CN109160593A - A kind of application of the composition of warm paste active material and persulfate in treatment of Organic Wastewater - Google Patents
A kind of application of the composition of warm paste active material and persulfate in treatment of Organic Wastewater Download PDFInfo
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- CN109160593A CN109160593A CN201811311083.0A CN201811311083A CN109160593A CN 109160593 A CN109160593 A CN 109160593A CN 201811311083 A CN201811311083 A CN 201811311083A CN 109160593 A CN109160593 A CN 109160593A
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- persulfate
- active material
- warm paste
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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
-
- 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
-
- 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
Abstract
The invention belongs to sewage treating material field, a kind of application of the composition of warm paste active material and persulfate in treatment of Organic Wastewater is disclosed.The application process are as follows: warm paste active material and persulfate are added into organic wastewater, carries out oxidation reaction, the organic matter in degrading waste water under normal temperature condition.The present invention utilizes the market being formed by combining with iron powder, vermiculite, active carbon that warm paste material activation persulfate is often used to generate SO4 ·‑Degradation Organic Pollutants In Water, system activation persulfate speed is fast, and degradable organic pollutant is high-efficient.And used warm paste active material source is wide, at low cost, and recycling can be recycled after reaction.Applicable pH value range is wide, and reaction condition is mild, easy to operate, is suitable for the processing of various organic wastewaters.
Description
Technical field
The invention belongs to sewage treating material fields, and in particular to a kind of composition of warm paste active material and persulfate
Application in treatment of Organic Wastewater.
Background technique
With rapid economic development, water pollution is got worse, the tradition water such as activated sludge, activated carbon adsorption and flocculation sedimentation
Processing method is difficult to effectively remove the persistent organic pollutants such as dyes and drug.Compared with large pollutant, dyestuff
Chemical structure it is complicated, inhibited to microorganism, conventional sewage processing method can not effectively remove it.
Therefore, more and more scholars have studied many new methods to solve the dirt of water caused by hardly degraded organic substance (dyestuff)
Dye problem.And high-level oxidation technology is with consersion unit is simple, excess sludge is few, applied widely and without secondary pollution and difficult
The advantages that degradable organic pollutant removal ability is strong shows great market potential.Wherein it is based on sulphuric acid free radical (SO4 ·-) with
The high-level oxidation technology (advanced oxidation processes, AOPs) of hydroxyl radical free radical (OH), since quantum produces
Rate is high, degradation rate is fast, is able to achieve the efficient removal of hardly degraded organic substance, Study on degradation has become hot spot both domestic and external.
High-level oxidation technology based on OH is Fe2+With H2O2It is generated in the Fenton or MODIFIED Fe nton system of composition
The oxidation technology of OH, and then the OH for realizing the degradation of organic pollutant, and generating with the service life, itself limit to by short, easy quenching etc.
Property.And with SO4 ·-For core high-level oxidation technology can not only make up traditional OH high-level oxidation technology defect, and
And it is equally reached the purpose of fast degradation organic matter.Based on SO4 ·-Persulfate (S2O8 2-) high-level oxidation technology is close
The novel water treatment technology that year grows up, SO4 ·-Influenced that small, degradation rate is fast and quantum yield is high by organic matter, in environment work
Journey field has huge applications potential.
S2O8 2-Self structure, which is easy to be activated, generates SO4 ·-.In practical application, the generation of free radical mainly passes through high temperature
Thermal activation, photocatalysis, microwave activation and the modes such as transition metal-catalyzed decompose persulfate.Wherein, under normal temperature and pressure
Activate the transition metal (Fe of persulfate2+、Co2+、Ag+Deng) catalysis technique, reaction rate is fast, and it is easy to operate, and without consumption
Extraneous energy, thus have more application prospect.In view of economy and safety, now most popular is Fe2+Activate persulfate
Degradable organic pollutant.However Fe2+Activating persulfate oxidation technology, there are still many deficiencies, such as 1. pH value of reaction system requirement
In acidity；2. Fe in solution2+Easily with the SO of generation4 ·-Reaction, reduces the utilization rate of persulfate；③Fe2+It is converted to non-catalytic
Active Fe3+, lead to Fe2+Effective rate of utilization reduces；4. with Fe in reaction process3+Generation, a large amount of iron cement can be generated,
Cause secondary pollution；⑤Fe2+Regeneration is difficult.
Based on traditional Fe2+Limitation existing for persulfate oxidation technology is activated, existing many scholars utilize Zero-valent Iron generation
For Fe2+, heterogeneous catalysis system is formed, to reach Fe in control solution2+The purpose of content reduces the several of side reaction generation
Rate.As China Patent No. CN103896388B is disclosed using nano cupric oxide and Zero-valent Iron (Fe0) the heterogeneous work of dual catalyst
Change the method for persulfate oxidation processing organic wastewater；CN104129841A discloses use by nano zero valence iron and charcoal group
At the method for the heterogeneous activation persulfate degradation Organic Pollutants In Water of activator composite material, but this method need to use grain
Diameter is the nano zero valence iron of 20~100nm, and activator composite material is that nano zero valence iron is evenly distributed on biological carbon surface, is caused
Material cost is high, and cannot reuse.
Warm paste is commonly called as warmer, and raw material is made of iron, vermiculite, active carbon, salt, water-absorbing resin etc., can oxygen in air
Exothermic reaction occurs under the action of gas, to achieve the effect that warm.Iron in warm paste is conventional reduction iron powder, powder diameter size
From 150 μm to 180 μm, and each ingredient is mixed through conventional in warm paste, is not necessarily to specific distribution, recycling, material can be recycled
Source is wide, at low cost.Having not yet to see as catalysis material to activate warm paste active material in persulfate oxidation water body has
The document and patent report of machine pollutant.
Summary of the invention
In place of the above shortcoming and defect of the existing technology, the primary purpose of the present invention is that providing a kind of warm paste
The composition of active material and persulfate.
The application that another object of the present invention is to provide above-mentioned compositions in treatment of Organic Wastewater.
The object of the invention is achieved through the following technical solutions:
A kind of composition of warm paste active material and persulfate is made of warm paste active material with persulfate.
Further, the warm paste active material is to commonly use warm paste active material in the market, and active component includes reduction
Iron powder, vermiculite and active carbon.
Further, in the warm paste active material active component mass percentage are as follows: reduced iron powder 68%~
85%, vermiculite 10%~20%, active carbon 1%~10%.
Further, reduced iron powder partial size is 150~180 μm in the warm paste active material.
Further, the persulfate is selected from least one of sodium peroxydisulfate, potassium peroxydisulfate and ammonium persulfate.
Application of the above-mentioned composition in treatment of Organic Wastewater, includes the following steps:
Warm paste active material and persulfate are added into organic wastewater, carries out advanced oxidation reaction under normal temperature condition, drops
Solve the organic matter in waste water.
Preferably, the pH value of the organic wastewater is 3~10.
Preferably, the organic wastewater is the waste water containing at least one of rhodamine B and methylene blue organic matter.
Preferably, the additional amount of the warm paste active material is 0.1~0.4g/L.
Preferably, the additional amount of the persulfate is 5~35 times of organic waste Organic substance in water mole.
Preferably, the time of the oxidation reaction is 10~30min.
Preferably, after the completion of the oxidation reaction, warm paste active material is recovered by filtration, is reused after dry.
Compared with the existing technology, the invention has the following advantages and beneficial effects:
(1) present invention utilizes the market being formed by combining with reduced iron powder, vermiculite, active carbon often to be activated with warm paste material
Sulfate generates SO4 ·-Degradation Organic Pollutants In Water, effectively improves single iron powder specific surface area and active site.Meanwhile it is multiple
Persulfate can also be activated by closing the metal ion of vermiculite itself and the carboxyl of activated carbon surface and hydroxyl group in catalysis material；
System activation persulfate speed is fast, and degradable organic pollutant is high-efficient.
(2) in the method for the present invention vermiculite, active carbon etc. by organic dirt be adsorbed onto material surface occur heterogeneous catalysis, together
When material in the collaborations activation persulfate such as reduced iron powder, vermiculite and active carbon decompose and generate SO4 ·-, solution can be effectively reduced
Middle Fe2+Consume SO4 ·-Side reaction, improve the utilization efficiency of persulfate.
(3) iron in warm paste active material used in the present invention is conventional reduction iron powder, and powder diameter size is from 150 μm
To 180 μm, and in warm paste, each ingredient is mixed through conventional, is not necessarily to specific distribution, and recycling can be recycled after reaction, and material comes
Source is wide, at low cost.
(4) active material provided by the invention activates persulfate oxidation processing technique because warm paste microparticle material makes system
Avoid the anion (Cl of molysite introducing-、SO4 2-Deng) caused by the Fe that newly pollutes, and be precipitated in system2+Concentration is not high, both
The a large amount of generations and subsequent processing of iron cement can be in turn avoided with effective activation persulfate.
(5) application of the present invention in treatment of Organic Wastewater is suitable for extensive pH value range (3.0~10.0), reacts item
Part is mild, easy to operate, is suitable for the processing of various organic wastewaters.
Detailed description of the invention
Fig. 1 is that TOC (total organic carbon) changes with time graph of relation in rhodamine B and solution in embodiment 5.
Specific embodiment
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Embodiment 1
Warm paste active material activation persulfate is applied to the processing simulated wastewater of rhodamine B containing 100mg/L by the present embodiment,
The specific steps of which are as follows:
(1) 4 parts of 100mL 100mg/L rhodamine B solution is prepared respectively in 250mL beaker, pH value of solution=4.6, respectively
Number is a, b, c, d, and is placed under six mechanical agitators, is stirred under the conditions of 200~600r/min.
(2) persulfate of 3mM is separately added into tri- beakers of above-mentioned b, c, d, a beaker is not added.
(3) it continues up to state and is separately added into newly the break a seal original warm paste of taking-up of 0.02g in a, d beaker reactor and urges
The used warm paste of 0.02g is added in c beaker and (is exposed to oxidation heat liberation in air for agent (the conventional warm paste bought in the market)
Warm paste afterwards), and any catalyst is added without in b beaker.It is reacted under room temperature, reaction time 30min.Processing result such as following table
Shown in 1:
1 different technology conditions treatment effect of table
| Process conditions | Rhodamine B degradation rate |
| The original warm paste of a | 8.7% |
| B persulfate | 25.7% |
| Used warm paste+the persulfate of c | 24.6% |
| Original warm paste+the persulfate of d | 99.1% |
Table 1 the result shows that, the original warm paste catalyst and persulfate that new Kaifeng is taken out are used alone to Luo Dan
Bright B not can be carried out effective degradation, and used warm paste activation persulfate technique is to the degradation rate of rhodamine B and persulfate
Effect without significant difference, and newly break a seal original warm paste activation persulfate 30min to rhodamine removal rate up to 99% with
On.Illustrate that original warm paste can activate persulfate and rhodamine of effectively degrading, and is exposed to oxidation heat liberation in air
Warm paste afterwards loses the catalytic activity to persulfate.
Embodiment 2
(1) rhodamine B of 1 part of 100mL 100mg/L and the methylene blue solution of 1 part of 100mL 100mg/L are prepared in burning
In cup, pH is adjusted to 7, stirs under the conditions of 200~600r/min.
(2) persulfate of 3mM and the original warm paste of 0.02g is respectively added in above-mentioned 2 reaction beakers.Room temperature
Lower reaction, reaction time 30min.Processing result is as shown in table 2.
The different disposal effect of dyeing wastewater of table 2
Table 2 is the results show that the present invention is useless to rhodamine B and methylene blue using warm paste activation of catalyst persulfate system
Water has good removal effect.
Embodiment 3
The present embodiment is applied to warm paste active material activation persulfate to handle different pH rhodamine B dyeing waste waters,
Specific step is as follows:
(1) prepare 5 parts of 100mL 100mg/L rhodamine B solutions be placed in 5 beakers, respectively adjust pH value be 3,5,7,
9,10, and stirred under the conditions of 200~600r/min.
(2) persulfate of 3mM is respectively added in above-mentioned 5 reaction beakers.
(3) the original warm paste catalysis that the new Kaifeng of 0.02g is taken out respectively is added in 5 beakers in step (2)
Agent (the conventional warm paste bought in the market).It is reacted under room temperature, reaction time 30min.Processing result is as shown in table 3.
Treatment effect under the conditions of the different initial pH of table 3
| PH value | Rhodamine B degradation rate |
| 3 | 99.3% |
| 5 | 99.3% |
| 7 | 99.1% |
| 9 | 99.1% |
| 10 | 98.8% |
Table 3 the result shows that, the heterogeneous activation persulfate degradation of organic waste water of warm paste catalyst established by the present invention
Method good degradation effect is all had to organic wastewater under acid, neutral, alkaline condition.The result shows that of the invention is warm
When pasting catalyst heterogeneous system degradation organic pollution aquifer, without preconditioning pH, it can be used within the scope of wider pH, effectively
It saves water body and pre-processes cost in ground.
Embodiment 4
The present embodiment repeatedly recycles warm paste active material, and then investigates the heterogeneous activation persulfuric acid of warm paste catalyst
The recycling effect of catalyst in salt treatment organic wastewater method, specific steps are as follows:
(1) it prepares 100mL 100mg/L rhodamine B solution to be placed in a beaker and stir, the pH=4.6 of solution, while
It is stirred under the conditions of 200~600r/min.Then the persulfate of 3mM and the original warm paste of 0.02g is added.It is anti-under room temperature
It answers, reaction time 10min, 30min sampling.
(2) spare after forced air drying 6h by the warm paste catalyst filtration after step (1) reaction.
(3) rhodamine B solution of configuration step (1), the warm paste being then recovered by filtration in addition step (2) are catalyzed again
Agent, then sodium peroxydisulfate 3mM is added, it reacts, is reacted for 10min, 30min sampling under room temperature.It repeats catalyst filtration recycling and urges
Change reaction process, processing result is as shown in table 4.
Effect is reused in the recycling of 4 catalyst of table
| Reuse number | 10min rhodamine B degradation rate | 30min rhodamine B degradation rate |
| 0 | 98.5 | 99.1% |
| 1 | 95.1 | 99.0% |
| 2 | 87.1 | 99.0% |
As warm paste catalyst reuses the increase of number, activation of catalyst persulfate it can be seen from 4 result of table
Much variations are had no to the processing capacity of waste water.Accordingly, with respect to existing catalysis persulfate technology, it is excellent that effect is recycled
More.On the basis of catalyst itself is cheap and easy to get, moreover it is possible to realize repeatedly recycling and reusing for resource.
Embodiment 5
Warm paste active material activation persulfate degradation Organic Pollutants In Water is investigated warm paste activity material by the present embodiment
Expect the relationship that changes with time with TOC (total organic carbon) in rhodamine B in persulfate system and solution.
Using the processing method rhodamine B degradation of case study on implementation 4, the initial concentration of rhodamine B is in the reaction system
100mg/L, persulfate 3mM, warm paste catalysis material 0.02g ((the original warm paste bought in the market).In treatment process
In, every 5min, 10min, 15min, 30min, 1h timing sampling carries out rhodamine B and TOC is measured.As a result as shown in Figure 1.
By Fig. 1 result it is found that rhodamine B is degraded 94% after 10min, and only degraded in TOC 10min in solution
30%；Rhodamine B is degraded (99%) substantially after 30min, and TOC degrades 45%；It is unchanged to 60min rhodamine B, and
TOC degradation 59%.According to the experimental results, after rhodamine B degradation, persulfate continuation is reacted with the intermediate product of rhodamine B
Until permineralization is carbon dioxide.
Embodiment 6
The present embodiment investigates warm paste active material activation persulfate degradation Organic Pollutants In Water different commercially available warm
Patch influences persulfate system rhodamine B degradation.
(1) it prepares 3 parts of 100mL 100mg/L rhodamine B solutions to be respectively placed in 3 beakers, pH value of solution=4.6, and
It is stirred under the conditions of 200~600r/min.
(2) persulfate of 3mM is respectively added in above-mentioned 3 reaction beakers.
(3) the commercially available warm paste 1, commercially available warm paste 2, commercially available warm paste 3 of 0.02g are added in 3 beakers in step (2) respectively
As catalyst.It is reacted under room temperature, reaction time 30min.The results are shown in Table 5.
The different commercially available warm paste catalytic effects of table 5
| Commercially available warm paste | Rhodamine B degradation rate |
| Commercially available warm paste 1 | 99.7% |
| Commercially available warm paste 2 | 99.9% |
| Commercially available warm paste 3 | 99.7% |
By 5 result of table as it can be seen that different commercially available warm pastes all have very rhodamine B as activation of catalyst persulfate
Good degradation effect.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of composition of warm paste active material and persulfate, it is characterised in that: by warm paste active material and persulfate
Composition.
2. the composition of a kind of warm paste active material and persulfate according to claim 1, it is characterised in that: described warm
The active component for pasting active material includes reduced iron powder, vermiculite and active carbon.
3. the composition of a kind of warm paste active material and persulfate according to claim 2, it is characterised in that described warm
Paste the mass percentage of active component in active material are as follows: reduced iron powder 68%~85%, vermiculite 10%~20%, active carbon
1%~10%.
4. the composition of a kind of warm paste active material and persulfate according to claim 2, it is characterised in that: described warm
Pasting reduced iron powder partial size in active material is 150~180 μm.
5. the composition of a kind of warm paste active material and persulfate according to claim 1, it is characterised in that: the mistake
Sulfate is selected from least one of sodium peroxydisulfate, potassium peroxydisulfate and ammonium persulfate.
6. application of the described in any item compositions of Claims 1 to 5 in treatment of Organic Wastewater, it is characterised in that including as follows
Step:
Warm paste active material and persulfate are added into organic wastewater, advanced oxidation reaction is carried out under normal temperature condition, degradation is useless
Organic matter in water.
7. application of the composition according to claim 6 in treatment of Organic Wastewater, it is characterised in that: the organic wastewater
PH value be 3~10；The organic wastewater is the waste water containing at least one of rhodamine B and methylene blue organic matter.
8. application of the composition according to claim 6 in treatment of Organic Wastewater, it is characterised in that: the warm paste activity
The additional amount of material is 0.1~0.4g/L；The additional amount of the persulfate is the 5~35 of organic waste Organic substance in water mole
Times.
9. application of the composition according to claim 6 in treatment of Organic Wastewater, it is characterised in that: the advanced oxidation
The time of reaction is 10~30min.
10. application of the composition according to claim 6 in treatment of Organic Wastewater, it is characterised in that: the oxidation is anti-
After the completion of answering, warm paste active material is recovered by filtration, is reused after dry.
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| CN112206744A (en) * | 2020-09-23 | 2021-01-12 | 武汉工程大学 | Recycling method of nondegradable solid domestic waste of self-heating warm patch |
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| CN115090316A (en) * | 2022-06-16 | 2022-09-23 | 哈尔滨工业大学 | Magnetic biochar based on flocs and preparation method and application thereof |
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Application publication date: 20190108 |