CN108439569A - A kind of method of low-temperature heat enhancing class Fenton processing highly acid disperse dyestuff waste water - Google Patents
A kind of method of low-temperature heat enhancing class Fenton processing highly acid disperse dyestuff waste water Download PDFInfo
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- CN108439569A CN108439569A CN201810475312.6A CN201810475312A CN108439569A CN 108439569 A CN108439569 A CN 108439569A CN 201810475312 A CN201810475312 A CN 201810475312A CN 108439569 A CN108439569 A CN 108439569A
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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Abstract
The present invention relates to the method that a kind of low-temperature heat enhancing class Fenton handles highly acid disperse dyestuff waste water, this method includes：Micron reproducibility subsieve iron powder and hydrogen peroxide are added into highly acid disperse dyestuff waste water, quick decolorization reaction is carried out under the conditions of stirring, the low-temperature heat that heating temperature is 50 80 DEG C.The processing method of the present invention can make highly acid disperse dyestuff waste water quick decolorization; quick decolorization can be completed in 5 15min; reaction speed is fast; high-volume waste water can be handled to scale in the smaller place of production; reaction time is far below same embryonic stem-like cells; further improving efficiency reduces cost, while can make the comprehensive utilization of energy resource, and then promotes the perfect of ecological Industrial Area function.
Description
Technical field
The present invention relates to the methods that a kind of low-temperature heat enhancing class Fenton handles highly acid disperse dyestuff waste water, belong to waste water
Handle field of environmental engineering.
Background technology
Disperse dyes Production in Chemical Plant waste water has that complicated component (raw material and intermediate), coloration are high, acid strong (pH is
0.1-2), the features such as COD (COD 10000-12000mg/L) is high, environmental hazard is big, biochemical poor processing effect；
After traditional alkali (lime or ammonium hydroxide) neutralizes plus the mode of decolorising agent progress decolorization will produce a large amount of hazardous waste sulfuric acid
Calcium or ammonium sulfate, these hazardous wastes all limit it containing a large amount of organic pollutant and recycle and will produce secondary dirt
Dye.There is literature research to show that the percent of decolourization of the treatment technologies such as ultrafiltration, wet oxidation, light electrolysis is higher, but its is of high cost, technique is multiple
It is miscellaneous, operation difficulty is big, it is difficult to promote the use of.
High-level oxidation technology is a kind of water process for removing the various organic pollutions in water removal using a variety of free-radical oxidations
Technology, the technology can not only improve it is various be difficult to biodegradation or to the organic pollution of the toxic effect of biology can biology
Degradability, and can reach the thorough mineralising removal to these organic matters.High-level oxidation technology type is various, including ozone oxygen
Change, ozone-ultraviolet combination, photochemical catalytic oxidation, Fenton and Fenton-like etc..Wherein, Fenton-like system refers to being catalyzed using ferrous salt
Hydrogen peroxide decomposes the reaction for generating hydroxyl radical free radical, and class Fenton is exactly that it is (such as ultraviolet to change some conditions using Fenton reagent
Illumination, electric Fenton) or the reaction that is doped with metal (copper, zinc, zirconium) other than ferrous iron etc..Fenton and class Fenton generate hydroxyl
The mode of base free radical is relatively easy, easily operated management, and used medicament molysite and hydrogen peroxide are environmentally friendly
Medicament, while the efficiency generated free radicals is relatively high, therefore Fenton oxidation technology is at a kind of waste water of potential green
Reason technology, the hydroxyl radical free radical which generates can decompose various hardly degraded organic substances without selectively efficient oxidation.
Since Fenton and Fenton-like optimal use pH value are between 3.0~4.0, it is needed before processing by waste water
PH value is adjusted to 3.0 or so, and pH value is adjusted to neutrality after reaction, and acid, alkali tune is adjusted to increase processing cost repeatedly, and generates a large amount of
Flocculation sediment, cause the secondary pollution of water body.And Fenton and Fenton-like generally require and add excessive mistake in actually using
Hydrogen oxide causes hydrogen peroxide largely remaining to reach good treatment effect, not only increases processing processing cost, remaining
Hydrogen peroxide, which is also constituted follow-up water treatment technology, to be influenced.
Some researches show that illumination can effectively enhance Fenton's reaction treatment effect, but the practice of this mode there are still
Prodigious problem, such as the translucency of waste water and useless Organic substance in water volatility.
In the boiler afterheat (recirculated cooling water, high-temperature flue gas etc.) of each industrial park or enterprises, process waste etc.
It is not fully utilized mostly, this not only causes the waste of resource, but also causes local air thermal pollution.
Invention content
In view of the shortcomings of the prior art with deficiency, the present invention provides a kind of low-temperature heat enhancing class Fenton processing highly acid point
Dissipate the method for waste water from dyestuff.
Summary of the invention：
The processing method of the present invention is under the conditions of low-temperature heat (boiler or process waste), micron order micron reproducibility subsieve
Iron powder is reacted with acid generates hydrogen and ferrous ion, and ferrous ion occurs Fenton's reaction with hydrogen peroxide and generates free radicals in turn
Decolored degradation is carried out to waste water from dyestuff.Iron powder improves the pH and temperature of reaction system of reaction system, Jin Eryou with sour reacting
Conducive to the progress of Fenton's reaction.The rate that a large amount of heat that Fenton's reaction is released can promote iron powder to be reacted with acid again.Reactant
The temperature change of system plays a decisive role to this chain type coupled reaction mutually promoted, when temperature reaches a certain critical value,
Violent redox reaction will be caused.The chain type coupling effect not only realizes the fast of highly acid disperse dyes production waste water
Fast decoloration, and the chemical requirement (COD) of production waste water is reduced, and then reduce the technological process of subsequent wastewater treatment and give up
The expense of water process.The recycling of the generation of simultaneous hydrogen, the clean energy resource gas can reduce being processed into for the waste water
This.
Detailed description of the invention：
This hair is realized by following proposal：
A kind of method of low-temperature heat enhancing class Fenton processing highly acid disperse dyestuff waste water, this method include：To strong acid
Property disperse dyestuff waste water in micron reproducibility subsieve iron powder and hydrogen peroxide is added, be 50-80 DEG C low in stirring, heating temperature
Quick decolorization reaction is carried out under warm heating condition.
According to currently preferred, after decoloring reaction, Magnetic Isolation recycling micron reproducibility subsieve iron powder simultaneously carries out
It recycles；Hydrogen is collected to utilize as energy recovery.
According to currently preferred, the COD a concentration of 10000-12000mg/L, pH of highly acid disperse dyestuff waste water are
0.1-2。
According to currently preferred, the grain size of the micron reproducibility subsieve iron powder is 10~40 μm.
According to currently preferred, iron content is 93.18~95.32% in the micron reproducibility subsieve iron powder,
Contain aluminium and silicon trace element simultaneously.
According to currently preferred, the dosage of the micron reproducibility subsieve iron powder is 5~15g/L waste water.
According to currently preferred, H used2O2Dosage and highly acid disperse dyestuff waste water volume ratio be (0.04~
0.08):1。
According to currently preferred, H used2O2Mass concentration be 30%.
According to currently preferred, low-temperature heat temperature is 50-70 DEG C.
According to currently preferred, the present invention is made by being passed through boiler afterheat or direct-fired mode into reaction system
Low-temperature heat temperature reaches 50-80 DEG C.
According to currently preferred, it is 5-9% that reaction, which generates density of hydrogen, be can be used as after gas enrichment purified treatment
Clean energy resource uses.
According to currently preferred,
The present invention mechanism be：
The production water reuse low-temperature heat of highly acid disperse dyes promotes Fe to react generation Fe with acid2+And hydrogen, the oxidation
The heat that reduction reaction generates further improves reaction rate；Secondly H+Quick consumption improve reaction system pH value and
Fe2+Quickly generate and all enhance subsequent Fenton's reaction rate, it is same that Fenton's reaction generates a large amount of free radical in a short time
When a large amount of heat of release promote reacting for iron powder and H+ again in turn.Thus, highly acid disperse dyes production waste water is quickly taken off
Color.This chain type coupling process mutually promoted causes violent redox reaction in a short time not only realizes highly acid
Disperse dyes produce the quick decolorization of waste water, and reduce the chemical requirement (COD) of production waste water, and then reduce follow-up useless
The technological process of water process and the expense of wastewater treatment；Simultaneously also with the generation of hydrogen, the recycling of the clean energy resource gas can
To reduce the processing cost of the waste water, therefore, under low-temperature heat existence condition, Fe+H2O2Reaction system can quickly and effectively drop
It solves highly acid disperse dyes production waste water and quick decolorization reaction occurs, after reacting 10min, highest percent of decolourization is 95.2%.
The present invention compared with the existing technology, has the following advantages and advantageous effect：
(1) present invention enhances Fenton's reaction with low-temperature heat, the heat source of low-temperature heat derive from most of industrial park or
The boiler or process waste of enterprise.This waste heat or waste heat not only derive from a wealth of sources, are cheap and easy to get, but also will make the comprehensive of energy resource
It closes and utilizes, and then promote the perfect of ecological Industrial Area function.
(2) present invention not only makes highly acid disperse dyes produce waste water quick decolorization, but also reduces the COD of waste water in turn
Lower follow-up cost of sewage disposal, while spent acid is utilized and produces clean energy resource hydrogen.
(3) processing method of the invention can make highly acid disperse dyestuff waste water quick decolorization, can be complete in 5-15min
At quick decolorization, reaction speed is fast, and high-volume waste water can be handled to scale in the smaller place of production, and the reaction time is far below
Same embryonic stem-like cells, further improving efficiency reduces cost.
(4) present invention process is easy, equipment requirement is low, efficient, utilizes this method treated highly acid disperse dyes
Production waste water quick decolorization rate is up to 95.2%.It can be widely used for processing weaving, dyestuff, papermaking, medical and health and chemical industry etc.
The waste water that field generates is suitble to industrial applications, has good social benefit, environmental benefit and economic benefit.
Description of the drawings
Fig. 1 is color throw block diagram of the application experiment example 2 to 100mL highly acids disperse dyes at different temperatures.
Specific implementation mode
With reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
In embodiment, micron reproducibility subsieve iron powder and hydrogen peroxide are commercial products, are purchased from Aladdin Co., Ltd, implement
Iron powder in example reaction is excessive, and highly acid disperse dyestuff waste water is derived from Peng Lai disperse dyes manufacturing enterprise, and waste water COD is
10586；COD concentration carries out quantitative analysis, hydrogen gas chromatographic analysis using potassium dichromate method.
Embodiment 1
A kind of method of low-temperature heat enhancing class Fenton processing highly acid disperse dyestuff waste water, steps are as follows：
Under 250r/min stir speed (S.S.)s, by 1gFe particle (grain sizes：10~40 μm) and 4mLH2O2Solution is added to 100mL
Highly acid disperse dyes produce in waste water, and 10min is heated under 50 DEG C of heating conditions.After the gas collection generated in reaction process
It is analyzed with gas-chromatography.After reaction, sampling centrifuges and measures the production of highly acid disperse dyes with potassium dichromate method and gives up
The COD of water, Magnetic Isolation micron reproducibility subsieve iron powder, recycles after being used in combination clear water to rinse.
Embodiment 2
A kind of method of low-temperature heat enhancing class Fenton processing highly acid disperse dyestuff waste water, steps are as follows：
Under 250r/min stir speed (S.S.)s, by 1gFe particle (grain sizes：10~40 μm) and 4mLH2O2Solution is added to 100mL
Highly acid disperse dyes produce in waste water, and 10min is heated under 60 DEG C of heating conditions.After the gas collection generated in reaction process
It is analyzed with gas-chromatography.After reaction, sampling centrifuges and measures the production of highly acid disperse dyes with potassium dichromate method and gives up
The COD of water, Magnetic Isolation micron reproducibility subsieve iron powder, recycles after being used in combination clear water to rinse.
Embodiment 3
A kind of method of low-temperature heat enhancing class Fenton processing highly acid disperse dyestuff waste water, steps are as follows：
Under 250r/min stir speed (S.S.)s, by 1gFe particle (grain sizes：10~40 μm) and 4mLH2O2Solution is added to 100mL
Highly acid disperse dyes produce in waste water, and 10min is heated under 70 DEG C of heating conditions.After the gas collection generated in reaction process
It is analyzed with gas-chromatography.After reaction, sampling centrifuges and measures the production of highly acid disperse dyes with potassium dichromate method and gives up
The COD of water, Magnetic Isolation micron reproducibility subsieve iron powder, recycles after being used in combination clear water to rinse.
Embodiment 4
A kind of method of low-temperature heat enhancing class Fenton processing highly acid disperse dyestuff waste water, steps are as follows：
Under 250r/min stir speed (S.S.)s, by 1gFe particle (grain sizes：10~40 μm) and 4mLH2O2Solution is added to 100mL
Highly acid disperse dyes produce in waste water, and 10min is heated under 80 DEG C of heating conditions.After the gas collection generated in reaction process
It is analyzed with gas-chromatography.After reaction, sampling centrifuges and measures the production of highly acid disperse dyes with potassium dichromate method and gives up
The COD of water, Magnetic Isolation micron reproducibility subsieve iron powder, recycles after being used in combination clear water to rinse.
Embodiment 5
A kind of method of low-temperature heat enhancing class Fenton processing highly acid disperse dyestuff waste water, steps are as follows：
Under 250r/min stir speed (S.S.)s, by 1gFe particle (grain sizes：10~40 μm) and 5mLH2O2Solution is added to 100mL
Highly acid disperse dyes produce in waste water, and 10min is heated under 70 DEG C of heating conditions.After the gas collection generated in reaction process
It is analyzed with gas-chromatography.After reaction, sampling centrifuges and measures the production of highly acid disperse dyes with potassium dichromate method and gives up
The COD of water, Magnetic Isolation micron reproducibility subsieve iron powder, recycles after being used in combination clear water to rinse.
Embodiment 6
A kind of method of low-temperature heat enhancing class Fenton processing highly acid disperse dyestuff waste water, steps are as follows：
Under 250r/min stir speed (S.S.)s, by 1gFe particle (grain sizes：10~40 μm) and 6mLH2O2Solution is added to 100mL
Highly acid disperse dyes produce in waste water, and 10min is heated under 70 DEG C of heating conditions.After the gas collection generated in reaction process
It is analyzed with gas-chromatography.After reaction, sampling centrifuges and measures the production of highly acid disperse dyes with potassium dichromate method and gives up
The COD of water, Magnetic Isolation micron reproducibility subsieve iron powder, recycles after being used in combination clear water to rinse.
Embodiment 7
A kind of method of low-temperature heat enhancing class Fenton processing highly acid disperse dyestuff waste water, steps are as follows：
Under 250r/min stir speed (S.S.)s, by 1gFe particle (grain sizes：10~40 μm) and 7mLH2O2Solution is added to 100mL
Highly acid disperse dyes produce in waste water, and 10min is heated under 70 DEG C of heating conditions.After the gas collection generated in reaction process
It is analyzed with gas-chromatography.After reaction, sampling centrifuges and measures the production of highly acid disperse dyes with potassium dichromate method and gives up
The COD of water, Magnetic Isolation micron reproducibility subsieve iron powder, recycles after being used in combination clear water to rinse.
Comparative example 1
A method of processing highly acid disperse dyestuff waste water, steps are as follows：
Under 250r/min stir speed (S.S.)s, by 1gFe particle (grain sizes：10~40 μm) and 6mLH2O2Solution is added to 100mL
Highly acid disperse dyes produce in waste water, react 30min under the conditions of room temperature (20 DEG C).After the gas collection generated in reaction process
It is analyzed with gas-chromatography.After reaction, sampling centrifuges and measures the production of highly acid disperse dyes with potassium dichromate method and gives up
The COD of water, Magnetic Isolation micron reproducibility subsieve iron powder, recycles after being used in combination clear water to rinse.
Comparative example 2
A method of processing highly acid disperse dyestuff waste water, steps are as follows：
Under 250r/min stir speed (S.S.)s, by 6mLH2O2Solution is added in 100mL highly acid disperse dyes production waste water,
30min is heated under 60 DEG C of heating conditions.It is analyzed with gas-chromatography after the gas collection generated in reaction process.Reaction knot
Shu Hou, sampling centrifugation simultaneously measure the COD that highly acid disperse dyes produce waste water, Magnetic Isolation micron reproducibility with potassium dichromate method
Subsieve iron powder recycles after being used in combination clear water to rinse.
Comparative example 3
A method of processing highly acid disperse dyestuff waste water, steps are as follows：
Under 250r/min stir speed (S.S.)s, by 1gFe particle (grain sizes：10~40 μm) it is added to 100mL highly acids dispersion dye
In material production waste water, 30min is heated under 60 DEG C of heating conditions.After the gas collection generated in reaction process with gas-chromatography into
Row analysis.After reaction, sampling centrifuges and measures the COD that highly acid disperse dyes produce waste water with potassium dichromate method, magnetic
Micron reproducibility subsieve iron powder is detached, is recycled after being used in combination clear water to rinse.
Application experiment example 1
By the method for embodiment 1-7 and the method for comparative example 1-3 for handling identical highly acid disperse dyestuff waste water, point
It COD value and hydrogen content, test result Ce Shi not take effect shown in table 1 after percent of decolourization, decoloration：
Influence of the 1 different disposal method of table to COD value and hydrogen content after percent of decolourization, decoloration
By upper table 1 as can be seen that comparative example 1：Fe+H at normal temperatures2O2In reaction system, the life of highly acid disperse dyes
The percent of decolourization for producing waste water is relatively low, and after reacting 120min, percent of decolourization is only 12.1%, this illustrates the hydroxyl generated in system under room temperature
Free radical is seldom, and for a concentration of 10000-12000mg/L of COD, the big highly acid disperse dyestuff waste water percent of decolourization of acidity is very low,
It is unfavorable for the progress of class Fenton's reaction under room temperature；Comparative example 2：In low-temperature heat (60 DEG C)+H2O2 reaction systems, highly acid dispersion
Waste water in dye production does not have that reduction-decolor reaction occurs substantially；Comparative example 3：Low-temperature heat (60 DEG C) and micron reproducibility subsieve iron
Powder exists, and the efficiency and rate of highly acid disperse dyes production waste water are all very low, and after reacting 30min, percent of decolourization is only 3.2%.
The experimental results showed that the quick decolorization method for producing waste water by highly acid disperse dyes provided herein is de-
Waste water after color, percent of decolourization is high, and highest can reach 95.2%, useless after the three kinds of bleaching agent bleachings provided far above comparative example
Water.Also, contribute to reduce the COD value of waste water after decolourizing, convenient follow-up further processing waste water is cost-effective.And it compares
Example changes very little since percent of decolourization is too low, to the content of organic matter, it is believed that almost unchanged COD value.
Application experiment example 2
Highly acid disperse dyestuff waste water is handled using the method for embodiment 1, unlike, by 1gFe particle (grain sizes：10~
40 μm) and 6mLH2O2Solution be added to 100mL highly acid disperse dyes production waste water in, respectively 20 DEG C, 30 DEG C, 40 DEG C, 50
DEG C, 60 DEG C, heat 10min under 70 DEG C of heating conditions, influence of the treatment of different temperature to percent of decolourization is as shown in Figure 1.
As seen in Figure 1, with the raising of temperature, percent of decolourization gradually increases, when temperature is increased to 50 DEG C, decoloration
It increased dramatically, when temperature is more than 50 DEG C, with the raising of temperature, percent of decolourization is in gentle ascendant trend, but with temperature
It increases, high energy consumption is of high cost, therefore the low-temperature heat temperature of the present invention is based on reaction efficiency, reaction cost and particular design
, processing method reaction speed of the invention is fast, and the reaction time is short, and reaction efficiency is high, can be completed in 5-15min quickly de-
Color, it is at low cost.
In conclusion the quick decolorization method of highly acid disperse dyes production waste water provided herein, using low temperature
The technology of enhancing Fenton oxidation has many advantages, such as simple and convenient, efficient, cleaning and non-secondary pollution, and percent of decolourization height, highest can be with
Reach 95.2%.The quick decolorization method, the quick decolorization and chemistry for not only realizing highly acid disperse dyes production waste water need
The efficient removal of (COD) is measured, also generates clean energy resource-by using spent acid waste water in dye production and boiler afterheat or waste heat
Hydrogen；To realize the efficient process of environmental contaminants and efficiently using for waste resource and the energy.
Claims (10)
1. a kind of method of low-temperature heat enhancing class Fenton processing highly acid disperse dyestuff waste water, this method include：To highly acid
Micron reproducibility subsieve iron powder and hydrogen peroxide are added in disperse dyestuff waste water, in stirring, the low temperature that heating temperature is 50-80 DEG C
Quick decolorization reaction is carried out under heating condition.
2. the method for low-temperature heat enhancing class Fenton processing highly acid disperse dyestuff waste water according to claim 1, special
Sign is, after decoloring reaction, Magnetic Isolation recycling micron reproducibility subsieve iron powder is simultaneously recycled；Hydrogen is collected to make
It is utilized for energy recovery.
3. the method for low-temperature heat enhancing class Fenton processing highly acid disperse dyestuff waste water according to claim 1, special
Sign is, the COD a concentration of 10000-12000mg/L, pH 0.1-2 of highly acid disperse dyestuff waste water.
4. the method for low-temperature heat enhancing class Fenton processing highly acid disperse dyestuff waste water according to claim 1, special
Sign is that the grain size of the micron reproducibility subsieve iron powder is 10~40 μm.
5. the method for low-temperature heat enhancing class Fenton processing highly acid disperse dyestuff waste water according to claim 1, special
Sign is that iron content is 93.18~95.32% in the micron reproducibility subsieve iron powder, contains aluminium simultaneously and silicon is micro
Element.
6. the method for low-temperature heat enhancing class Fenton processing highly acid disperse dyestuff waste water according to claim 1, special
Sign is that the dosage of the micron reproducibility subsieve iron powder is 5~15g/L waste water.
7. the method for low-temperature heat enhancing class Fenton processing highly acid disperse dyestuff waste water according to claim 1, special
Sign is, H used2O2The volume ratio of dosage and highly acid disperse dyestuff waste water be (0.04~0.08):1.
8. the method for low-temperature heat enhancing class Fenton processing highly acid disperse dyestuff waste water according to claim 1, special
Sign is, H used2O2Mass concentration be 30%.
9. the method for low-temperature heat enhancing class Fenton processing highly acid disperse dyestuff waste water according to claim 1, special
Sign is that low-temperature heat temperature is 50-70 DEG C.
10. the method for low-temperature heat enhancing class Fenton processing highly acid disperse dyestuff waste water according to claim 1, special
Sign is that the present invention makes low-temperature heat temperature by being passed through boiler/process waste or direct-fired mode into reaction system
Reach 50-80 DEG C, it is 5-9% that reaction, which generates density of hydrogen, can be used as clean energy resource use after gas enrichment purified treatment.
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| 白无瑕编著: "《高考易错题解析》", 31 August 2011, 中国青年出版社 * |
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