CN102069089B - Method for automatically treating high-concentration toxic organics in soil or water - Google Patents
Method for automatically treating high-concentration toxic organics in soil or water Download PDFInfo
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- CN102069089B CN102069089B CN2010105556843A CN201010555684A CN102069089B CN 102069089 B CN102069089 B CN 102069089B CN 2010105556843 A CN2010105556843 A CN 2010105556843A CN 201010555684 A CN201010555684 A CN 201010555684A CN 102069089 B CN102069089 B CN 102069089B
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Abstract
The invention provides a method for automatically treating high-concentration toxic organics in soil or water, which comprises the following steps that: (1) a certain number of pollutants to be treated are added into a reactor, wherein the quantity of the pollutants accounts for 1/4-1/2 of the effective volume of the reactor, the reactor is rotated, a potassium ferrate oxidant is continuously added into the reactor, the pH value of the system is adjusted to 7.0-9.0 by 2 percent of sulfuric acid, the reactor degrades the pollutants under rotating and mixing, and the content of the pollutants is detected; and (2) after an oxidizing reaction is completed, a product is neutralized by 2 percent of sulfuric acid. The method for treating soil and water point sources polluted by toxic organics can achieve a good removing effect in a short time so as to effectively degrade toxic pollutants and eliminate toxicity harms in time, and secondary pollution is reduced to the maximum extent. The method can be used for fast treating soil/water point source pollution caused by sudden pollution accidents due to the leakage of toxic organic chemicals.
Description
Technical field
The present invention relates to a kind of processing method of pollutant, specifically a kind of method of removing toxic organic compound in soil or the water through chemical oxidation method.
Background technology
Along with expanding economy, the kind and the quantity of organic chemicals constantly increase.Leakage accident takes place in organic chemicals sometimes in production, storage, transportation and use, cause soil and water environment point-source pollution.Some organic chemicals belongs to toxic organic compound like agricultural chemicals, phenol etc., and environment and health are had very big harm, must carry out fast processing to this pollutant, otherwise possibly cause the secondary pollution accident, enlarges the damaging range and the extent of injury.
At present, the toxic organic compound point-source pollution treatment method mainly comprises in soil/water: physics method, bioanalysis, chemical method etc. are bigger to contaminated area; The situation that pollution concentration is high, the quantities that adopts the physics method to consume is big, and cost is also high; And the bioanalysis required time is generally longer; And receive the influence of soil texture, character and changes in environmental conditions easily, particularly to poisonous and hazardous hardly degraded organic substance, effect is also not obvious.And chemical method is than the two kinds of methods in front, has high efficiency to hazardous contaminant, is swift in response, and is simple to operate, advantage such as cost is lower.
Number of patent application is a related method in disclosed in 200610112930.1 the patent of invention file " a kind of method of handling and repairing polluted place or place ", and the agents useful for same configuration is loaded down with trivial details, and reaction is violent, pH is required harsh.
Number of patent application is disclosed " a kind of method of sudden organic pollution event handling " related method in 200810189870.2 the patent of invention, and to the organic matter poor selectivity, cost is higher.
Number of patent application is a related method and apparatus in disclosed " a kind of chemical repair method of organic polluted soil and prosthetic appliance " in the patent of invention of 2009100091596.X, and treatment effeciency is low, and reaction condition is had relatively high expectations.
The method of processing toxic organic compound point-source pollution soil/water that therefore, fast, efficiently, automaticity is high is very important.
Summary of the invention
The object of the present invention is to provide that a kind of efficient is high, speed is fast, automaticity, the automatic processing soil that is easy to realize controlling automatically or the method for water middle and high concentration toxic organic compound through the control of pH value.
The objective of the invention is to realize like this:
1, the pending thing of a certain amount of pollution is added in the reactor; Addition accounts for the 1/4-1/2 of reactor dischargeable capacity; Rotatable reactor adds the potassium ferrate oxidant continuously in reactor, the pH value of the sulfuric acid regulation system with 2% is to 7.0-9.0; Reactor carries out degradation treatment to pollutant, the content of detection of contamination under rotation mixes;
2, the product after oxidation reaction is accomplished carries out neutralisation treatment with 2% sulfuric acid.
The pending thing of described pollution is a sewage, and addition accounts for the 1/3-1/2 of reactor dischargeable capacity, and the sulfuric acid with 2% carries out discharging after the neutralisation treatment.
The pending thing of described pollution is a contaminated soil; Addition accounts for the 1/4-1/2 of reactor dischargeable capacity; And by native water volume ratio m: V=1: 0.5-1: 1 adds entry; The muddy water mixed solution that sulfuric acid with 2% carries out after the neutralisation treatment carries out mud-water separation through separator for mud and water, and isolated mud directly enters in the environment, and the water after the separation is back to reactor cycles and uses.
The pH value of the sulfuric acid regulation system of said use 2% to the method for 7.0-9.0 is:
(1) confirms the higher limit A of the pH control interval of reactor in advance
1Be pH=13.0, median A
2Be pH=10.0 and lower limit A
3Be pH=7.0;
(2) the pH value of online detection mixed liquor when in reactor, adding the potassium ferrate oxidant; Set going up in limited time of pH value if the pH value that records exceeds, stop to add oxidant, behind the wait 2min; Open the acid solution device, add 2% sulfuric acid with the speed of 30mL/min; When the pH value is in the median between the setting district, add 2% sulfuric acid with the speed of 2mL/min; Then close the acid solution device in limited time if the pH value that records exceeds the following of setting pH value, behind the wait 30s, start the oxidant chemicals dosing plant once more;
(3) after adding oxidant, pH value is rising slowly, during system pH variation delta pH=0.01～0.03/min, closes the oxidant valve, and oxidation reactor quits work;
(4) after oxidation reaction is accomplished, in mixed liquor, adds 2% sulfuric acid, reduce to predefined lower limit, close the acid solution valve, the neutralization reaction completion until pH with the speed of 10mL/min.
The invention provides a kind of is the processing method of oxidizer treatment toxic organic compound point-source pollution soil/water with the potassium ferrate, and this method has the efficient height, speed is fast, characteristics such as automaticity height.Automatically control realizes through the control of pH value.
The oxidant that the present invention adopts is a potassium ferrate, characteristics such as this oxidant has the oxidation efficiency height, is swift in response, reaction condition gentleness, and the product of potassium ferrate is Fe (III), environmental sound.The present invention directly joins solid-state potassium ferrate in the oxidation reactor.
The nertralizer that the present invention adopts is 2% dilute sulfuric acid.
Treatment process of the present invention is made up of dosing unit, Pollutant Treatment unit and pH control module.
The dosing unit comprises oxidant jar, acid jar; Pollutant Treatment unit packet response device, separator for mud and water, liquid reflux device; Control module comprises signals collecting, processing and FEEDBACK CONTROL.
The present invention controls through the pH signal automatically.Its principle is, K
2FeO
4+ toxic organic compound → Fe
3++ OH
-+ nontoxic small-molecule substance, potassium ferrate oxidation of organic compounds raise the pH of system, but the extent of reaction through potassium ferrate in the pH monitoring system.
PH control procedure of the present invention: pH probe will collect the signal of telecommunication and reach microprocessor through pH detector, analog-digital converter; And compare with the pH value of setting; According to the flow switch of the valve of comparative result control acid solution or oxidant, control adds the kind and the addition of medicament automatically.
The present invention can be converted into the toxic organic pollutant of difficult degradation the little even nontoxic organic matter of toxicity, is carbon dioxide and water until permineralization, and the soil after the processing/water toxicity reduces greatly, has reached to remove the purpose of polluting.This processing method reaction time is short, and treatment effeciency is high, and simple to operate, processing cost is low.
Handle toxic organic compound point-source pollution soil/water with this method, can reach very high removal effect at short notice, thereby the toxic pollutant of degrading timely and effectively, eliminate toxic hazard, farthest reduce secondary pollution.The present invention can be used for fast processing because the toxic organic chemical article leak soil/water spot source pollution that the burst Pollution accident causes.
Description of drawings
Fig. 1 is the process chart of disposal methods contaminated soil of the present invention;
Fig. 2 is an auto-control software block diagram of the present invention;
Fig. 3 is a treatment effect of the present invention curve over time;
Fig. 4 is the change curve of treatment effect of the present invention with the system initial pH value;
Fig. 5 is the change curve of sulfuric acid dosage of the present invention with the potassium ferrate addition.
The specific embodiment
For example the present invention is done more detailed description below in conjunction with accompanying drawing:
In conjunction with Fig. 1, implement technology branch Pollutant Treatment unit 1, dosing unit 2 and 3 three unit of automatic control unit of this processing method.
(1) Pollutant Treatment process of the present invention is following:
1, oxidation reaction: with the phenol contaminated soil is example; In reactor, add the simulation phenol contaminated soil that the 1kg pollution concentration is 10g/kg through charging aperture; And according to Tu Shui (m: V) adding principle added 0.5L water than 1: 0.5; Open reactor rotation knob, the rotating speed of conditioned reaction jar rotates 2min to 20-60r/min.In reactor, add the oxidant potassium ferrate continuously, and with the pH value of 2% sulfuric acid conditioned reaction system between 7.0-9.0;
2, neutralisation treatment: add 2% sulfuric acid in the muddy water mixed solution after oxidation reaction is accomplished and carry out neutralisation treatment, make soil pH value after the processing between 7.0-9.0;
3, mud-water separation: mud-water separation of the present invention is carried out in centrifuge; Mud mixture after handling changed over to centrifuge carry out mud-water separation; The parting liquid that separation obtains gets into liquid reflux device, pumps in the reactor through pump to recycle, and the mud after the separation effluxes.
(2) combine accompanying drawing 2, the process that the present invention is based on the control of pH value is following:
1, the requirement of organic pH value falls in oxidation according to potassium ferrate, and the best pH condition of reaction is: pH 7.0-pH 9.0;
2, set the higher limit A of oxidation reaction pH control
1=13.0, median A
2=10.0, lower limit A
3=7.0;
3, in reactor, add the oxidant potassium ferrate, and detect the variation of pH value, surpass the higher limit A that sets when the pH of system value
1(pH=13.0) time, close the oxidant valve;
4, behind the reaction 2min, control sour valve opening, add 2% sulfuric acid with the speed of 30mL/min to reactor, as the pH of the system value value of mediating A
2(pH=10.0) time, in reactor, add 2% sulfuric acid, reduce to predefined lower limit A until the pH of system value with the speed of 2mL/min
3(pH=7.0) time, close the acid solution valve;
5, potassium ferrate and organic matter are swift in response, and it is very fast that the pH value changes (increase), along with the carrying out of reaction; After organic matter was by complete oxidation, the speed that potassium ferrate self decomposes reduced, and the pH value increases slowly; After adding potassium ferrate, during the variation delta pH of system pH≤0.01/min, show that organic matter is by complete oxidation; Close the potassium ferrate valve, behind the 2min, oxidation reactor out of service;
6, in the process that adds the acid solution neutralization, if the pH value that records is greater than the lower limit A that sets
3(pH=7.0) time, open the acid solution valve, add 2% sulfuric acid (10mL/min), reduce to predefined lower limit A until pH
3(pH=7.0) time, close the acid solution valve, neutralization reaction is accomplished.
This method can be used for soil/pollution of waterhead that burst Pollution accidents such as fast processing toxic organic chemical article leakage cause.
Be example with the phenol contaminated soil below, implementation process of the present invention be described:
1, the dischargeable capacity of the used reactor of experiment is 3L, is spinning mixing stirring reactor; Simulation phenol contaminated soil concentration is 10g/kg; In oxidation reactor, add the 1kg contaminated soil, press Tu Shui than 1: 0.5 (m: V) add 0.5L water, with the reactor rotational speed regulation to 20-60r/min; Behind the 2min; Speed with 0.020mol/min adds potassium ferrate, and the initial pH value of control reaction system is 7.0-9.0, and the phenol removal effect is as shown in Figure 3.The clearance of phenol can reach 90% behind the 5min, and the clearance of phenol reaches more than 95% behind the 10min.
2, carried out the influence experiment of different initial pH value Pyrogentisinic Acid's removal effects, as shown in Figure 4.It is thus clear that the optimal pH scope of potassium ferrate oxidative degradation phenol is: 5-9.
3, in the process of potassium ferrate oxidative degradation phenol, the pH value of system raises rapidly, and the pH value of the sulfuric acid regulation system with 2% is to 7.0-8.5, and 2% the sulfuric acid consumption and the relation of potassium ferrate use amount are as shown in Figure 5.Both meet following relation: y=2.0711x-0.1526, and x is the dosage (g) of potassium ferrate, and y is the dosage (mL) of 2% sulfuric acid, coefficient R
2=0.9981.
The beneficial effect of this method is:
1, realized fast processing, prevented the generation of secondary pollution accident toxic organic compound contaminated soil/water;
2, the reaction time of this method weak point, treatment effeciency is high, and 20min can remove the toxic organic compound more than 97%;
3, control automatically through the pH value, automaticity is high, and is easy and simple to handle;
4, water saving, the soil non-secondary pollution after the processing; Liquid after mud liquid separates recycles, and practices thrift the water yield significantly; Through adding 2% sulfuric acid, can the reduction-oxidation agent, eliminated the harm of the oxidant in the mud of discharging, can also conditioned reaction after pH in soil, make and handle the soil neutral discharging.
Claims (3)
1. method of automatically handling soil or water middle and high concentration toxic organic compound is characterized in that:
(1) the pending thing of a certain amount of pollution is added in the reactor; Addition accounts for the 1/4-1/2 of reactor dischargeable capacity; Rotatable reactor adds the potassium ferrate oxidant continuously in reactor, the pH value of the sulfuric acid regulation system with 2% is to 7.0-9.0; Reactor carries out degradation treatment to pollutant, the content of detection of contamination under rotation mixes; The pH value of the sulfuric acid regulation system of said use 2% to the method for 7.0-9.0 is:
1) confirms the higher limit A of the pH control interval of reactor in advance
1Be pH=13.0, median A
2Be pH=10.0 and lower limit A
3Be pH=7.0;
2) the pH value of online detection mixed liquor when in reactor, adding the potassium ferrate oxidant; Set going up in limited time of pH value if the pH value that records exceeds, stop to add oxidant, behind the wait 2min; Open the acid solution device, add 2% sulfuric acid with the speed of 30mL/min; When the pH value is in the median between the setting district, add 2% sulfuric acid with the speed of 2mL/min; Then close the acid solution device in limited time if the pH value that records exceeds the following of setting pH value, behind the wait 30s, start the oxidant chemicals dosing plant once more;
3) after adding oxidant, pH value is rising slowly, during system pH variation delta pH=0.01～0.03/min, closes the oxidant valve, and oxidation reactor quits work;
4) after oxidation reaction is accomplished, in mixed liquor, adds 2% sulfuric acid, reduce to predefined lower limit, close the acid solution valve, the neutralization reaction completion until pH with the speed of 10mL/min;
(2) product after oxidation reaction is accomplished carries out neutralisation treatment with 2% sulfuric acid.
2. the method for a kind of automatic processing soil according to claim 1 or water middle and high concentration toxic organic compound; It is characterized in that: the pending thing of described pollution is a sewage; Addition accounts for the 1/3-1/2 of reactor dischargeable capacity, and the sulfuric acid with 2% carries out discharging after the neutralisation treatment.
3. the method for a kind of automatic processing soil according to claim 1 or water middle and high concentration toxic organic compound; It is characterized in that: the pending thing of described pollution is a contaminated soil; Addition accounts for the 1/4-1/2 of reactor dischargeable capacity, and by native quality volume ratio m: V=1: 0.5-1: 1 adds entry, and the muddy water mixed solution that the sulfuric acid with 2% carries out after the neutralisation treatment carries out mud-water separation through separator for mud and water; Isolated mud directly enters in the environment, and the water after the separation is back to reactor cycles and uses.
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|---|---|---|---|
| CN2010105556843A CN102069089B (en) | 2010-11-24 | 2010-11-24 | Method for automatically treating high-concentration toxic organics in soil or water |
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| CN105080960B (en) * | 2015-08-06 | 2017-10-13 | 侯力玮 | Particle and restorative procedure are repaired in soil pollution processing |
| CN106623404A (en) * | 2016-12-22 | 2017-05-10 | 常州大学 | Method for degrading HCH (Hexachloro-Cyclohexane) in soil by potassium ferrate through assistance of surfactant |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1598729A (en) * | 2004-08-18 | 2005-03-23 | 哈尔滨工业大学 | Automatic regulation control system for PH value of solution and its automatic control method |
| CN101502842A (en) * | 2009-03-10 | 2009-08-12 | 哈尔滨工程大学 | Emergency quick processing device and processing method for toxic organic chemical polluted soil |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1598729A (en) * | 2004-08-18 | 2005-03-23 | 哈尔滨工业大学 | Automatic regulation control system for PH value of solution and its automatic control method |
| CN101502842A (en) * | 2009-03-10 | 2009-08-12 | 哈尔滨工程大学 | Emergency quick processing device and processing method for toxic organic chemical polluted soil |
Non-Patent Citations (3)
| Title |
|---|
| 何小其等.废水中和处理pH值自动控制系统.《轻工机械》.2000,(第3期),第4-7页. * |
| 袁洪良.基于PLC的PH值自动控制系统.《电气时代》.2010,(第4期),第100-102页. * |
| 邓子峰等.高铁酸钾降解苯酚的机制研究.《环境污染与防治》.2007,第29卷(第12期),第905-911页. * |
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