CN103252340A

CN103252340A - Resource utilization method of Fenton iron sludge

Info

Publication number: CN103252340A
Application number: CN2013101842498A
Authority: CN
Inventors: 王双飞; 陈永利; 张娟
Original assignee: Guangxi University
Current assignee: Guangxi University
Priority date: 2013-05-17
Filing date: 2013-05-17
Publication date: 2013-08-21
Anticipated expiration: 2033-05-17
Also published as: CN103252340B

Abstract

The invention discloses a resource utilization method of Fenton iron sludge. The method comprises the following steps of: (1) treating Fenton; adding the rest of ferrum into concentrated sulfuric acid; and controlling the temperature to be between 70 and 75 DEG C to stir for 30 minutes; (2) adding excessive quantities of scrap iron chips into an iron sludge solution obtained in the step (1) to reduce; detecting Fe3<+> by using a phenol solution until Fe<3+> is totally reduced into Fe<2+>; and (3) after the reduction is finished, standing for precipitating for 30 minutes; extracting supernate; adding ethanol according to the proportion that V(supernate)/V(ethanol) is equal to 10 to 1 and shortening the crystallizing time of ferrous sulfate; and after the crystallization is finished, obtaining an industrial FeSO4.7H2O finished product. According to the method, the bottle neck problem of Fenton technology promotion can be solved, the resource utilization of solid wastes is realized, and Fenton iron sludge is turned from waste into treasure, so that sustainable development of human society is facilitated.

Description

The method that a kind of Fenton iron mud resource utilizes

Technical field

The present invention relates to the recycling of solid wastes processing technology field, particularly relate to the resource utilization method that a kind of Fenton treatment technology produces iron mud.

Technical background

French scientist H.J.Fenton had found Fe in 1894 ²⁺Can pass through H ₂O ₂The oxidation of catalysis malic acid effectively, the later combination that studies show that the two all is a kind of effective oxidant to the organic matter of numerous species.The descendant is the scientist of this greatness in honor of, with Fe ²⁺And H ₂O ₂The reagent called after Fenton reagent of forming uses the reaction of this reagent to claim Fenton reaction.1964, Canada scholar H.R.Eisenhaner successfully is applied to Fenton reagent in the wastewater treatment, Fenton reagent successfully applies to the processing of various industrial sewage in the research of nearly more than ten years, has become most widely used general, technology that technology is the most ripe in the waste water advanced treatment technology at present.

Why Fenton reagent has very strong oxidability, is because of H in the Fenton reagent ₂O ₂By Fe ²⁺Catalytic decomposition generates hydroxyl radical free radical (OH), and hydroxyl radical free radical (OH) has following critical nature:

(1) oxidability is strong

Its oxidizing electrode current potential (E) is 2.80V, is only second to F in known oxidant ₂, this means that hydroxyl radical free radical (OH) oxidability is considerably beyond common chemical oxidizing agent.Therefore, can the most organic matters of oxidation.

(2) hydroxyl radical free radical (OH) has very high electrophilicity or electronegativity

Have higher electronegativity or electron affinity energy (569.3kJ), the easy high cloud density point of attack, this electrophilicity of hydroxyl radical free radical (OH) has determined Fenton reagent to contain organic matters such as chloro, sulfonic group, nitro in processing and has had unique advantage.

(3) hydroxyl radical free radical (OH) has addition

When carbon-carbon double bond exists, unless had highly active hydrocarbon key by the molecule of attack, otherwise, addition reaction will take place.

The organic essence of Fenton agent treatment is exactly that hydroxyl radical free radical and organic matter react, up to the thorough mineralising of organic matter is become CO ₂And H ₂O ₂

When the Fenton method is handled organic wastewater with difficult degradation thereby, have the incomparable advantage of additive method, successfully apply to the processing of various industrial wastewaters so far.But the Fenton oxidizing process can produce a certain amount of chemical sludge in processing procedure, if improper conducting oneself well comprehended a lot of harm of generation, such as: take a large amount of soils; Mud is stacked through wind and weather can produce high temperature or other chemical reaction, can destroy the structure of soil; Directly discharge alluvial riverbed, severe contamination water body; Mud discharges pernicious gas, dust etc. after being decomposed by microbiological oxidation, can increase the weight of the pollution of atmosphere; After a large amount of the stacking, contain enteric bacteria, parasite and virus etc. in the mud, serious harm is to human beings'health.Therefore the processing of Fenton iron mud has become the key that restriction Fenton technology is promoted.

This case inventor researchs and analyses the performance of Fenton iron mud, and the content of iron is more than 50% in the Fenton iron mud, and wherein main form with ferric ion exists, so the recycling of ferro element is had very big using value.

Summary of the invention

Technical problem to be solved by this invention provides the method that a kind of Fenton iron mud resource utilizes, and by utilizing Fenton iron mud to produce ferrous sulfate iron mud is turned waste into wealth, thereby makes Fenton iron mud obtain abundant recycling.

The present invention solves the problems of the technologies described above with following technical scheme:

The method that a kind of Fenton iron of the present invention mud resource utilizes may further comprise the steps:

(1) get Fenton and handle the chemical iron mud adding of the back residue concentrated sulfuric acid, the volume ratio of the chemical Tie Ni ︰ concentrated sulfuric acid=10 ︰ 1 is heated to temperature and stirs 30min down at 70～75 ℃, gets iron mud solution;

(2) add excessive waste iron filing in the iron mud solution that obtains to step (1) and reduce, detect Fe with phenol solution ³⁺, up to Fe ³⁺Be reduced into Fe fully ²⁺, quiescent setting 30min after finishing extracts supernatant, lower sediment dehydration landfill disposal;

(3) press supernatant: the volume ratio of ethanol=10:1 adds ethanol, shortens the crystallization time of ferrous sulfate, the industrial FeSO that gets product after fully to be crystallized ₄7H ₂O.

The moisture content control of the residue chemistry iron mud of described step (1) can adopt dilution or concentrated method to make its moisture content reach this value 93～96%.

The time that described step (2) is reduced with waste iron filing is 60～70min.

The present invention produces ferrous sulfate by utilizing Fenton iron mud, iron mud is turned waste into wealth, thereby make Fenton iron mud obtain abundant recycling.

Description of drawings

Fig. 1 is the process chart of the inventive method.

The specific embodiment

Embodiment 1:

Raw material: Fenton technology advanced treating paper pulp papermaking waste water residue iron mud, Fe ₂O ₃Content 53.2%, the content of organic matter 28.5%.

Treatment step:

(1) gets above-mentioned Fenton iron mud through concentrating the chemical iron mud 1m that obtains moisture content 95.5% ³, add the industrial concentrated sulfuric acid of mass concentration 98% by volume ratio=10 ︰ 1 of chemical Tie Ni ︰ sulfuric acid, and be heated to 70 ℃, fully stir 30min, form iron mud solution;

(2) 1.1m that obtains to step (1) ³Add the 24kg waste iron filing in the iron mud solution and reduce, behind the recovery time 70min, detect Fe with phenol solution ³⁺, Fe ³⁺Be reduced into Fe fully ²⁺, quiescent setting 30min after finishing extracts supernatant, lower sediment dehydration landfill disposal;

(3) industrial alcohol that adds purity 99% by V (supernatant)/V (ethanol)=10:1 in supernatant gets FeSO to shorten the crystallization time of ferrous sulfate effectively after the crystallization fully ₄7H ₂O.FeSO after testing ₄7H ₂O content reaches 98.34%, and other indexs also all reach GB10531-89 water treatment agent ferrous sulfate high-class product standard.Ferrous sulfate can be back to the Fenton system or be used as other purposes.

Embodiment 2:

Raw material: Fenton technology advanced treating alcohol waste water residue iron mud, Fe ₂O ₃Content 55.8%, the content of organic matter 25.4%.

Treatment step:

(1) gets above-mentioned Fenton iron soiled ends and concentrate the chemical iron mud 1m that obtains moisture content 94.8% ³, adding the industrial concentrated sulfuric acid of mass concentration 98% by volume ratio=10 ︰ 1 of chemical Tie Ni ︰ sulfuric acid, temperature is controlled at 75 ℃, fully stirs 30min, forms iron mud solution;

(2) 1.1m that obtains to step (1) ³Add the 22kg waste iron filing in the iron mud solution and reduce, behind the reduction 60min, detect Fe with phenol solution ³⁺, Fe ³⁺Be reduced into Fe fully ²⁺, quiescent setting 30min after finishing extracts supernatant, lower sediment dehydration landfill disposal;

(3) industrial alcohol that adds purity 99% by V (supernatant)/V (ethanol)=10:1 in supernatant gets FeSO to shorten the crystallization time of ferrous sulfate effectively after the crystallization fully ₄7H ₂O.FeSO after testing ₄7H ₂O content reaches 98.52%, and other indexs also all reach GB10531-89 water treatment agent ferrous sulfate high-class product standard.

Embodiment 3:

Raw material: Fenton technology deep treatment of pharmaceutical waste water residue iron mud, Fe ₂O ₃Content 55.1%, the content of organic matter 26.9%.

Treatment step:

(1) gets above-mentioned Fenton iron mud obtains moisture content 93.5% after concentration chemical iron mud 1m ³, adding the industrial concentrated sulfuric acid of mass concentration 98% by volume ratio=10 ︰ 1 of chemical Tie Ni ︰ sulfuric acid, temperature is controlled at 73 ℃, fully stirs 30min, forms iron mud solution;

(2) 1.1m that obtains to step (1) ³Add the 23kg waste iron filing in the iron mud solution and reduce, behind the reduction 65min, detect Fe with phenol solution ³⁺, Fe ³⁺Be reduced into Fe fully ²⁺, quiescent setting 30min after finishing extracts supernatant, lower sediment dehydration landfill disposal;

(3) industrial alcohol that adds purity 99% by V (supernatant)/V (ethanol)=10:1 in supernatant gets FeSO to shorten the crystallization time of ferrous sulfate effectively after the crystallization fully ₄7H ₂O.FeSO after testing ₄7H ₂O content reaches 98.47%, and other indexs also all reach GB10531-89 water treatment agent ferrous sulfate high-class product standard.

Claims

1. the method utilized of a Fenton iron mud resource is characterized in that may further comprise the steps:

(3) in supernatant, press the volume ratio of Shang Qing Ye ︰ ethanol=10 ︰ 1 and add ethanol, shorten the crystallization time of ferrous sulfate, the industrial FeSO that gets product after fully to be crystallized ₄7H ₂O.

2. the method for utilizing according to the described Fenton iron of claim 1 mud resource is characterized in that, the moisture content control of the residue chemistry iron mud of step (1) is 93～96%.

3. the method for utilizing according to the described Fenton iron of claim 1 mud resource is characterized in that the time that described step (2) is reduced with waste iron filing is 60～70min.