid hydrogen salt and photochemical catalyst BiVO4The method of purifying dyestuff waste water - Google Patents
One kind utilizes persulfuric acid hydrogen salt and photochemical catalyst BiVO4The method of purifying dyestuff waste water Download PDFInfo
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- CN107973366A CN107973366A CN201711251158.6A CN201711251158A CN107973366A CN 107973366 A CN107973366 A CN 107973366A CN 201711251158 A CN201711251158 A CN 201711251158A CN 107973366 A CN107973366 A CN 107973366A
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- persulfuric acid
- water
- acid hydrogen
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- hydrogen salt
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
One kind utilizes persulfuric acid hydrogen salt and photochemical catalyst BiVO4The method of purifying dyestuff waste water, it is related to a kind of photochemical catalyst under oxidant persulfuric acid hydrogen salt synergistic effect, utilizes the method for visible light catalytic processing waste water from dyestuff.The invention aims to solve the problems, such as that existing waste water from dyestuff purified treatment cost is higher low with removal rate.Method：（1）Persulfuric acid hydrogen salt is mixed with the pretreated water containing dyestuff；（2）Adjust pH value in reaction；（3）Photochemical catalyst is added in pretreated water；（4）Mixed solution is irradiated using visible light source；（5）Separate photochemical catalyst BiVO4.Dyestuff in water removal is gone to can reach 85%~95% using the method for the present invention.The present invention can effectively realize that waste water from dyestuff purifies.
Description
Technical field
The present invention relates to a kind of method for treating water.
Background technology
Industrial dye waste water is the main source of water pollution.The dyestuffs such as rhodamine B, methyl orange are due to bright in colour, fixation
The features such as rate is high, dyefastness is good and be widely used as industrial dye, and dosage is very big.But waste water from dyestuff due to colourity is high,
Strong toxicity, difficult degradation, and it is easily carcinogenic and become an important problem of environmental pollution.Its rhodamine B with Typical Representative etc.
Common industrial type dye, has preferable water solubility, is easy to analyze, and is widely used in the dyeing of the fabrics such as manufacture paint and acrylic fibers
And the dyeing of biological products, be directly discharged into water to organism produce toxicity it is larger, serious prestige is also brought to health
The side of body.Conventional physical treatment process, method of chemical treatment and biological treatment all cannot effectively realize the degraded of waste water from dyestuff.Therefore,
Urgently exploitation new processing method realizes the degraded of waste water from dyestuff.In recent years, the high-level oxidation technology based on potentiometric titrations
It is widely used in the research of stain disease processing.Ultraviolet light（UV）, heat, the persulfate of the technique such as metal ion activation, molecule
Internal peroxide bridge can break to form potentiometric titrations, its oxidability is suitable with hydroxyl radical free radical, and with selectivity more
By force, the advantages that half-life period is longer.On the other hand there is degradation efficiency using solar energy photocatalytic degraded Industry Waste Organic substance in water
High, the advantages that salinity is high, easy to operate, easily controllable, non-secondary pollution, there are tremendous expansion potentiality.
In today that environmental energy problem becomes increasingly conspicuous, Photocatalitic Technique of Semiconductor relies on its energy saving, efficient, safety, nothing
The characteristics such as poison are shown one's talent in numerous high-level oxidation technologies, are at present TiO with most photocatalyst materials2。BiVO4Make
For a kind of newer conductor photocatalysis material, sunlight catalytic can be utilized, there is non-toxic, high stability, be
A kind of environment-friendly type semiconductor catalyst of function admirable, has broad application prospects.BiVO4Have one under visible light conditions
Fixed catalytic activity, compensate for TiO2Equivalence classes catalyst can not under visible light photocatalysis degradation organic contaminant lack
Point, and improve the removal rate of pollutant.So far, there is not yet based on potentiometric titrations collaboration BiVO4Light degradation water
The patent and paper of middle pollutant.
The content of the invention
The invention aims to solve the problems, such as that existing dye wastewater treatment process efficiency is low, complex process, carry
Persulfuric acid hydrogen salt and photochemical catalyst BiVO are utilized for one kind4The method of purifying dyestuff waste water.
One kind utilizes persulfuric acid hydrogen salt and photochemical catalyst BiVO4The method of purifying dyestuff waste water, specifically according to the following steps
Complete：
First, persulfuric acid hydrogen salt is mixed with the pretreated water containing dyestuff：Persulfuric acid hydrogen salt is mixed with the water pre-processed, then
At room temperature with mixing speed to stir 20min ~ 45min under conditions of the r/min of 160 r/min ~ 250, obtain persulfuric acid hydrogen salt and
The mixed solution of pretreated water；
Persulfuric acid hydrogen salt described in step 1 is in potassium hydrogen persulfate, hydrogen persulfate ammonium, hydrogen persulfate sodium and hydrogen persulfate calcium
One kind or wherein several mixtures；
The mass ratio of the quality of persulfuric acid hydrogen salt described in step 1 and the water of pretreatment is 1:(1000~10000)；
The dye strength in pretreated water described in step 1 is 1~1000 mg/L：
2nd, reaction pH values are adjusted：Low whipping speed under conditions of the r/min of 150 r/min~200 using 0.1 mol/L ~
The sodium hydroxide solution of the mol/L of the perchloric acid of 100 mol/L and 0.1 mol/L ~ 100 is by persulfuric acid hydrogen salt and pretreated water
The pH values of mixed solution adjust to 6.5 ~ 7.5, the mixing of persulfuric acid hydrogen salt and pretreated water after adjusted pH values is molten
Liquid；
3rd, photochemical catalyst is added in pretreated water：By photochemical catalyst BiVO4The hydrogen persulfate being added to after adjusting pH values
In the mixed solution of salt and pretreated water, the magnetic force under conditions of room temperature and mixing speed is the r/min of 160 r/min~250
The min of 5 min~10 is stirred, obtains the mixing suspension solution of waste water from dyestuff；
Photochemical catalyst BiVO described in step 34Dosage be the g/L of 0.01 g/L ~ 50.0；
4th, mixed solution is irradiated using visible light source：It is irradiated using mixing suspension solution of the visible ray to waste water from dyestuff, instead
After the min of 10 min between seasonable ~ 240, obtain containing photochemical catalyst BiVO4Water；
A length of 420 ~ 700 nm of visible light wave in step 4；
The visible light source power in step 4 is the W of 100 W ~ 1000；
5th, photochemical catalyst BiVO is separated4：Aperture is used to contain photochemical catalyst BiVO for 0.45 μm of glass fibre membrane4Water
Filtered, obtain removing the water of dyestuff.
The principle of the present invention：
In photochemical catalyst BiVO in the present invention4Surface under visible light illumination, positioned at the photoelectron transition of forbidden band, forms hole electricity
Son is right（h+-eCB -）.BiVO in reaction system4The photoelectron on surface and the HSO in persulfuric acid hydrogen salt5 -Or SO5 2-Generation electronics turns
Move, so that persulfuric acid hydrogen radical is cracked into SO4 -With OH-；In addition, the O in solution2It is same raw under photoelectron effect
Into the superoxide radical reactive oxygen species with strong oxidizing property, the purification rate of dye molecule is accelerated；On the other hand stop
In photochemical catalyst BiVO4The hole on surface has strong oxidizing property, can further speed up the oxidative degradation of target organic.
Embodiment
Embodiment one：Present embodiment is that one kind utilizes persulfuric acid hydrogen salt and photochemical catalyst BiVO4Purifying dyestuff
The method of waste water is completed according to the following steps：
First, persulfuric acid hydrogen salt is mixed with the pretreated water containing dyestuff：Persulfuric acid hydrogen salt is mixed with the water pre-processed, then
At room temperature with mixing speed to stir 20min ~ 45min under conditions of the r/min of 160 r/min ~ 250, obtain persulfuric acid hydrogen salt and
The mixed solution of pretreated water；
Persulfuric acid hydrogen salt described in step 1 is in potassium hydrogen persulfate, hydrogen persulfate ammonium, hydrogen persulfate sodium and hydrogen persulfate calcium
One kind or wherein several mixtures；
The mass ratio of the quality of persulfuric acid hydrogen salt described in step 1 and the water of pretreatment is 1:(1000~10000)；
The dye strength in pretreated water described in step 1 is 1~1000 mg/L：
2nd, reaction pH values are adjusted：Low whipping speed under conditions of the r/min of 150 r/min~200 using 0.1 mol/L ~
The sodium hydroxide solution of the mol/L of the perchloric acid of 100 mol/L and 0.1 mol/L ~ 100 is by persulfuric acid hydrogen salt and pretreated water
The pH values of mixed solution adjust to 6.5 ~ 7.5, the mixing of persulfuric acid hydrogen salt and pretreated water after adjusted pH values is molten
Liquid；
3rd, photochemical catalyst is added in pretreated water：By photochemical catalyst BiVO4The hydrogen persulfate being added to after adjusting pH values
In the mixed solution of salt and pretreated water, the magnetic force under conditions of room temperature and mixing speed is the r/min of 160 r/min~250
The min of 5 min~10 is stirred, obtains the mixing suspension solution of waste water from dyestuff；
Photochemical catalyst BiVO described in step 34Dosage be the g/L of 0.01 g/L ~ 50.0；
4th, mixed solution is irradiated using visible light source：It is irradiated using mixing suspension solution of the visible ray to waste water from dyestuff, instead
After the min of 10 min between seasonable ~ 240, obtain containing photochemical catalyst BiVO4Water；
A length of 420 ~ 700 nm of visible light wave in step 4；
The visible light source power in step 4 is the W of 100 W ~ 1000；
5th, photochemical catalyst BiVO is separated4：Aperture is used to contain photochemical catalyst BiVO for 0.45 μm of glass fibre membrane4Water
Filtered, obtain removing the water of dyestuff.
The principle of present embodiment：
In photochemical catalyst BiVO in present embodiment4Surface under visible light illumination, positioned at the photoelectron transition of forbidden band, is formed empty
Cave electronics pair（h+-eCB -）.BiVO in reaction system4The photoelectron on surface and the HSO in persulfuric acid hydrogen salt5 -Or SO5 2-Generation electricity
Son transfer, so that single over cure acid group is cracked into SO4 -With OH-；In addition, the O in solution2Under photoelectron effect, together
Sample generates the superoxide radical reactive oxygen species with strong oxidizing property, accelerates the purification rate of dye molecule；On the other hand
Rest on photochemical catalyst BiVO4The hole on surface has strong oxidizing property, can further speed up the oxidative degradation of target organic.
The advantages of present embodiment：
First, present embodiment is easy to operate, and degradation by-products are nontoxic；
2nd, present embodiment is to be reacted at normal temperatures and pressures, saves the energy, and the method phase of the dyestuff in water removal is gone with other
Than reducing cost 45% ~ 70%；
3rd, the visible light catalyst synthesized by present embodiment can be easier to recycle and regenerate；
4th, present embodiment has good removal rate to dyestuff in water, and up to 80%~95%.
Embodiment two：Present embodiment is with one difference of embodiment：Pre- place described in step 1
The dyestuff managed in water is rhodamine B, methyl orange, methyl blue, orange red 7, methylene blue, it is Congo red in one or more of mixing
Thing.Other steps are identical with embodiment one.
Embodiment three：Present embodiment is with one of embodiment one or two difference：Institute in step 1
The mass ratio of the quality for the persulfuric acid hydrogen salt stated and the water of pretreatment is 1:(1000 ~ 5000), other steps and specific embodiment party
Formula one or two is identical.
Embodiment four：Present embodiment is with one of embodiment one to three difference：Institute in step 1
The mass ratio of the quality for the persulfuric acid hydrogen salt stated and the water of pretreatment is 1:(5000 ~ 8000), other steps and specific embodiment party
Formula one to three is identical.
Embodiment five：Present embodiment is with one of embodiment one to four difference：Institute in step 3
The BiVO stated4Dosage be the g/L of 0.01 g/L ~ 0.1, other steps are identical with embodiment one to four.
Embodiment six：Present embodiment is with one of embodiment one to five difference：Institute in step 3
The BiVO stated4Dosage be the g/L of 0.1 g/L ~ 10, other steps are identical with embodiment one to five.
Embodiment seven：Present embodiment is with one of embodiment one to six difference：In step 4
A length of 500 ~ 700 nm of visible light wave, other steps are identical with embodiment one to six.
Embodiment eight：Present embodiment is with one of embodiment one to seven difference：Can in step 4
See that radiant power is identical with embodiment one to seven for the W of 300 W ~ 1000, other steps.
Beneficial effects of the present invention are verified using tests below：
Experiment one：A kind of method using persulfuric acid hydrogen salt and visible light catalyst purifying dyestuff waste water
First, persulfuric acid hydrogen salt is mixed with the pretreated water containing dyestuff, then at room temperature with mixing speed for 160 r/min ~
The min of 20 min ~ 45 is stirred under conditions of 250 r/min, obtains the mixed solution of persulfuric acid hydrogen salt and pretreated water；
Persulfuric acid hydrogen salt described in step 1 is potassium hydrogen persulfate；
The dyestuff in pretreated water described in step 1 is rhodamine B；
The concentration of dyestuff is 20 mg/L in pretreated water described in step 1：
The mass ratio of the quality of persulfuric acid hydrogen salt described in step 1 and the water of pretreatment is 1:2000；
2nd, reaction pH values are adjusted：Low whipping speed under conditions of the r/min of 150 r/min~200 using 0.1 mol/L ~
The sodium hydroxide solution of the mol/L of the perchloric acid of 100 mol/L and 0.1 mol/L ~ 100 is by persulfuric acid hydrogen salt and pretreated water
The pH values of mixed solution adjust to 6.5 ~ 7.5, the mixing of persulfuric acid hydrogen salt and pretreated water after adjusted pH values is molten
Liquid；
3rd, photochemical catalyst is added in pretreated water：By photochemical catalyst BiVO4The hydrogen persulfate being added to after adjusting pH values
In the mixed solution of salt and pretreated water, the magnetic force under conditions of room temperature and mixing speed is the r/min of 160 r/min~250
The min of 5 min~10 is stirred, obtains the mixing suspension solution of waste water from dyestuff；
Photochemical catalyst BiVO described in step 34Dosage be 0.1 g/L；
4th, mixed solution is irradiated using visible light source：It is irradiated using mixing suspension solution of the visible ray to waste water from dyestuff, instead
Between seasonable after 30 min, obtain containing photochemical catalyst BiVO4Water；
A length of 500 nm of visible light wave in step 4；
The visible light source power in step 4 is 300 W；
5th, photochemical catalyst BiVO is separated4：Aperture is used to contain photochemical catalyst BiVO for 0.45 μm of glass fibre membrane4Water
Filtered, obtain removing the water after dyestuff.
The advantages of this experiment：
First, this test operation is simple, and degradation by-products are nontoxic；
2nd, this experiment is to be reacted at normal temperatures and pressures, saves the energy, compared with the method that other remove the dyestuff in water removal,
Reduce cost 50%；
3rd, the synthesized visible light catalyst of this experiment can be easier to recycle and regenerate；
4th, this experiment has good removal rate up to 98% to dyestuff in water.
Experiment two：The contrast test of dyestuff in water removal is gone using activated carbon, is specifically realized by the following steps：
24 h of dyestuff in pretreated water is adsorbed for the coconut husk granular activated carbon of the nm of 4 nm ~ 100 using particle diameter, obtains removing dye
Water after material；
Dyestuff is rhodamine B in the pretreated water, and the concentration of rhodamine B is 20 mg/L；
Removal in experiment two using particle diameter for dyestuff in the coal quality granular activated carbon Adsorption pretreated water of the nm of 4 nm ~ 100
Rate is 53%.
Experiment three：Use ultraviolet light and H2O2The contrast test of purifying dyestuff waste water, is specifically realized by the following steps：
The H that concentration is 2 mg/L is added into the water of pretreatment2O2, in 250 μ W/cm of ultraviolet light intensity2Ultraviolet light locate in advance
0.5 h of water of reason, obtains removing the water after dyestuff；
Dyestuff is rhodamine B in the pretreated water, and the concentration of rhodamine B is 20 mg/L；
Experiment three uses ultraviolet light and H2O2The removal rate for removing dyestuff in pretreated water is 68%.
Experiment four：The contrast test of dyestuff in water is removed using persulfuric acid hydrogen salt, is specifically realized by the following steps：
The persulfuric acid hydrogen salt of 2 mg/L is added into pretreated water, reacts 2 h, obtains removing the water after dyestuff；
Dyestuff is rhodamine B in the pretreated water, and the concentration of rhodamine B is 20 mg/L；
Experiment four is 12% using the removal rate that persulfuric acid hydrogen salt removes dyestuff in pretreated water.
Experiment five：Use visible ray and catalyst BiVO4The contrast test of purifying dyestuff waste water, specifically according to the following steps
Complete：
The catalyst BiVO that concentration is 100 mg/L is added into the water of pretreatment4, 1.0 h are handled using radiation of visible light, are obtained
Water to after removal dyestuff；
Dyestuff is rhodamine B in the pretreated water, and the concentration of rhodamine B is 20 mg/L；
Experiment five uses visible ray and catalyst BiVO4The removal rate of dyestuff is 27% in pretreated water.
Experiment two goes dyestuff in water removal, experiment three to use ultraviolet and H using cocoanut active charcoal2O2Go dyestuff in water removal, experiment
Four remove dyestuff and experiment five in water using persulfuric acid hydrogen salt uses visible ray and catalyst BiVO4Go the removal of dyestuff in water removal
Rate is respectively 53%, 68%, 12% and 27%, and the removal rate of experiment one is 98%, it was demonstrated that experiment one is contaminated for removing in pretreated water
Expect excellent.
Claims (8)
1. one kind utilizes persulfuric acid hydrogen salt and photochemical catalyst BiVO4The method of purifying dyestuff waste water, it is characterised in that one kind utilized
Disulfate and photochemical catalyst BiVO4The method of purifying dyestuff waste water comprises the steps of：
First, persulfuric acid hydrogen salt is mixed with the pretreated water containing dyestuff：Persulfuric acid hydrogen salt is mixed with the water pre-processed, then
At room temperature persulfuric acid hydrogen salt is obtained to stir the min of 20 min ~ 45 under conditions of the r/min of 160 r/min ~ 250 with mixing speed
With the mixed solution of pretreated water；
Persulfuric acid hydrogen salt described in step 1 is in potassium hydrogen persulfate, hydrogen persulfate ammonium, hydrogen persulfate sodium and hydrogen persulfate calcium
One kind or wherein several mixtures；
The mass ratio of the quality of persulfuric acid hydrogen salt described in step 1 and the water of pretreatment is 1:(1000~10000)；
The dye strength in pretreated water described in step 1 is 1~1000 mg/L：
2nd, reaction pH values are adjusted：Low whipping speed under conditions of the r/min of 150 r/min~200 using 0.1 mol/L ~
The sodium hydroxide solution of the mol/L of the perchloric acid of 100 mol/L and 0.1 mol/L ~ 100 is by persulfuric acid hydrogen salt and pretreated water
The pH values of mixed solution adjust to 6.5 ~ 7.5, the mixing of persulfuric acid hydrogen salt and pretreated water after adjusted pH values is molten
Liquid；
3rd, photochemical catalyst is added in pretreated water：By photochemical catalyst BiVO4The persulfuric acid hydrogen salt being added to after adjusting pH values
In the mixed solution of pretreated water, magnetic force stirs under conditions of room temperature and mixing speed is the r/min of 160 r/min~250
The min of 5 min~10 is mixed, obtains the mixing suspension solution of waste water from dyestuff；
Photochemical catalyst BiVO described in step 34Dosage be the g/L of 0.01 g/L ~ 50.0；
4th, mixed solution is irradiated using visible light source：It is irradiated using mixing suspension solution of the visible ray to waste water from dyestuff, instead
After the min of 10 min between seasonable ~ 240, obtain containing photochemical catalyst BiVO4Water；
A length of 420 ~ 700 nm of visible light wave in step 4；
The visible light source power in step 4 is the W of 100 W ~ 1000；
5th, photochemical catalyst BiVO is separated4：Aperture is used to contain photochemical catalyst BiVO for 0.45 μm of glass fibre membrane4Water
Filtered, obtain removing the water of dyestuff.
2. one kind according to claim 1 utilizes persulfuric acid hydrogen salt and photochemical catalyst BiVO4The method of purifying dyestuff waste water,
It is characterized in that the dyestuff in pretreated water described in step 1 is rhodamine B, methyl orange, methyl blue, orange red 7, methylene
One kind or wherein several mixtures in blue, Congo red.
3. one kind according to claim 1 utilizes persulfuric acid hydrogen salt and photochemical catalyst BiVO4The method of purifying dyestuff waste water,
It is characterized in that the quality of persulfuric acid hydrogen salt and the mass ratio of pretreated water described in step 1 are 1:(1000~5000).
4. one kind according to claim 1 utilizes persulfuric acid hydrogen salt and photochemical catalyst BiVO4The method of purifying dyestuff waste water,
It is characterized in that the quality of persulfuric acid hydrogen salt and the mass ratio of pretreated water described in step 1 are 1:(5000~8000).
5. one kind according to claim 1 utilizes persulfuric acid hydrogen salt and photochemical catalyst BiVO4The method of purifying dyestuff waste water,
It is characterized in that the BiVO described in step 34Dosage be the g/L of 0.01 g/L ~ 0.1.
6. one kind according to claim 1 utilizes persulfuric acid hydrogen salt and photochemical catalyst BiVO4The method of purifying dyestuff waste water,
It is characterized in that the BiVO described in step 34Dosage be the g/L of 0.1 g/L ~ 10.
7. one kind according to claim 1 utilizes persulfuric acid hydrogen salt and photochemical catalyst BiVO4The method of purifying dyestuff waste water,
It is characterized in that a length of 500 ~ 700 nm of visible light wave in step 4.
8. one kind according to claim 1 utilizes persulfuric acid hydrogen salt and photochemical catalyst BiVO4The method of purifying dyestuff waste water,
It is characterized in that visible light source power is the W of 300 W ~ 1000 in step 4.
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| CN109626492A (en) * | 2018-11-29 | 2019-04-16 | 中国地质大学（武汉） | A kind of photocatalysis oxidation method of the rhodamine B degradation based on HKUST-1 |
| CN114291864A (en) * | 2021-11-19 | 2022-04-08 | 山东大学 | Based on MoS2/BiVO4Method for degrading pollutants by using photo-Fenton system with photocatalyst activated peroxymonosulfate |
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