CN105945062A - Method for chelating heavy metal in contaminated soil through temperature-sensitive polymer - Google Patents

Method for chelating heavy metal in contaminated soil through temperature-sensitive polymer Download PDF

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Publication number
CN105945062A
CN105945062A CN201610406576.7A CN201610406576A CN105945062A CN 105945062 A CN105945062 A CN 105945062A CN 201610406576 A CN201610406576 A CN 201610406576A CN 105945062 A CN105945062 A CN 105945062A
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China
Prior art keywords
sensitive polymer
temperature
temperature sensitive
heavy metal
chelating
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Pending
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CN201610406576.7A
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Chinese (zh)
Inventor
高旻天
李文
郑琴
胡佳俊
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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Priority to CN201610406576.7A priority Critical patent/CN105945062A/en
Publication of CN105945062A publication Critical patent/CN105945062A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
    • B09C1/08Reclamation of contaminated soil chemically

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  • Life Sciences & Earth Sciences (AREA)
  • Soil Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention discloses a method for chelating heavy metal in contaminated soil through temperature-sensitive polymer. The method includes the steps that firstly, a certain amount of the contaminated soil is added into a temperature-sensitive polymer aqueous solution for chelating reaction, natural settling is conducted, and temperature-sensitive polymer supernatant containing chelating heavy metal is obtained for 1 hour; secondly, when the supernatant is heated to 40-60 DEG C, the phase of the temperature-sensitive polymer supernatant containing chelating heavy metal is changed at phase change temperature for centrifugal separation, and temperature-sensitive polymer precipitates of chelated heavy metal are obtained; thirdly, hydrochloric acid is added dropwise into the temperature-sensitive polymer of the separated chelated heavy metal, the heavy metal is separated out from the temperature-sensitive polymer, and separated temperature-sensitive polymer is obtained; fourthly, the temperature-sensitive polymer is steamed dry, then deionized water is added for dissolving, freezing and drying are conducted, and the temperature-sensitive polymer is obtained again. The heavy metal can be separated very easily by means of the phase change characteristic of the temperature-sensitive polymer, the temperature-sensitive polymer can be recycled, cost is reduced, and the method is easy to operate and easy to apply and popularize.

Description

A kind of method utilizing temperature sensitive polymer chelating Heavy Metals in Contaminated Soils
Technical field
The present invention relates to a kind of method utilizing temperature sensitive polymer chelating Heavy Metals in Contaminated Soils, belong to contaminated soil Treatment process field.
Background technology
In the last few years along with modern industrialization and the fast development of urbanization, the Soil Environmental Pollution problem that China faces is increasingly serious.Various industrial wastewaters, waste gas, feces of livestock and poultry, fertilizer and pesticide, sewage irrigation etc. become heavy metal-polluted soil (As, Cd, Hg, Pb etc.) main source, and this makes soil receive the most serious destruction.
Toxic heavy metal during soil pollution incubation period length, non-degradable and reparation difficulty big etc. so that the soil fertility of heavy metal pollution reduces, and crop yield declines, but also easily polluted underground water accumulating in human body, animal body and in plant.According to statistics, there have been 20,000,000 hm in China2Cultivated area is polluted (Cd, As, Pb, Hg, Zn etc.) in various degree, constitutes about the 20% of total cultivated area.The whole nation there are about 1.3 × 10 at present4 hm 2 Plough and polluted by Cd, there are about 3.2 × 104 hm 2Arable land polluted by hydrargyrum, it addition, also have other heavy metal contaminated soil in various degree, indirectly give the mankind health cause serious harm.
At present, method for administering and repairing heavy metal in soil pollutes has a lot, mainly has physical engineering measure, electrochemical rehabilitation, chemical, biological control measure, Agro-ecology measure etc., but processing cost is high, investment cost is high, it is possible to create the shortcomings such as secondary pollution.A kind of the most the more commonly used method is to use chemical improvement agent reparation and heavy metal chelant repairing method, and heavy metal chelant repairing method is to apply heavy metal chelant to the soil surface of solids, improves the available state of heavy metal in soil, makes it easy to flowing and absorbs.EDTA is the most frequently used a kind of chelating agen, but price and be difficult to be degraded, limit its extensive utilization, and be not easy to recycle, EDTA is a kind of to define, with heavy metal ion, the complex that stability is the strongest, affect stability and the animal migration of heavy metal, add intractability and the cost of waste water.
Temperature responsive polymer is one of of paramount importance type in intelligent polymer.This base polymer is generally of a minimum critical solution temperature (LCST).Below this temperature, polymer is in good dissolved state in water, when temperature rise to occur the temperature (LCST) of phase in version and above time, hydrogen bond action between polymer chain and water is destroyed, polymer chain starts dehydration, subsiding therewith generation segment and assemble, corresponding aqueous solution is also heterogeneous from being homogeneously changed into, and this process typically has reversibility.Temperature sensitivity tree shaped polymer combines temperature sensitive polymer and has the feature of respondent behavior and the mode of tree shaped polymer non-linear structure to temperature, structure can easily be accommodated and functionalization feature.But, the most do not find about temperature sensitive polymer report of concrete application aspect in heavy-metal contaminated soil.The present invention is to utilize temperature sensitive polymer to chelate heavy metal in soil;After chelating, utilize the phase transformation separating beavy metal of temperature sensitive polymer.It is applied to heavy-metal contaminated soil administer.
Summary of the invention
It is an object of the invention to provide a kind of method utilizing temperature sensitive polymer chelating Heavy Metals in Contaminated Soils, the method can effectively be administered the soil of heavy metal pollution, and can be recycled temperature sensitive polymer.
For achieving the above object, the technical solution adopted in the present invention is: a kind of method utilizing temperature sensitive polymer chelating Heavy Metals in Contaminated Soils, comprises the steps of:
(1). weigh a certain amount of contaminated soil, a certain amount of temperature sensitive polymer aqueous solution, by a certain amount of contaminated soil, add temperature sensitive polymer aqueous solution to, vibrate 12 hours at being warmed up to 20-40 DEG C, temperature sensitive polymer and heavy metal carry out chelatropic reaction, natural subsidence 1 hour, obtains the supernatant containing the temperature sensitive polymer chelating heavy metal;
(2). after chelatropic reaction terminates, during by above-mentioned supernatant heating temperature to 40-60 DEG C, temperature sensitive polymer supernatant containing chelating heavy metal undergoes phase transition when its phase transition temperature, it is centrifuged separating, the rotating speed of centrifugation is 5000rpm-10000rpm, time is 2-10min, obtains chelating the temperature sensitive polymer precipitum of heavy metal after being centrifuged;
(3). dripping hydrochloric acid in the temperature sensitive polymer of the chelating heavy metal after separating, heavy metal parses from temperature sensitive polymer, the temperature sensitive polymer after being resolved;
(4). first it is evaporated the temperature sensitive polymer after above-mentioned parsing, adds deionized water dissolving, after dialysing three days, lyophilization, retrieve temperature sensitive polymer, this temperature sensitive polymer can recycle.
The beneficial effects of the present invention is:
When the method for the present invention utilizes temperature sensitive polymer, heavy metal is sequestered on temperature sensitive polymer, makes heavy metal in soil concentration decline to a great extent, plays the effect of rehabilitating soil;Utilize the phase-change characteristic of temperature sensitive polymer, can particularly simple separating beavy metal, temperature sensitive polymer reusable edible, reduce cost;The method popularization and application simple to operate, easy.
Accompanying drawing explanation
Fig. 1 is the structural representation of the temperature sensitive polymer used in the method for the present invention.
Fig. 2 is the cadmium ion comparision contents figure in embodiment 1 in the temperature sensitive polymer heavy metal contaminated soil of preparation, in figure, vertical coordinate is the content of Cadmium in Soil, abscissa be by heavy-metal contaminated soil sample and through temperature sensitive polymer heavy metal contaminated soil of the present invention process after pedotheque.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further.
Embodiment
Soil used in the present embodiment is Shanghai University's East Semen Maydis experiment field soil, and pedotheque natural air drying, after crossing 2mm sieve, utilizes CdCl2Aqueous solution oscillation treatment 24 hours;Then filter, wash twice, dry, cross 2mm sieve.A kind of described method utilizing temperature sensitive polymer chelating Heavy Metals in Contaminated Soils, its step is as follows:
(1). weigh the contaminated soil of 1g, 10mL concentration is the temperature sensitive polymer solution of 0.05mmol/L, the contaminated soil of 1g is added in the temperature sensitive polymer aqueous solution that 10mL concentration is 0.05mmol/L, it is warmed up to 37 DEG C, vibrate 12 hours, temperature sensitive polymer and heavy metal carry out chelatropic reaction, natural subsidence 1 hour, obtains the supernatant containing the temperature sensitive polymer chelating heavy metal;
(2). above-mentioned supernatant is heated to 45 DEG C, temperature sensitive polymer supernatant containing chelating heavy metal is centrifuged when its phase transformation separating, the rotating speed of centrifugation is 10000rpm, and the time is 10min, obtains the temperature sensitive polymer precipitum of chelating heavy metal after being centrifuged;
(3). dripping hydrochloric acid in the temperature sensitive polymer precipitum of the chelating heavy metal after separating, heavy metal parses from temperature sensitive polymer, the temperature sensitive polymer after being resolved;
(4). first it is evaporated the temperature sensitive polymer after above-mentioned parsing;Add deionized water dissolving, after dialysing three days, lyophilization, retrieve temperature sensitive polymer, or go to step (1) recycling.
The temperature sensitive polymer used in the present embodiment, as shown in Figure 1.
As in figure 2 it is shown, from figure 2 it can be seen that adding to of temperature sensitive polymer prepared by embodiments of the invention can decrease the concentration of cadmium ions in cadmium pollution soil in cadmium pollution soil, reach the effect of rehabilitating soil.

Claims (1)

1. the method utilizing temperature sensitive polymer chelating Heavy Metals in Contaminated Soils, it is characterised in that comprise the steps of:
Weigh a certain amount of contaminated soil, a certain amount of temperature sensitive polymer aqueous solution, by a certain amount of contaminated soil, add temperature sensitive polymer aqueous solution to, Vibrating 12 hours at being warmed up to 20-40 DEG C, temperature sensitive polymer and heavy metal carry out chelatropic reaction, natural subsidence 1 hour, obtain the supernatant containing the temperature sensitive polymer chelating heavy metal;
After chelatropic reaction terminates, during by above-mentioned supernatant heating temperature to 40-60 DEG C, temperature sensitive polymer supernatant containing chelating heavy metal undergoes phase transition when its phase transition temperature, it is centrifuged separating, the rotating speed of centrifugation is 5000rpm-10000rpm, time is 2-10min, obtains chelating the temperature sensitive polymer precipitum of heavy metal after being centrifuged;
Dripping hydrochloric acid in the temperature sensitive polymer of the chelating heavy metal after separating, heavy metal parses from temperature sensitive polymer, the temperature sensitive polymer after being resolved;
First it is evaporated the temperature sensitive polymer after above-mentioned parsing, adds deionized water dissolving, after dialysing three days, lyophilization, retrieve temperature sensitive polymer, this temperature sensitive polymer can recycle.
CN201610406576.7A 2016-06-12 2016-06-12 Method for chelating heavy metal in contaminated soil through temperature-sensitive polymer Pending CN105945062A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103554514A (en) * 2013-10-30 2014-02-05 江苏上田环境修复有限公司 Chelating agent for recovering heavy metal-contaminated soil, and preparation and usage methods thereof
CN104672466A (en) * 2015-02-12 2015-06-03 同济大学 Dithiocarbamic acid functionalized alkylenediamine core dendritic polymer serving as soil heavy metal passivative remediation agent and preparation method of dithiocarbamic acid functionalized alkylenediamine core dendritic polymer
CN104802298A (en) * 2015-03-03 2015-07-29 广州市金龙峰环保设备工程有限公司 Heavy metal contaminated soil treatment method and device implementing same
CN105080959A (en) * 2015-08-06 2015-11-25 张自学 Method for repairing heavy metal contaminated soil and soil heavy metal contamination repairing passivator
CN105295061A (en) * 2015-10-28 2016-02-03 上海大学 Temperature-sensitive polymer containing heavy metal chelate group and preparation method and application of temperature-sensitive polymer
CN105363773A (en) * 2015-12-08 2016-03-02 湖南康盟环保科技有限公司 Heavy metal fixing agent and in-situ repair method for heavy metal contaminated soil
CN105598152A (en) * 2015-11-05 2016-05-25 深圳多元拓展环保科技有限公司 Soil heavy metal pollution in-suit capturing treating method

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103554514A (en) * 2013-10-30 2014-02-05 江苏上田环境修复有限公司 Chelating agent for recovering heavy metal-contaminated soil, and preparation and usage methods thereof
CN104672466A (en) * 2015-02-12 2015-06-03 同济大学 Dithiocarbamic acid functionalized alkylenediamine core dendritic polymer serving as soil heavy metal passivative remediation agent and preparation method of dithiocarbamic acid functionalized alkylenediamine core dendritic polymer
CN104802298A (en) * 2015-03-03 2015-07-29 广州市金龙峰环保设备工程有限公司 Heavy metal contaminated soil treatment method and device implementing same
CN105080959A (en) * 2015-08-06 2015-11-25 张自学 Method for repairing heavy metal contaminated soil and soil heavy metal contamination repairing passivator
CN105295061A (en) * 2015-10-28 2016-02-03 上海大学 Temperature-sensitive polymer containing heavy metal chelate group and preparation method and application of temperature-sensitive polymer
CN105598152A (en) * 2015-11-05 2016-05-25 深圳多元拓展环保科技有限公司 Soil heavy metal pollution in-suit capturing treating method
CN105363773A (en) * 2015-12-08 2016-03-02 湖南康盟环保科技有限公司 Heavy metal fixing agent and in-situ repair method for heavy metal contaminated soil

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Application publication date: 20160921