CN108057715A - The method of outer source additive-mechanical mill chemical degradation 2,4- Dichlorophenols - Google Patents
The method of outer source additive-mechanical mill chemical degradation 2,4- Dichlorophenols Download PDFInfo
- Publication number
- CN108057715A CN108057715A CN201711335067.0A CN201711335067A CN108057715A CN 108057715 A CN108057715 A CN 108057715A CN 201711335067 A CN201711335067 A CN 201711335067A CN 108057715 A CN108057715 A CN 108057715A
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- China
- Prior art keywords
- ball
- dichlorophenols
- outer source
- abrading
- soil
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
- B02C17/10—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls with one or a few disintegrating members arranged in the container
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
- B02C17/18—Details
- B02C17/20—Disintegrating members
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C23/00—Auxiliary methods or auxiliary devices or accessories specially adapted for crushing or disintegrating not provided for in preceding groups or not specially adapted to apparatus covered by a single preceding group
- B02C23/06—Selection or use of additives to aid disintegrating
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- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The method of outer 2,4 Dichlorophenol of source additive mechanical mill chemical degradation of the present invention, belongs to soil remediation application field.It carries out as steps described below：The soil that 2,4 Dichlorophenols will be contained is placed in ball grinder, and the concentration of 2,4 Dichlorophenols is all 1wt.% in soil；According to abrading-ball and the material ratio 4 of soil:1 is put into the different abrading-ball of size, adds in different outer source additives, and the material ratio of outer source additive and soil is 1:10.Ball mill is milled to the predetermined time with setting speed 400r/min, you can reaches the purpose of 2,4 Dichlorophenol of degradation.The present invention's adds in different outer source additives in abrading-ball and can shorten Ball-milling Time, reduces energy consumption.
Description
Technical field
The invention belongs to soil remediation application fields, and in particular to a kind of outer source additive-mechanical mill chemical method 2,
The method of 4- Dichlorophenol experimental study on degradation.
Background technology
2,4- Dichlorophenols are white solid, there is that phenol is smelly, are used for the manufacture of nitrofen more.China is large agricultural country, is
Raising yield herbicide is widely used, therefore has driven the construction in the chemical plant of large quantities of production herbicides, while also band
2,4- Dichlorophenol soil contamination problems are carried out.Since 21st century, reinforcement and social section with people's environmental consciousness
The progress of skill, chemical plant are largely closed, but the soil contamination problem that it is carried over is not resolved.
The research of mechanical mill chemical method degradation persistent organochlorine pesticides has increasingly caused the concern of people so that ball
Grinding mechanochemical reaction becomes one of the hot issue in organic chlorine degradation field.Mechanical mill chemical method to object by applying machinery
Can, change the arrangement of interior of articles particle, induced chemical reaction changes physical object chemical property, so that organic matter occurs
It decomposes, achievees the purpose that degradation.Mechanical mill method is of low cost due to easy to operate, and the secondary pollution of generation is small, by
The organic matter being widely used in degradation soil.But mechanical mill chemical method, since Ball-milling Time is long, it is suitable to find
Additives reduce Ball-milling Time and have become the emphasis of research.
Correlation scholar has relevant report, such as Patent No. to additives in mechanical mill chemical method both at home and abroad
201410089044.6 disclose a kind of side of iron zinc bimetallic mechanical chemistry ball-milling treatment high concentration organic co-contaminated soil
Method：The mass ratio of iron powder and zinc powder is 1:1~5:Between 1, the quality and iron powder and zinc powder total mass ratio of soil are 2:1~10:1
Between, the ratio of material weight is 7:1~28:1, ball grinder rotating speed is between 400-500rpm, when the reaction time is 2-8 small, knot
Fruit shows that more than 99% degradation rate can be reached after when reaction 4 is small.A.Nasser et al. adds in birnessite mixed grinding, as a result
Display birnessite greatly shortens milling time, and as electron acceptor, it has loaded the degradation of DCP90%.Defend cherry flower bud et al.
When carrying out mechanochemical reaction ball milling to bioxin in flying dust, discarded egg shell is added in, the results show that ball milling 8h Hou bioxin
Mass fraction and toxic equivalent be below 50%.
The present invention, for research object, has investigated calcium oxide, aluminium oxide, birnessite and potassium permanganate etc. with 2,4- Dichlorophenols
The influence that outer source additive degrades to 2,4- Dichlorophenols, and their economic benefit has been investigated, filter out optimal external source addition
Agent provides reference for laboratory research and practical application.
The content of the invention
The purpose of the present invention is be directed to mechanical mill chemical method degrading high concentration soil polluted by organic chloride Ball-milling Time to grow this
One problem is degradation object with 2,4- Dichlorophenols contaminated soil, has carried out outer source additive and the degradation of mechanical mill chemical method is imitated
Fruit Optimum Experiment is studied.
The direct ball-milling method cardinal principle of the present invention is to be based on mechanochemical reaction principle, i.e.,：Mechanical mill chemical method passes through
Mechanical energy is applied to object, changes the arrangement of interior of articles particle, induced chemical reaction changes physical object chemical property, from
And organic matter is made to decompose, achieve the purpose that degradation.
Technical scheme is as follows：A kind of side of outer source additive-mechanical mill chemical method degradation 2,4- Dichlorophenols
Method carries out as steps described below：
The soil that 2,4- Dichlorophenols will be contained is placed in ball grinder, and the concentration of 2,4- Dichlorophenols is all 1wt.% in soil；
According to abrading-ball and the material ratio 4 of soil:1 is put into the different abrading-ball of size, adds in different outer source additives, outer source additive with
The material ratio of soil is 1:10.Ball mill is milled to the predetermined time with setting speed 400r/min, you can reaches degradation 2,4- bis-
The purpose of chlorophenol.
The different abrading-ball of the size is diameter 20mm abrading-balls 3,10mm abrading-balls 20,5mm abrading-balls 40.
The outer source additive is calcium oxide, aluminium oxide, birnessite or potassium permanganate.
The predetermined time is 0.5h-4h.
A kind of method of above-mentioned outer source additive-mechanical mill chemical method degradation 2,4- Dichlorophenols, calcium oxide is as external source
Degraded additives rate is 75%, and Ball-milling Time can be greatly shortened.
A kind of method of above-mentioned outer source additive-mechanical mill chemical method degradation 2,4- Dichlorophenols, aluminium oxide is as external source
Degraded additives rate is 68%, and Ball-milling Time can be greatly shortened.
A kind of method of above-mentioned outer source additive-mechanical mill chemical method degradation 2,4- Dichlorophenols, birnessite is as outer
Source additive degradation rate is 75%, can effectively shorten Ball-milling Time.
A kind of method of above-mentioned outer source additive-mechanical mill chemical method degradation 2,4- Dichlorophenols, potassium permanganate is as outer
Source additive degradation rate is 94%, can effectively shorten Ball-milling Time.
A kind of method of above-mentioned outer source additive-mechanical mill chemical method degradation 2,4- Dichlorophenols, considers scale
Change utilization and economic benefit, calcium oxide is optimal outer source additive.
Main advantages of the present invention：
Ball-milling Time can be shortened, reduce energy consumption.
Specific embodiment
(1) acquisition and preservation of soil
Soil collection used in experiment is 10-20cm topsoils in the free of contamination vacant lot in suburb, pedotheque, is placed under the sun
It dries, break into pieces, 14 mesh sieve excessively go to cut weeds and stone, are stored in hermetic bag for use.After testing 2,4- is not contained in soil
Dichlorophenol.
(2) ball milling is tested
The concentration of 2,4- Dichlorophenols is all 1wt.% in the soil degraded in experiment.Every time experiment weigh 50g soil and
0.5g 2,4- Dichlorophenol are placed in ball grinder, according to ratio of grinding media to material 4:1 is put into the different abrading-ball of size, i.e. diameter 20mm abrading-balls 3
A, 10mm abrading-balls 20,5mm abrading-balls 40.Add in different outer source additive (calcium oxide, aluminium oxide, birnessite, Gao Meng
Sour potassium).Ball mill with setting speed 400r/min, be milled to the predetermined time (0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h,
4h), sampling analysis.
(3) in ball milling product 2,4- Dichlorophenols extraction
The native 5g for weighing corresponding Ball-milling Time is placed in 100mL conical flasks, adds in 50mL methanol solutions, ultrasonic extraction
20min, constant temperature oscillation 2h, centrifugation 20min (4000r/min) cross miillpore filter, take supernatant 5mL, with water constant volume to 100mL,
It is to be measured.
(4) 2,4- Dichlorophenols content assaying method
Ultraviolet spectrophotometry, wavelength 286nm, distilled water are reference liquid.Survey calculation obtains 2,4- Dichlorophenol standard curves
For：A=0.0126x+0.0106, R2=0.9993, A are absorbance, x 2,4- Dichlorophenol mass concentrations, recovery of standard addition
98%~102%.
4 embodiments presented below further illustrate the present invention.Embodiment is used to illustrate present invention rather than limit
Present invention.
Embodiment 1
Influence of the calcium oxide to 2,4- Dichlorophenol degradation effects
50g soil and 0.5g 2 are weighed, 4- Dichlorophenols are placed in ball grinder, according to ratio of grinding media to material 4:1 is put into the different mill of size
Ball, i.e. diameter 20mm abrading-balls 3,10mm abrading-balls 20,5mm abrading-balls 40.5g calcium oxide is added in as outer source additive.Ball milling
Machine is milled to predetermined time (0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h), sampling point with setting speed 400r/min
Analysis, is tested by specific steps (3) and (4).With the increase by 2 of Ball-milling Time, the degradation rate of 4- Dichlorophenols is also increasing, and adds
Up to 84% or so when adding CaO；In ball milling 0.5h, 2, the 4- dichloro Phenol degradation rates for adding CaO have reached 75%, and do not have
There is 2, the 4- dichloros Phenol degradation rate of addition CaO less than 10%, just reach 80% after ball milling 19h.Therefore, calcium oxide is as external source
Degraded additives rate is 75%, and Ball-milling Time can be greatly shortened.
Embodiment 2
Influence of the aluminium oxide to 2,4- Dichlorophenol degradation effects
50g soil and 0.5g 2 are weighed, 4- Dichlorophenols are placed in ball grinder, according to ratio of grinding media to material 4:1 is put into the different mill of size
Ball, i.e. diameter 20mm abrading-balls 3,10mm abrading-balls 20,5mm abrading-balls 40.5g aluminium oxide is added in as outer source additive.Ball milling
Machine is milled to predetermined time (0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h), sampling point with setting speed 400r/min
Analysis, is tested by specific steps (3) and (4).It is better than the effect for not adding aluminium oxide to add the degradation effect of aluminium oxide, in ball
The degradation rate that aluminium oxide is added when grinding 0.5h has reached 68%, there was only 5% or so without adding aluminium oxide degradation rate, with ball
The increase of time consuming, the degradation rate for adding aluminium oxide reach more than 70%, without adding aluminium oxide, just reach after ball milling 4h
40%.Therefore, aluminium oxide is 68% as external source degraded additives rate, and Ball-milling Time can be greatly shortened.
Embodiment 3
Influence of the birnessite to 2,4- Dichlorophenol degradation effects
50g soil and 0.5g 2 are weighed, 4- Dichlorophenols are placed in ball grinder, according to ratio of grinding media to material 4:1 is put into the different mill of size
Ball, i.e. diameter 20mm abrading-balls 3,10mm abrading-balls 20,5mm abrading-balls 40.5g birnessites are added in as outer source additive.Ball
Grinding machine is milled to predetermined time (0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h), sampling point with setting speed 400r/min
Analysis, is tested by specific steps (3) and (4).In ball milling 0.5h, the degradation rate for adding birnessite reaches 75%, and does not have
The degradation rate for having addition birnessite is 5% or so, with the increase of Ball-milling Time, after 1h, adds the 2,4- of birnessite
Dichloro Phenol degradation rate reduces, it is possible to create new chlorinated compound.It is not added with the degradation rate of birnessite as time increases
Degradation rate is slowly increasing, inefficiency, high energy consumption.Therefore, birnessite is 75% as external source degraded additives rate, energy
Enough effective shortening Ball-milling Times.
Embodiment 4
Influence of the potassium permanganate to 2,4- Dichlorophenol degradation effects
50g soil and 0.5g 2 are weighed, 4- Dichlorophenols are placed in ball grinder, according to ratio of grinding media to material 4:1 is put into the different mill of size
Ball, i.e. diameter 20mm abrading-balls 3,10mm abrading-balls 20,5mm abrading-balls 40.5g potassium permanganate is added in as outer source additive.Ball
Grinding machine is milled to predetermined time (0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h), sampling point with setting speed 400r/min
Analysis, is tested by specific steps (3) and (4).In ball milling 0.5h, the degradation rate for adding potassium permanganate reaches 94%, with
The increase of Ball-milling Time, degradation rate are basically unchanged, but the degradation rate for being not added with potassium permanganate just reaches 40% or so in 4h, says
Bright potassium permanganate has the degradation of 2,4- Dichlorophenols good removal effect, but specific degradation pathway needs further to be ground
Study carefully.Therefore, potassium permanganate is 94% as external source degraded additives rate, can effectively shorten Ball-milling Time.
Embodiment 5
Economic and Efficiency Analysis
In view of mechanical mill chemical method scale application, therefore it must take into consideration the cost problem of outer source additive.With 4 kinds
External source additive treating 1t soil is calculated, CaO, aluminium oxide, birnessite, the amount of money of potassium permanganate is respectively 280 yuan,
420 yuan, 2086 yuan, 780 yuan, therefore CaO is minimum as the cost of outer source additive.The main component of useless egg shell is CaCO3,
Whether can also achieve the effect that CaO up for further studying using useless egg shell as outer source additive, if it is possible to which realization can
To realize waste utilization, research cost can be further reduced, realizes that the scale of mechanical mill chemical method utilizes.
Claims (5)
1. the method for a kind of outer source additive-mechanical mill chemical method degradation 2,4- Dichlorophenols, it is characterised in that according to following steps
It is rapid to carry out：
The soil that 2,4- Dichlorophenols will be contained is placed in ball grinder, and the concentration of 2,4- Dichlorophenols is all 1wt.% in soil；According to
The material ratio 4 of abrading-ball and soil:1 is put into the different abrading-ball of size, adds in different outer source additives, outer source additive and soil
Material ratio be how many 1:10；Ball mill is milled to the predetermined time with setting speed 400r/min, you can reaches degradation 2,4- bis-
The purpose of chlorophenol.
2. a kind of method of outer source additive according to claim 1-mechanical mill chemical method degradation 2,4- Dichlorophenols,
It is diameter 20mm abrading-balls 3,10mm abrading-balls 20,5mm abrading-balls 40 to be characterized in that the different abrading-ball of the size.
3. a kind of method of outer source additive according to claim 1-mechanical mill chemical method degradation 2,4- Dichlorophenols,
It is calcium oxide, aluminium oxide, birnessite or potassium permanganate to be characterized in that the outer source additive.
4. a kind of method of outer source additive according to claim 1-mechanical mill chemical method degradation 2,4- Dichlorophenols,
It is 0.5h-4h to be characterized in that the predetermined time.
5. a kind of method of outer source additive according to claim 3-mechanical mill chemical method degradation 2,4- Dichlorophenols,
It is optimal outer source additive to be characterized in that calcium oxide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109092455A (en) * | 2018-07-31 | 2018-12-28 | 南京林业大学 | A method of using mechanochemical reaction degradation 5a,6,9,9a-hexahydro-6,9-methano-2,4 |
| CN113814264A (en) * | 2021-07-28 | 2021-12-21 | 北京师范大学 | Method for degrading lindane in different types of soil by additive and mechanochemical method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3532623A (en) * | 1966-08-05 | 1970-10-06 | British Petroleum Co | Oleophilic metals |
| CN1100663A (en) * | 1992-12-18 | 1995-03-29 | 技术资源有限公司 | Toxic material disposal |
| JP2005028291A (en) * | 2003-07-14 | 2005-02-03 | Kitakyushu Foundation For The Advancement Of Industry Science & Technology | Production method for organic chlorine compound removal agent |
| US7026084B2 (en) * | 2002-12-02 | 2006-04-11 | Eastman Kodak Company | Cocrystals containing high-chlorine titanyl phthalocyanine and low concentration of titanyl fluorophthalocyanine, and electrophotographic element containing same |
-
2017
- 2017-12-14 CN CN201711335067.0A patent/CN108057715A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3532623A (en) * | 1966-08-05 | 1970-10-06 | British Petroleum Co | Oleophilic metals |
| CN1100663A (en) * | 1992-12-18 | 1995-03-29 | 技术资源有限公司 | Toxic material disposal |
| US7026084B2 (en) * | 2002-12-02 | 2006-04-11 | Eastman Kodak Company | Cocrystals containing high-chlorine titanyl phthalocyanine and low concentration of titanyl fluorophthalocyanine, and electrophotographic element containing same |
| JP2005028291A (en) * | 2003-07-14 | 2005-02-03 | Kitakyushu Foundation For The Advancement Of Industry Science & Technology | Production method for organic chlorine compound removal agent |
Non-Patent Citations (2)
| Title |
|---|
| 张冬格等: "CaO机械化学法去除土壤中DDTs的工艺参数优化", 《环境科学研究》 * |
| 胡汉芳等: "机械化学法对含氯有机物的脱氯研究进展", 《工业安全与环保》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109092455A (en) * | 2018-07-31 | 2018-12-28 | 南京林业大学 | A method of using mechanochemical reaction degradation 5a,6,9,9a-hexahydro-6,9-methano-2,4 |
| CN113814264A (en) * | 2021-07-28 | 2021-12-21 | 北京师范大学 | Method for degrading lindane in different types of soil by additive and mechanochemical method |
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