CN102757121B - Mineralized refuse participating method for treating organic waste water by homogeneous Fenton - Google Patents

Mineralized refuse participating method for treating organic waste water by homogeneous Fenton Download PDF

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Publication number
CN102757121B
CN102757121B CN 201210286312 CN201210286312A CN102757121B CN 102757121 B CN102757121 B CN 102757121B CN 201210286312 CN201210286312 CN 201210286312 CN 201210286312 A CN201210286312 A CN 201210286312A CN 102757121 B CN102757121 B CN 102757121B
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China
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waste water
mineralized
waste
mineralized refuse
fenton
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CN 201210286312
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Chinese (zh)
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CN102757121A (en
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马建锋
李良银
姚超
李定龙
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常州大学
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Abstract

The invention provides a mineralized refuse participating method for treating organic waste water by homogeneous Fenton. The method includes the following steps that a ferrous ion salt, hydrogen peroxide (H2O2) and mineralized refuse are directly added into the waste water, the solid-liquid mass ratio between the mineralized refuse and the waste water is 1:(500-5000), the ferrous ion charge mole number accounts for 50 % to 100% of added mineralized refuse cation exchange capacity, the molar ratio between the Fe2+ and the H2O2 is (500-1000):1, the potential of hydrogen (pH) value is adjusted to 5 to 6, a stirring reaction is performed for 5 to 10 minutes, a solid-liquid separation is performed, and the waste water can be discharged when reaching the standard. The mineralized refuse participating method for treating the organic waste water by the homogeneous Fenton has the advantages that series of cumbersome synthetic steps of prior load type iron oxide catalysts before application are omitted, a cation exchange characteristic of the mineralized refuse is utilized, iron ions can be exchanged to the surface of the mineralized refuse while the iron ions exert an catalytic action, the iron ions are prevented from losing, the iron ions in water are prevented from being polluted, and the possibility of reutilization is improved.

Description

The homogeneous phase Fenton that a kind of mineralized waste participates in is processed the method for organic waste water
Technical field
The present invention relates to the environmental pollution control technique field, the homogeneous phase Fenton that relates in particular to a kind of mineralized waste participation is processed the method for organic waste water.
Background technology
Fenton (Fenton) reagent generally refers to Fe 2+and H 2o 2the oxidation system formed, in invention in 1894, be a kind ofly not need High Temperature High Pressure by French scientist H.J.H.Fenton, and the simple chemical oxidation water technology of equipment.Early stage Fenton reagent is mainly used in organic analytical chemistry and organic synthesis, and 1964, the Eisenhouser technology using Fenton's reaction as wastewater treatment first used, and succeeds in phenol and alkylbenzene wastewater treatment experiment.Traditional Fenton's reaction can cause iron ion to run off, for addressing this problem, progressively developed heterogeneous Fenton's reaction, normally by catalytic performance, the strongest iron ion loads on different carriers this reaction system, is keeping its catalytic activity to obtain the solid-liquid separating power simultaneously, avoid secondary pollution.Heterogeneous Fenton's reaction system has that high, the effective pH of reaction efficiency haves a wide reach and the advantage such as catalyzer reproducible utilization, is an advanced oxidation technique that has development potentiality.At present, the carrier of multiphase Fenton catalyzer mainly contains three classes such as gac, zeolite molecular sieve, clay.Gac is relatively expensive, and zeolite molecular sieve is also to pass through synthetic, and clay class mineral need to be seen mining site content, and the low Distribution Area of some rare mineral content is few, needs long-distance transport, and expense is higher.
Mineralized waste refers in landfill yard landfill (in Shanghai generally at least more than 8-10, northern area is more than 10 years) for many years, substantially reaches stabilization, can exploit the rubbish utilized.Existing tens health of China and accurate sanitary city household refuse landfill sites and general stockyard, inserted or several ten million tons of heap garbages.Some central rubbish, after the degraded of 8-10, have basically reached stabilization of state, thereby have been called as mineralized waste.In Shanghai City, this mineralized waste has 4,000 ten thousand tons (2,000 ten thousand tons of old port refuse landfills, nearly 2,000 ten thousand tons of urban district and suburb stockyards, ,Jiang town, stockyard over the years etc.) at least.The mineralized waste that store up in the cities such as Beijing, Tianjin, Guangzhou estimates also there are several ten million tons.Therefore the resource of these mineralized wastes is very sufficient, and it is wide to distribute, and there is refuse landfill in each big city substantially, and through degraded for a long time, some can be exploited, and can think the novel material not to the utmost of using without cease of getting.
Loading type is that the process of heterogeneous Fenton catalyzed reaction degradation of contaminant is: (1) Kaolinite Preparation of Catalyst loads to ferriferous oxide on the carriers such as gac, zeolite molecular sieve, clay; (2) catalyzed degradation, drop into loaded catalyst in organic waste water and use.In this process, Kaolinite Preparation of Catalyst is crucial step, at first need to select suitable carrier, require specific surface area large, stable, and to pass through a series of loading process, such as load ferric oxide between bentonite bed (Chemosphere.2006,65 (7): 1249-1255.) in the process of reaction, dissolve Fe 2+, participate in Fenton's reaction.This process can affect speed of response, and all dissolvings of the ferric oxide of load, can affect reaction efficiency like this.
Summary of the invention
The objective of the invention is for the deficiencies such as in prior art, multiphase Fenton catalyzer building-up process is complicated, carrier is expensive, the method for the homogeneous phase Fenton processing organic waste water that provides a kind of mineralized waste to participate in are provided.
For addressing the above problem the technical solution used in the present invention, be: its step is as follows: directly add ferrous ion salt, H in waste water 2o 2and mineralized waste, the solid-liquid mass ratio of mineralized waste and waste water is 1:500 ~ 5000, ferrous ion electric charge mole number is add of 50 ~ 100% of mineralized waste cation exchange capacity, such as the cation exchange capacity of mineralized waste is 50mmol/g, the ferrous ion added is 10mmol, its electric charge is 20mmol, the mineralized waste amount added is 0.4g, the permutable positively charged ion amount of mineralized waste is 20mmol, can just 100% existing ferrous ion in exchange solution, if the amount of the mineralized waste added is 0.8g, ferrous ion electric charge mole number is add of 50% of mineralized waste cation exchange capacity, Fe 2+with H 2o 2mol ratio is 500 ~ 1000:1, regulates pH value to 5 ~ 6, stirring reaction 5 ~ 10min, precipitation solid-liquid separation, but waste water qualified discharge.
Described ferrous ion salt is water-soluble ferrous ion salt, comprises FeCl 2or FeSO 4.
Described mineralized waste is through 8 ~ 15 years landfills, pulverizes, and crosses the mineralized waste of 50 ~ 100 mesh sieves.
Beneficial effect of the present invention is:
(1) save a series of loaded down with trivial details synthesis step of original loading type ferric oxide catalyst before application.
(2) the organic wastewater purifying treatment time shortens, and efficiency improves.Be equivalent in this process have homogeneous phase Fenton catalyzed reaction in waste water, compare traditional heterogeneous Fenton's reaction speed and will improve much.
(3) with general soil, compare, mineralized waste has that unit weight is less, porosity is high, cation exchange capacity (CEC) is large, absorption and the strong characteristics of exchange capacity.Cation exchange capacity particularly, the cation exchange capacity of mineralized waste, especially up to more than 0.068mol/100g, exceeds decades of times (Tongji University's journal: natural science edition, the 34th the 10th phase of volume, 1360 pages) than common sand.Its porosity is high in addition, and specific surface area is large, is a kind of desirable catalytic carrier, cheap and easy to get.
(4) utilize the cation exchange properties of mineralized waste, in iron ion performance katalysis, it is exchanged to the mineralized waste surface, avoided the loss of iron ion, avoided the pollution of iron ion in water and improved the possibility of recycling.
Embodiment
3 embodiment of the present invention below further are provided:
Embodiment 1
In 1L concentration, be directly to add FeCl in 30mg/L gold orange II waste water 2, H 2o 2with through 15 years landfills, pulverize, cross the mineralized waste powder of 100 mesh sieves, Fe 2+: H 2o 2=500:1(mol ratio), ferrous ion electric charge mole number is add of 50% of mineralized waste cation exchange capacity, the solid-to-liquid ratio of mineralized waste and waste water is the 1:5000(mass ratio), regulate pH value to 6, stirring reaction 10min, the precipitation solid-liquid separation, the clearance of measuring the pollutent obtained is 90.5%; The solid circulation that separation is obtained is used, and joins in the waste water of same amount, adds the H of same amount 2o 2, regulate pH value to 6, stirring reaction 10min, solid-liquid separation, the clearance of measuring the pollutent obtained is 89.6%.
Traditional homogeneous phase Fenton's reaction, for same waste water, under similarity condition, adds FeCl 2and H 2o 2, but do not add mineralized waste, in the identical treatment time, pollutants removal rate is 75.1%, and Fe 2+can't reuse, and heterogeneous Fenton's reaction needs through the series of steps such as synthetic.
Embodiment 2
In 1L concentration, be directly to add FeSO in 30mg/L methylene blue waste water 4, H 2o 2with through 8 years landfills, pulverize, cross the mineralized waste powder of 50 mesh sieves, Fe 2+: H 2o 2=1000:1(mol ratio), ferrous ion electric charge mole number is add of 100% of mineralized waste cation exchange capacity, the solid-to-liquid ratio of mineralized waste and waste water is the 1:500(mass ratio), regulate pH value to 5, stirring reaction 5min, the precipitation solid-liquid separation, the clearance of measuring the pollutent obtained is 92.5%; The solid circulation that separation is obtained is used, and joins in the waste water of same amount, adds the H of same amount 2o 2, regulate pH value to 5, stirring reaction 5min, solid-liquid separation, the clearance of measuring the pollutent obtained is 91.6%.
Traditional homogeneous phase Fenton's reaction, for same waste water, under similarity condition, adds FeSO 4and H 2o 2, but do not add mineralized waste, in the identical treatment time, pollutants removal rate is 71.3%, and Fe 2+can't reuse, and heterogeneous Fenton's reaction needs through the series of steps such as synthetic.
Embodiment 3
In 1L concentration, be directly to add FeCl in the 30mg/L phenolic waste water 2, H 2o 2with through 15 years landfills, pulverize, cross the mineralized waste powder of 50 mesh sieves, Fe 2+: H 2o 2=800:1(mol ratio), ferrous ion electric charge mole number is add of 100% of mineralized waste cation exchange capacity, the solid-to-liquid ratio of mineralized waste and waste water is the 1:1000(mass ratio), regulate pH value to 6, stirring reaction 10min, the precipitation solid-liquid separation, the clearance of measuring the pollutent obtained is 92.6%; The solid circulation that separation is obtained is used, and joins in the waste water of same amount, adds the H of same amount 2o 2, regulate pH value to 5, stirring reaction 10min, solid-liquid separation, the clearance of measuring the pollutent obtained is 91.1%.
Traditional homogeneous phase Fenton's reaction, for same waste water, under similarity condition, adds FeCl 2and H 2o 2, but do not add mineralized waste, in the identical treatment time, pollutants removal rate is 61.9%, and Fe 2+can't reuse, and heterogeneous Fenton's reaction needs through the series of steps such as synthetic.

Claims (3)

1. the homogeneous phase Fenton of a mineralized waste participation is processed the method for organic waste water, and it is characterized in that: step is as follows:
Directly add ferrous ion salt, H in waste water 2o 2and mineralized waste, the solid-liquid mass ratio of mineralized waste and waste water is 1:500 ~ 5000, ferrous ion electric charge mole number is add 50 ~ 100% of mineralized waste cation exchange capacity, Fe 2+with H 2o 2mol ratio is 500 ~ 1000:1, regulates pH value to 5 ~ 6, stirring reaction 5 ~ 10min, precipitation solid-liquid separation, but waste water qualified discharge.
2. the homogeneous phase Fenton that mineralized waste according to claim 1 participates in is processed the method for organic waste water, and it is characterized in that: described ferrous ion salt is FeCl 2or FeSO 4.
3. the homogeneous phase Fenton that mineralized waste according to claim 1 participates in is processed the method for organic waste water, it is characterized in that: described mineralized waste, for through 8 ~ 15 years landfills, is pulverized, and crosses the mineralized waste of 50 ~ 100 mesh sieves.
CN 201210286312 2012-08-13 2012-08-13 Mineralized refuse participating method for treating organic waste water by homogeneous Fenton CN102757121B (en)

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CN102992442A (en) * 2012-12-12 2013-03-27 常州大学 Organic wastewater treatment method by cooperation of bentonite and Fenton reaction

Citations (3)

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CN1351969A (en) * 2000-11-07 2002-06-05 同济大学 Purifying treatment method for diffusion water of garbage burying ground
CN1468816A (en) * 2002-07-19 2004-01-21 上海电力学院 Catalytic oxydization and biochemical method and apparatus for treating waste water with hard-to-degrad organism
CN101838053A (en) * 2009-03-20 2010-09-22 宝山钢铁股份有限公司 Method for constructing artificial wetland through aged refuse for processing sewage

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CN101905925B (en) * 2009-06-04 2012-05-09 环境保护部南京环境科学研究所 Method for treating dispersed domestic sewage in rural areas by using sequencing batch mineralized waste wetland bed
JP5756516B2 (en) * 2010-05-28 2015-07-29 エンパイア テクノロジー ディベロップメント エルエルシー System and method for oxidizing methane
CN101913723B (en) * 2010-08-18 2012-07-18 常州大学 Recycling device and method for treating organic waste water with organic bentonite

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1351969A (en) * 2000-11-07 2002-06-05 同济大学 Purifying treatment method for diffusion water of garbage burying ground
CN1468816A (en) * 2002-07-19 2004-01-21 上海电力学院 Catalytic oxydization and biochemical method and apparatus for treating waste water with hard-to-degrad organism
CN101838053A (en) * 2009-03-20 2010-09-22 宝山钢铁股份有限公司 Method for constructing artificial wetland through aged refuse for processing sewage

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