CN105254067B - The resource utilization method of advanced treatment of wastewater Fenton process sludge - Google Patents
The resource utilization method of advanced treatment of wastewater Fenton process sludge Download PDFInfo
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- CN105254067B CN105254067B CN201510709116.7A CN201510709116A CN105254067B CN 105254067 B CN105254067 B CN 105254067B CN 201510709116 A CN201510709116 A CN 201510709116A CN 105254067 B CN105254067 B CN 105254067B
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Abstract
The present invention relates to a kind of resource utilization method of advanced treatment of wastewater Fenton process sludge, concretely comprise the following steps：Advanced treating added H2O2And FeSO4Waste water, its pH value is 2.0~4.5 after Fenton's reaction, and products therefrom is passed through chemical reaction units, adds liquid caustic soda thereto, is stirred, and control final ph as 5.5~6.0；Subsequent products therefrom enters precipitation unit, and gained sediment is iron cement, and iron cement Main Ingredients and Appearance is γ FeOOH and α FeOOH；Gained sediment iron cement is used into conventional dewatering process, it is 65~85% to control its moisture content；Liquid caustic soda is added in the supernatant obtained after to precipitation, neutralization reaction is carried out, is stirred, the final ph for controlling gained supernatant is 6.5~7.5；Minimal amount of suspension can be still formed during neutralization reaction, the suspension is removed by contact filtration unit, final discharged wastewater met the national standard.The present invention not only no longer needs payment processes disposal costs, and turn into valuable resource to caused iron cement in advanced treatment of wastewater.
Description
Technical field
The present invention relates to field of water pollution control, and in particular to a kind of recycling profit of advanced treatment of wastewater Fenton process sludge
Use method.
Background technology
Fenton process is famous catalytic oxidation, is found by chemist Fenton HJ within 1893.Although region of chemistry and ring
Border scientific circles have early furtherd investigate to this method, but history of the large-scale application also less than 10 years in sewage disposal.Especially
In China, wastewater discharge standard is increasingly strict in recent years, and traditional bioremediation is unable to reach to numerous industrial wastewaters
Discharge standard, therefore advanced treatment process starts one after another.In numerous handling process, only Fenton process the most reliably with stably,
As the leading technology of advanced treatment of wastewater.It is reported that in China, several families surpass the sewage of 100,000 ton per day treatment scales at present
Treatment plant employs Fenton process advanced treatment process.Production practices show：For general chemical industrial park waste water, through Fenton process depth
After processing can stably reaching standard, its water treatment agent cost is in the acceptable scope of engineering economy；But problem appear to is that：Produce
Sludge quantity it is too many, engineering economy is difficult to endure.There is such case and come from Fenton process in itself：Catalytic oxidation must be in acid
Property condition（pH < 3.5）Lower progress, still need to waste water to be adjusted to neutrality after reaction（Discharge standard requirement）, reaction must also have Fe2+
Catalysis, therefore need to add substantial amounts of acid, alkali and FeSO using Fenton process4Salt.By taking actual sewage factory as an example, water outlet after biochemical treatment
Add FeSO4Salt amount is about 1000mg/L, and about 5.8 tons/ten thousand tons water of theoretical sludge output, this mud is essentially the compound of iron（With
Lower abbreviation " iron cement "）, about five times of municipal wastewater treatment plant sludge output.So, in advanced treating water treatment agent per ton take and electricity
Take only about 1.6 yuan, and produce treatment of sludge expense and be also about 1.6 yuan.Not only processing cost is substantially increased, and it is dirty also to bring generation
The secondary pollution problem of mud.Therefore, the outlet and resource utilization method that iron cement is produced in advanced treating are sought, to reducing sewage
Processing cost, solve the problems, such as that secondary pollution has its important meaning.
The content of the invention
It is an object of the invention to propose a kind of resource utilization method of advanced treatment of wastewater Fenton process sludge.The present invention
To caused iron cement in advanced treatment of wastewater, payment processes disposal costs are not only no longer needed, and turn into valuable resource.
General sewage treatment process（Such as coagulating sedimentation）In caused sediment due to containing substantial amounts of impurity, and be difficult to provide
Sourceization utilizes.But found by analysis：Iron cement caused by advanced treatment of wastewater Fenton process is an exception.The waste water after biochemical treatment
In suspension and dissolving labile organic compound be substantially removed, waste water is in colourless, tasteless, transparent state, only deposits a small amount of dissolving
Property organic matter.By taking actual treatment technique as an example, certain factory organic concentration COD after advanced treating is down to 70mg/L from 140mg/L,
If in terms of actual organic matter dry weight, residual volume is less than 26 mg/L, and caused iron cement amount is about 580 after catalytic oxidation
Mg/L, if 10% organic matter is adsorbed by rear caused sediment, adsorbance 2.6/580, less than 0.5%, meet general
The industrial standard of Light absorbing impurty in material.
Fe2+Fe is easily oxidized in an oxidizing environment3+, and formed under different pH, condition of different temperatures not of the same race
Fe (III) compound precipitation of class, different crystal forms.The present invention thinking be：In advanced treatment process after Fenton oxidation, pH is adjusted
Value, is precipitated step by step, Fe (III) compound precipitation conditions of particular types and crystal formation is created, to improve the value of sediment.
The resource utilization method of advanced treatment of wastewater Fenton process sludge proposed by the present invention, is comprised the following steps that：
（1）Advanced treating added H2O2And FeSO4Waste water, after Fenton's reaction its pH value be 2.0~4.5, Fenton
Gained waste water is passed through chemical reaction units after reaction treatment, adds liquid caustic soda thereto, is stirred, and controls final gained wastewater pH
It is worth for 5.5~6.0；Subsequent products therefrom enters precipitation unit, and gained sediment is iron cement, and iron cement Main Ingredients and Appearance is γ-FeOOH
And alpha-feooh；
（2）By step（1）Gained sediment iron cement uses conventional dewatering process, and it is 65~85% to control its moisture content；
（3）To step（1）Liquid caustic soda is added in the supernatant obtained after precipitation, neutralization reaction is carried out, is stirred, controls institute
The final ph for obtaining supernatant is 6.5~7.5；Minimal amount of suspension, the suspension can be still formed during neutralization reaction
Removed by contact filtration unit, the discharged wastewater met the national standard after final process.
In the present invention, step（1）And step（3）Described in liquid caustic soda be NaOH solution.
In the present invention, step（1）In, in the fall, winter or spring be when running, and when maximum temperature temperature is less than 28 DEG C, gives up
When water water temperature is less than 22 DEG C, γ-FeOOH contents are larger in obtained iron cement.Temperature is lower, and γ-FeOOH ratios are higher, catalysis
O3The effect of oxidation is better.Now, by step（2）Gained iron cement carries out natural air drying（Do not heat）, control moisture content 20% with
Under.Obtain the preferable catalysis material raw material of quality.
In the present invention, in summer operation, when maximum temperature temperature is higher than 28 DEG C, and waste water water temperature is higher than 22 DEG C, obtain
Iron cement in alpha-feooh content it is larger, γ-FeOOH are low small, be catalyzed O3The effect of oxidation is poor.Now, can be by step（2）It is de-
Water iron cement heat drying（Common process）, moisture content as little as less than 10%, the higher alpha-feooh raw material of purity is obtained, industry can be used as
Raw material application.
The beneficial effects of the present invention are：Iron cement caused by existing advanced treating Fenton process, treats as producing in general sewage disposal
Raw sludge is, it is necessary to carry out subsequent processes and disposal, for the iron cement of moisture content 80%, " landfill " processing cost is generally more than 100
Yuan/ton, and heat treatment method, the expense such as burning are higher, more than 300 yuan/ton.And obtained when being run by autumn, winter or spring
The iron cement arrived, there is stronger catalysis O3The effect of, be another advanced treatment of wastewater advanced oxidization method catalyst, add
Value is higher；It can also be used for producing inorganic pigment etc..The iron cement obtained during to passing through summer operation, it is the important source material in chemical industry,
Available for production inorganic pigment etc., there is certain value.
Embodiment
The present invention is further illustrated below by embodiment.
Embodiment 1：Preparation rich in γ-FeOOH iron cements
（1）Winter, 5 DEG C of water temperature, dyeing and finishing and Chemical Industry Park advanced treatment of wastewater.Added H2O2And FeSO4Waste water,
Its pH value is 2.5 after Fenton's reaction.Chemical precipitation reaction member is introduced to, adds liquid caustic soda（NaOH solution）, it is stirred, finally
PH value is controlled 5.5；Precipitation unit is subsequently entered, γ-FeOOH are more than 60% in its sediment iron cement.
（2）Iron cement after precipitation, using conventional dewatering process, moisture content is allowed in 65~85% scopes.
（3）Iron cement natural air drying, moisture content to less than 20% will be dehydrated.Obtain the preferable catalysis material raw material of quality.
Embodiment 2：Preparation rich in γ-FeOOH iron cements
（1）Autumn, 22 DEG C of water temperature, the highest temperature are less than 28 DEG C.Added H2O2And FeSO4Waste water, after Fenton's reaction its
PH value is 4.5.Chemical precipitation reaction member is introduced to, adds liquid caustic soda（NaOH solution）, it is stirred, final ph control exists
6.0；Precipitation unit is subsequently entered, γ-FeOOH are more than 30% in its sediment iron cement.
（2）Iron cement after precipitation, using conventional dewatering process, moisture content is allowed in 65~85% scopes.
（3）Iron cement natural air drying, moisture content to less than 20% will be dehydrated.Obtain the preferable catalysis material raw material of quality.
Embodiment 3：Preparation rich in alpha-feooh iron cement
（1）Summer, water temperature is more than 22 DEG C, and the highest temperature is more than 28 DEG C.Added H2O2And FeSO4Waste water, Fenton's reaction
Its pH value is 4.5 afterwards.Chemical precipitation reaction member is introduced to, adds liquid caustic soda（NaOH solution）, it is stirred, final ph control
6.0；Precipitation unit is subsequently entered, its alpha-feooh of its sediment iron cement is more than 70%.
（2）Iron cement after precipitation, using conventional dewatering process, moisture content is allowed in 65~85% scopes.
（3）Iron cement heat drying will be dehydrated（Common process）, moisture content as little as less than 10%, obtain the higher alpha-feooh of purity
Raw material, raw material of industry application can be used as.
Claims (4)
1. the resource utilization method of advanced treatment of wastewater Fenton process sludge, it is characterised in that comprise the following steps that：
（1）Advanced treating added H2O2And FeSO4Waste water, after Fenton's reaction its pH value be 2.0~4.5, Fenton's reaction
Gained waste water is passed through chemical reaction units after processing, adds liquid caustic soda thereto, is stirred, and controls the pH value of final gained waste water
For 5.5~6.0；Subsequent products therefrom enters precipitation unit, and gained sediment is iron cement, iron cement Main Ingredients and Appearance be γ-FeOOH with
α-FeOOH；
（2）By step（1）Gained sediment iron cement uses conventional dewatering process, and it is 65~85% to control its moisture content；
（3）To step（1）Liquid caustic soda is added in the supernatant obtained after precipitation, neutralization reaction is carried out, is stirred, on control gained
The final ph of clear liquid is 6.5~7.5；Minimal amount of suspension can be still formed during neutralization reaction, the suspension passes through
Contact filtration unit removes, the discharged wastewater met the national standard after final process.
2. the resource utilization method of advanced treatment of wastewater Fenton process sludge according to claim 1, it is characterised in that step
Suddenly（1）In, in the fall, winter or spring be when running, and when maximum temperature temperature is less than 28 DEG C, and waste water water temperature is less than 22 DEG C, obtains
To iron cement in γ-FeOOH contents it is larger；Temperature is lower, and γ-FeOOH ratios are higher, is catalyzed O3The effect of oxidation is better；Will
Step（2）Gained iron cement does not heat, and directly carries out natural air drying, control moisture content obtains quality and preferably urged below 20%
Change material feedstock.
3. the resource utilization method of advanced treatment of wastewater Fenton process sludge according to claim 1, it is characterised in that
During summer operation, when maximum temperature temperature is higher than 28 DEG C, and waste water water temperature is higher than 22 DEG C, alpha-feooh content in obtained iron cement
Larger, γ-FeOOH are smaller, are catalyzed O3The effect of oxidation is poor；By step（2）It is dehydrated iron cement heat drying, moisture content as little as 10%
Hereinafter, the higher alpha-feooh raw material of purity is obtained, raw material of industry application can be used as.
4. the resource utilization method of advanced treatment of wastewater Fenton process sludge according to claim 1, it is characterised in that step
Suddenly（1）And step（3）Described in liquid caustic soda be NaOH solution.
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| CN108821405A (en) * | 2018-06-14 | 2018-11-16 | 黑龙江大学 | A kind of method and its application removing nitrate from waste water |
| CN109020134A (en) * | 2018-09-17 | 2018-12-18 | 四川农业大学 | A kind of method of two steps annealing method recycling Fenton sludge |
| CN113501598A (en) * | 2021-08-04 | 2021-10-15 | 岳阳振兴中顺新材料科技有限公司 | Preparation process of activated carbon-based carbon nanotube based on hydrogen peroxide wastewater treatment |
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| CN101486518B (en) * | 2009-02-27 | 2011-06-15 | 哈尔滨工业大学 | Fenton-like-fluidized bed sewage processor and sewerage treating method therefor |
| CN102642997A (en) * | 2012-05-03 | 2012-08-22 | 山东博洋环境资源有限公司 | Recycling treatment method for sludge generated by fenton treatment technology |
| CN103523966A (en) * | 2013-10-31 | 2014-01-22 | 东莞理文造纸厂有限公司 | Advanced wastewater treatment system and treatment method |
| CN103553200B (en) * | 2013-11-15 | 2015-03-04 | 山东省环境保护科学研究设计院 | Fenton oxidation wastewater treatment method and system |
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