CN108097221A - Heavy metal and organic matter adsorption gel material, gel adsorption body and its preparation method and application - Google Patents
Heavy metal and organic matter adsorption gel material, gel adsorption body and its preparation method and application Download PDFInfo
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- CN108097221A CN108097221A CN201711225038.9A CN201711225038A CN108097221A CN 108097221 A CN108097221 A CN 108097221A CN 201711225038 A CN201711225038 A CN 201711225038A CN 108097221 A CN108097221 A CN 108097221A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/14—Soil-conditioning materials or soil-stabilising materials containing organic compounds only
- C09K17/16—Soil-conditioning materials or soil-stabilising materials containing organic compounds only applied in a physical form other than a solution or a grout, e.g. as platelets or granules
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract
The invention belongs to the adsorption technology fields of heavy metal in soil and organic matter, are related to a heavy metal species and organic matter adsorption gel material, gel adsorption body and its preparation method and application.Heavy metal and organic matter adsorption gel material provided by the invention is mainly prepared by resin or filler, DTPA modified materials and acrylamide gel solution；Wherein, the resin includes XAD18, and the filler includes C18.The heavy metal of the present invention and organic matter adsorption gel material or gel adsorption body are applied into heavy metal and organic matter in soil is adsorbed, have the characteristics that adsorption capacity is good greatly with dissociation performance, eluting rate is high, and soil available organic matter is measured using DGT original positions dynamic sampling technology, it overcomes tradition and combines that phase material dissociation efficiency is low, adsorption energy force difference and the shortcomings that time-consuming, it is strong with adsorption capacity, the advantages of raw material sources are wide, of low cost.
Description
Technical field
The invention belongs to the adsorption technology fields of heavy metal in soil and organic matter, and in particular to heavy metal species and organic
Object adsorption gel material, gel adsorption body and its preparation method and application.
Background technology
Soil is one of elemental of environment, has irreplaceable role in natural ecosystems.With industry
Development, urbanization and agricultural production modernization, the pollution problem of soil is increasingly prominent.The pollution source of soil is extensive, bag
Include the exhaust gas of the industrial discharges such as mining, smelting, intermetallic composite coating, chemical industry, refuse battery processing, electronics, process hides and dyestuff, waste water, useless
Slag, agrochemical and pesticide etc. cause more and more agricultural land soil quality to decline.Soil pollution not only changes soil physical chemistry
Property makes soil degenerate, and pollutant hinders or inhibit the fauna composition and vital movement of geobiont, influences soil nutrient
The conversion of substance and energy conversion cause reduction of the degeneration of soil, crop yield and quality etc..It is particularly acute, soil
Harmful heavy metal accumulation in earth to a certain extent will generate soil_plant_atmosphere continuum murder by poisoning or even the weight of some exchangeable species
Metal is directly absorbed by crops, is enriched with, and directly threatens the life and health of the mankind.Since toxic heavy metal is in Department of Soil
Pollution course in system has the characteristics that concealment, chronicity and irreversibility；Therefore, the pollutant in soil system includes
The reparation and prevention of malicious heavy metal pollution and organic contamination are always international difficult point and hot research problem.
And accurately to take soil pollutant be soil monitoring, determine soil contamination grade and effectively carries out soil remediation
Premise.At present, the acquisition method of organic matter can be divided into situ sampling and two kinds of sampling of offing normal in soil, and wherein in situ sampling has
Can handle simultaneously multiple pollutant, it is efficient the advantages of.Wherein, heavy metal, antibiotic and the compound available state high-resolution of pesticide hang down
Straight distribution in situ sampling technology, mainly has the characteristics that：(1) it can realize that heavy metal, antibiotic and pesticide gather altogether；(2) energy
Realize heavy metal, antibiotic and the acquisition of pesticide available state；(3) in-situ acquisition of sample collection can be realized；(4) resolution ratio can be realized
Down to 1 centimetre of high-resolution vertical distribution sample collection.
And the key for implementing heavy metal, antibiotic and the compound available state high-resolution vertical distribution in situ sampling technology of pesticide exists
In, how effectively sampling medicament (such as adsorbent, oxidant, reducing agent) is uniformly added into soil underground environment, and
It smoothly takes out, rapidly dissociates sampling medicament with organic matter, it is ensured that the accuracy of subsequent detection result；And how to carry
It is high to adsorb heavy metal in soil, antibiotic and pesticide and the ability of other organic matters simultaneously, in acquisition, transport, processing procedure
In, the pollution or loss of sample are avoided, ensures accuracy of result etc., is the technical barrier faced at this stage；Also become in recent years
Come one of soil environment detection and the research hotspot for repairing field.
In consideration of it, special propose the present invention.
The content of the invention
The first object of the present invention is to provide a heavy metal species and organic matter adsorption gel material, can effectively adsorb soil
Middle pollutant such as heavy metal, pesticide, antibiotic, plasticiser and polycyclic aromatic hydrocarbon etc., adsorption capacity is strong, and raw material sources are wide, at low cost
It is honest and clean.
The second object of the present invention is to provide a kind of gel adsorption body, heavy metal and organic matter can efficiently be inhaled using state
The surface of gel adsorption body is attached to, realizes the synchronous high-efficiency adsorption equilibrium of soil vertical distribution.
The third object of the present invention is to provide a kind of preparation method of gel adsorption body, and this method is easy to operate, condition
Mildly, it is at low cost without complicated synthesis step and special equipment, it is efficient.
The fourth object of the present invention is that providing a kind of heavy metal and organic matter adsorption gel material or gel inhales
Application of the attached body in terms of absorption heavy metal in soil and organic matter, can adsorb heavy metal in soil, pesticide, antibiosis simultaneously
Element, plasticiser, polycyclic aromatic hydrocarbon and persistence organic pollutant, adsorption capacity is strong, and with good desorption performance, is supervised for soil
It surveys, determine that soil contamination grade and the effective soil remediation that carries out provide strong guidance.
To achieve the above object, the technical solution adopted by the present invention is：
According to an aspect of the present invention, the present invention provides a heavy metal species and organic matter adsorption gel material, mainly by
Resin or filler, DTPA modified materials and acrylamide gel solution are prepared；
Wherein, the resin includes XAD18, and the filler includes C18.
As further preferred technical solution, the weight ratio of the resin or filler and DTPA modified materials for (0.5~
3)：(0.5~3) is preferably (1~2)：(1~2), further preferably 1：1；
Preferably, the resin or filler and DTPA modified materials are mixed to form mixture, the mixture and acryloyl
The weight ratio of amine gel solution is (1~4)：(8~12) are preferably (2~3)：(9~11), further preferably 3：10.
As further preferred technical solution, the resin further includes one in XAD16N, XAD1600N and XAD1180N
Kind or a variety of mixtures；
The filler further includes one or more mixtures in C8, C2 and HLB.
According to another aspect of the present invention, the present invention also provides a kind of gel adsorption body, including above-mentioned heavy metal and
Organic matter adsorption gel material.
As further preferred technical solution, the shape of the gel adsorption body is column, sheet, bulk, strip or
It is annular.
As further preferred technical solution, ammonium persulfate and tetramethylethylenediamine are further included.
According to another aspect of the present invention, the present invention also provides a kind of preparation method of above-mentioned gel adsorption body, institutes
The method of stating comprises the following steps：
After resin or filler are mixed in proportion with DTPA modified materials, then it is abundant in proportion with acrylamide gel solution
Mixing, obtains mixed liquor；Ammonium persulfate and tetramethylethylenediamine are added in after supersound process, obtains suspension；
The suspension is rapidly injected in supporting body, Low- temperature culture and constant temperature and humidity culture is carried out successively, then takes out
Into the water, taken out after a period of time, obtain the gel adsorption body.
As further preferred technical solution, the weight ratio of the resin or filler and DTPA modified materials for (0.5~
3)：(0.5~3) is preferably (1~2)：(1~2), further preferably 1：1；
The resin or filler and DTPA modified materials are mixed to form mixture, and the mixture and acrylamide gel are molten
The weight ratio of liquid is (1~4)：(8~12) are preferably (2~3)：(9~11), further preferably 3：10；
The volume ratio of the ammonium persulfate and mixed liquor is (2~5)：(400~600) are preferably (3~4)：(450~
550) it is more preferably, 3：500；
The volume ratio of the tetramethylethylenediamine and mixed liquor is (2~5)：(1500~300) are preferably (3~4)：
(1800~2200), further preferably 3：2000；
Preferably, the temperature of supersound process is 3~6 DEG C, and the time is 3~8min；
Preferably, the temperature of Low- temperature culture is 4~10 DEG C, and the time is 40~60min；The temperature of constant temperature and humidity culture is 45
~55 DEG C, the time is 1~3min；
Preferably, described a period of time is 20~40min.
According to another aspect of the present invention, the present invention also provides a kind of heavy metals and organic matter attractive gel material
The application of material or gel adsorption body in terms of absorption heavy metal in soil and organic matter.
As further preferred technical solution, the organic matter includes pesticide, antibiotic, plasticiser, polycyclic aromatic hydrocarbon and holds
Long property organic pollution；
Preferably, use gel adsorption body absorption soil in heavy metal and organic matter method for：First soil is got into the cave, then
The gel adsorption body is inserted into hole, after 23~25h, taking-up；
Preferably, the elution process of the heavy metal on gel adsorption body and organic matter is：First using the NaCl's containing 1M
Acetonitrile elutes, and the eluting rate of pesticide and antibiotic uses volume ratio as 1 up to more than 90%：1 n-hexane and dichloromethane is washed
De-, the eluting rate of plasticiser, polycyclic aromatic hydrocarbon and persistence organic pollutant is up to more than 90%, then the HNO using 2M3Elution, weight
The eluting rate of metal is up to 100%.
Compared with prior art, the beneficial effects of the present invention are：
1st, heavy metal of the invention and organic matter adsorption gel material, by the resin of DTPA modified materials, XAD18 types
Or the filler of C18 types is mixed with acrylamide gel solution, passes through DTPA modified materials and the effect energy of XAD18 or C18
Heavy metal and organic matter enough effectively in capture soil especially can effectively adsorb the heavy metal in soil, pesticide and resist simultaneously
Raw element, moreover it is possible to adsorb plasticiser, polycyclic aromatic hydrocarbon and persistence organic pollutant, improve to heavy metal in soil and organic matter
Adsorption capacity, adsorption capacity is big, adaptable, and heavy metal in soil cannot effectively be adsorbed by alleviating existing ordinary gel material
The defects of with organic matter or poor absorption property.
It is effigurate to be fabricated to tool by the 2nd, gel adsorption body of the invention for heavy metal and organic matter adsorption gel material
Object can be directly placed into the acquisition that sample is carried out in soil, make it is simple, it is easy to use, by heavy metal, organic matter such as pesticide and
Antibiotic etc. can utilize state efficient absorption, and on the surface of gel adsorption body, the synchronous high-efficiency absorption of realization soil vertical distribution is put down
Weighing apparatus, sampling is accurate, and adsorption capacity is high, and desorption performance is good, and actual application value is high, and environmental benefit is good.
Meanwhile heavy metal of the invention and the raw material sources of organic matter adsorption gel material and gel adsorption body are wide, cost
Cheap, raw material is environmental-friendly, to environment non-secondary pollution, application easy to spread.
3rd, preparation method of the invention is simple, and preparation process is easily operated, mild condition, and whole process is without complicated conjunction
Into step and the equipment of Special complex, production cost is reduced, improves production efficiency, and material property obtained is stablized, surely
Qualitative good, environmental benefit is good, is easy to industrialized production.
4th, the heavy metal of the present invention and organic matter adsorption gel material or gel adsorption body are applied in soil is adsorbed
Heavy metal, pesticide, antibiotic, plasticiser, polycyclic aromatic hydrocarbon and persistence organic pollutant, have that adsorption capacity is strong, capacity is big and
The characteristics of performance is good, eluting rate is high is dissociated, and soil available organic matter is measured using DGT original positions dynamic sampling technology, gram
Taken low traditional combination phase material dissociation efficiency, adsorption energy force difference and the shortcomings that time-consuming, improve DGT detections precision and
Accuracy, shortens DGT application times, and high resolution is conducive to embody the heavy metal of soil different levels and point of organic matter
Cloth feature, while adsorption process carries out at normal temperatures, it is easy to operate, it is convenient and practical, for soil monitoring, determine soil contamination grade
And the effective soil remediation that carries out provides strong guidance.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment and embodiment, but this field skill
Art personnel will be understood that following embodiments and embodiment are merely to illustrate the present invention, and be not construed as the model of the limitation present invention
It encloses.Based on the embodiments of the present invention, those of ordinary skill in the art are obtained without making creative work
Every other embodiment, belongs to the scope of protection of the invention.Actual conditions person is indicated, is suggested according to normal condition or manufacturer
Condition carry out.Reagents or instruments used without specified manufacturer is the conventional products that can be obtained by commercially available purchase.
In a first aspect, present embodiment provides a heavy metal species and organic matter adsorption gel material, mainly by resin or fill out
Material, DTPA modified materials and acrylamide gel solution are prepared；
Wherein, the resin includes XAD18, and the filler includes C18.
XAD18 belongs to large aperture adsorption resin, is a kind of aromatic polymer, available for medium molecular substance such as antibiotic, day
The recycling and purifying of right product, water-soluble steroidal, enzyme, amino acid and protein etc., are used as layer in biomedicine field at present
Analysis separation or chromatographic isolation it is more.
C18 fillers are commonly used in reverse phase C18 chromatographic columns, are the reverse phase silica gel fillers of octadecyl modification, and C18 fillers have
Have and separate substance is retained without strong, the characteristics of separative efficiency is high, can easily recycle, and nontoxic and pollution-free.
Acrylamide gel solution, chemical property are stablized, flexible in a certain concentration, good mechanical property, and to pH
The variation of value and temperature is stablized, and sample separation is reproducible.
It should be noted that the Patent No. of DTPA modified materials in the present invention using applicant's earlier application
" a kind of DTPA modified materials and its release DGT combinations phase preparation method of the quick complete solution of preparation " disclosed in CN105148846A
In DTPA modified materials.
The DTPA modified materials, method of modifying are as follows：(1) ammonium hydroxide is added in into water, by volume V (NH4(OH))：VI
(H2O)=1：3 mixings, then add in DTPA and methanol, and weight is W (DTPA)：WI(H2O)=5：11, W (CH4O)：WI(H2O)
=5：366 it is fully dissolved after it is spare, be solution I；(2) a beaker is separately taken to add in a certain amount of water and ammonium hydroxide, volume V
(NH4(OH))：VII(H2O)=1：3, it is spare after abundant mixing, it is solution II；By above two solution be added to simultaneously containing
MgCl2·6H2O、AlCl3·6H2Solution III is obtained in the solution of O, wherein weight ratio is W (MgCl2·6H2O)：WIII
(H2O)=2：59, W (AlCl3·6H2O)：W3(H2O)=5：62, volume is solution I：Solution II：Solution III=1：8：21, it fills
After dividing mixing, pH is adjusted up to more than 9；It is dried after 10~20min of high-speed stirred, 50~80min of aging using spray dried form
It is DTPA modified materials into the fine grained less than 75 μm.
The present invention by largely test to heavy metal in soil and organic matter adsorption gel material and preparation method thereof into
Row exploration discovery：DTPA modified materials, XAD18 or C18 with acrylamide gel solution are combined, can effectively adsorb weight in soil
With heavy metal stronger complexing, XAD18 or C18 and pesticide occur for metal, pesticide and antibiotic, wherein DTPA modified materials
Stronger complexing occurs with antibiotic, adsorption capacity is big, and adsorption capacity is strong, and stability is good, has reached preferable effect, this
Outside, pesticide and antibiotic can not only be adsorbed, moreover it is possible to adsorb plasticiser, polycyclic aromatic hydrocarbon and persistence organic pollutant.It overcomes
Existing ordinary gel material cannot effectively adsorb heavy metal in soil and organic matter or adsorption effect is bad and cost of material
The defects of high, difficult purchase, there is stronger actual application value.
Therefore, heavy metal of the invention and organic matter adsorption gel material can not only effectively adsorb pesticide, antibiotic, plasticizing
Agent, polycyclic aromatic hydrocarbon and persistence organic pollutant can also have more heavy metal Cu, Zn, Pb, Cd, Ni, Fe, Mn, Al and Hg etc.
High adsorbance, better dissociation effect are easily dynamically extracted available for above-mentioned heavy metal, have the short all dissociation of adsorption time
Effect, overcome that the dissociation such as previous heavy metal, pesticide and antibiotic are slow and incomplete shortcoming, and material therefor is inexpensively easy
, non-secondary pollution, good application effect.
In a kind of optional embodiment, the weight ratio of the resin or filler and DTPA modified materials for (0.5~
3)：(0.5~3) is preferably (1~2)：(1~2), further preferably 1：1；
Preferably, the resin or filler and DTPA modified materials are mixed to form mixture, the mixture and acryloyl
The weight ratio of amine gel solution is (1~4)：(8~12) are preferably (2~3)：(9~11), further preferably 3：10.
In the present invention, the weight ratio of resin or filler and DTPA modified materials is typical but non-limiting to be：0.5：
1、0.5：1.5、0.5：2、0.5：2.5、0.5：3、1： 0.5、1.5：0.5、2：0.5、2.5：0.5、3：0.5、1：1.5、1.5：1、
1： 2、2：1 or 1：1.The weight ratio of mixture and acrylamide gel solution is typical but non-limiting to be：1：8、1：
9、1：10、1：11、1：12、2：8、2：9、2： 10、2：11、2：12、3：8、3：9、3：10、3：11、3：12、4：8、4： 9、4：
10、4：11 or 4：12.Material is modified in suitable resin or filler and DTPA modified materials proportioning and resin or filler and DTPA
Expect the mixture that is mixed to form under the weight ratio of acrylamide gel solution, enabling to proportioning more scientific and reasonable, up to
While to good adsorption effect, cost is reduced, it is good and at low cost to achieve the purpose that have both effect.
In a kind of optional embodiment, the resin further includes one in XAD16N, XAD1600N and XAD1180N
Kind or a variety of mixtures；
The filler further includes one or more mixtures in C8, C2 and HLB.
Need exist for explanation, the present invention in resin be preferably XAD18, with its XAD16N with similarity,
XAD1600N and XAD1180N resins, it may have certain adsorption effect is mixed available for acrylamide gel solution, to soil
Organic matter in earth is adsorbed, and in practical application, can be made choice as needed, and that the present invention recommends is XAD18.
Equally, the filler in the present invention is preferably C18 fillers, with its C8 and C2 and HLB with similarity, it may have certain
Adsorption effect, mixed available for acrylamide gel solution, the organic matter in soil adsorbed, in practical application,
It can make choice as needed, and that the present invention recommends is C18.
Second aspect, present embodiment provide a kind of gel adsorption body, solidifying including above-mentioned heavy metal and organic matter absorption
Glue material.
The gel adsorption body includes above-mentioned heavy metal and organic matter adsorption gel material, may also include certain load
Body or other auxiliary agents.
When in the prior art to carrying out absorption acquisition to heavy metal in soil and organic matter using gel rubber material, mainly face
Following problem：First, common gel adsorption material is poor for the absorption property for adsorbing heavy metal, pesticide and antibiotic simultaneously,
Adsorption effect is bad；It second is that adsorbent cannot be homogeneously added into soil environment, and smoothly takes out, rapidly by adsorbent
It is dissociated with heavy metal, pesticide and antibiotic, to facilitate detection, and ensures the accuracy of testing result.
And the gel rubber material of heavy metal in soil and organic matter with splendid absorption property will be made with one in the present invention
The object of setting shape can be directly placed into the acquisition that sample is carried out in soil, take out, eluted after a period of time, uniformly
Degree is good, and adsorption efficiency is high, and makes simply, easy to use, and heavy metal and organic matter can be utilized state efficient absorption solidifying
The surface of glue adsorbent realizes the synchronous high-efficiency adsorption equilibrium of soil vertical distribution, the accuracy of testing result is effectively ensured, can
The existence form of objective reaction heavy metal in soil, pesticide and antibiotic etc., actual application value are high.
In a kind of optional embodiment, the shape of the gel adsorption body is column, sheet, bulk, strip or
It is annular.
In a kind of optional embodiment, ammonium persulfate and tetramethylethylenediamine (TEMED) are further included.
It needs exist for illustrating, the gel adsorption body in the present invention is preferably shaped to column and sheet, wherein column
Alternatively referred to as rodlike, including cylindric and cubic, but it is not limited to this, can also be other shapes such as block, bar shaped
Shape or ring-type etc., as long as convenient for being put into the acquisition that sample is carried out in soil.
The third aspect, present embodiment provide a kind of preparation method of above-mentioned gel adsorption body, and the described method includes following
Step：
PA17041592TJ
After resin or filler are mixed in proportion with DTPA modified materials, then it is abundant in proportion with acrylamide gel solution
Mixing, obtains mixed liquor；Ammonium persulfate and tetramethylethylenediamine are added in after supersound process, obtains suspension；
The suspension is rapidly injected in supporting body, Low- temperature culture and constant temperature and humidity culture is carried out successively, then takes out
Into the water, taken out after a period of time, obtain the gel adsorption body.
The preparation method of the present invention is simple, and preparation process is easily operated, mild condition, and whole process is without complicated synthesis
The equipment of step and Special complex, reduces production cost, improves production efficiency, and material property obtained is stablized, and stablizes
Property is good, and environmental benefit is good, is easy to industrialized production.
Supporting body therein is the carrier being adapted with the shape of gel adsorption body, such as can be dismountable glass column
Or tablet slot etc., wherein glass column correspond to columnar gel adsorption body, tablet slot corresponds to the gel adsorption body of sheet.
Optionally, by after suspension under cryogenic 3~5min of ultrasound, then it is rapidly injected with the removable of certain internal diameter
It unloads in glass column or tablet slot, and after being covered with glass cover, then be transferred in low temperature incubator and cultivate.
Optionally, the preparation method of acrylamide gel solution is：1.8g gel cross-linkages agent (modified agarose) is weighed, it will
It is dissolved in 90ml water, adds in 285ml deionized waters afterwards, mixture is shaken up.90g acrylamides are weighed, are dissolved in
In 225ml water, acrylamide solution is formed, acrylamide solution and said mixture are mixed, shaken up, is stored in 4 DEG C
It is spare in refrigerator.
In a kind of optional embodiment, the weight ratio of the resin or filler and DTPA modified materials for (0.5~
3)：(0.5~3) is preferably (1~2)：(1~2), further preferably 1：1；
The resin or filler and DTPA modified materials are mixed to form mixture, and the mixture and acrylamide gel are molten
The weight ratio of liquid is (1~4)：(8~12) are preferably (2~3)：(9~11), further preferably 3：10；
The volume ratio of the ammonium persulfate and mixed liquor is (2~5)：(400~600) are preferably (3~4)：(450~
550) it is more preferably, 3：500；
The volume ratio of the tetramethylethylenediamine and mixed liquor is (2~5)：(1500~300) are preferably (3~4)：
(1800~2200), further preferably 3：2000；
Preferably, the temperature of supersound process is 3~6 DEG C, and the time is 3~8min；
Preferably, the temperature of Low- temperature culture is 4~10 DEG C, and the time is 40~60min；The temperature of constant temperature and humidity culture is 45
~55 DEG C, the time is 1~3min；
Preferably, described a period of time is 20~40min.
In the present invention, the volume ratio of ammonium persulfate and mixed liquor is typical but non-limiting to be：2：400、2：450、
2：500、2：550、2：600、3：400、3：450、 3：500、3：550、3：600、4：400、4：450、4：500、4：550、4：
600、5：400、5：450、5：500、5：550 or 5：600.
In the present invention, the volume ratio of tetramethylethylenediamine and mixed liquor is typical but non-limiting to be：2：1500、2：
1800、2：2000、2：2200、2：2500、2：2800、 2：3000、3：1500、3：1800、3：2000、3：2200、3：2500、
3：2800、 3：3000、4：1500、4：1800、4：2000、4：2200、4：2500、4：2800、 4：3000、5：1500、5：
1800、5：2000、5：2200、5：2500、5：2800 or 5：3000.
In a detailed embodiment, optionally, the temperature of supersound process is 3 DEG C, 4 DEG C, 5 DEG C or 6 DEG C, and the time is
3min, 4min, 5min, 6min, 7min or 8min；The temperature of Low- temperature culture is 4 DEG C, 5 DEG C, 6 DEG C, 7 DEG C, 8 DEG C, 9 DEG C or 10 DEG C,
Time is 40min, 42min, 44min, 45min, 46min, 48min, 50min, 50min, 54min, 55min, 56min, 58min
Or 60min；The temperature of constant temperature and humidity culture for 45 DEG C, 46 DEG C, 47 DEG C, 48 DEG C, 49 DEG C, 50 DEG C, 51 DEG C, 52 DEG C, 53 DEG C, 54
DEG C or 55 DEG C, time 1h, 1.5h, 2h, 2.5h or 3h；A period of time is 20min, 30min or 40min.
The preparation method of the present invention, has considered the performance of each raw material and the preparation characteristic of gel rubber material, each operation step
Rapid and parameter cooperates so that preparation process more science, rationally, more stable so as to prepare performance, adsorption effect is more preferable
Gel adsorption body.
Fourth aspect, present embodiment provide a kind of heavy metal and organic matter adsorption gel material or gel adsorption
Application of the body in terms of absorption heavy metal in soil and organic matter.
In a kind of optional embodiment, the organic matter includes pesticide, antibiotic, plasticiser, polycyclic aromatic hydrocarbon and holds
Long property organic pollution；
Preferably, use gel adsorption body absorption soil in heavy metal and organic matter method for：First soil is got into the cave, then
The gel adsorption body is inserted into hole, after 23~25h, taking-up；
Wherein, it is preferred to use get into the cave with earth boring auger of the gel adsorption body with similary diameter；
Preferably, the elution process of the heavy metal on gel adsorption body and organic matter is：First using the NaCl's containing 1M
Acetonitrile elutes, and the eluting rate of pesticide and antibiotic is up to more than 90%, then uses volume ratio as 1：1 n-hexane and dichloromethane is washed
De-, the eluting rate of plasticiser, polycyclic aromatic hydrocarbon and persistence organic pollutant is up to more than 90%, then the HNO using 2M3Elution, weight
The eluting rate of metal is up to 100%.
The present invention has the characteristics that adsorption capacity is strong, capacity is big and dissociation performance is good, eluting rate is high and in situ using DGT
Dynamic sampling technology measures soil available heavy metal and organic matter, overcomes tradition and combines that phase material dissociation efficiency is low, inhales
It is attached can force difference and the shortcomings that time-consuming, improve the precision and accuracy of DGT detections, shorten DGT application times, resolution ratio
Height is conducive to embody the distribution characteristics of the organic matter of soil different levels, while adsorption process carries out at normal temperatures, operation letter
Just, it is convenient and practical, for soil monitoring, determine that soil contamination grade and the effective soil remediation that carries out provide strong guidance.
Explanation is needed exist for, gel adsorption body of the invention has the characteristics that adsorption capacity is strong, can adsorb a variety of
The organic matter of type when being eluted, can be used different eluant, eluents and be washed for different types of making choice property of organic matter
It takes off or does not elute, to meet the needs of experiment.
It is preferably carried out in one kind in mode, it is former using heavy metal, pesticide and antibiotic available state high-resolution vertical distribution
Heavy metal, pesticide and antibiotic etc. can be utilized state efficient absorption in the gel adsorption body surface face of the present invention, tool by position sampling technique
Body process is：
(a) it is (1~2) according to weight ratio by XAD18 or C18 and DTPA modified materials：(1~2) is mixed, then with
Acrylamide gel solution is (2~3) according to weight ratio：(9~11) are sufficiently mixed uniformly, obtain mixed liquor；
(b) mixed liquor under the conditions of temperature is 3~6 DEG C is ultrasonically treated 3~8min, then adds in 10% mistake
The volume ratio of ammonium sulfate, ammonium persulfate and mixed liquor is (3~4)：(450~550), while tetramethylethylenediamine is added in, tetramethyl
The volume ratio of base ethylenediamine and mixed liquor is (3~4)：(1800~2200), obtain suspension；
(c) by after suspension under cryogenic 3~5min of ultrasound, then it is rapidly injected the detachable glass with certain internal diameter
In glass column or tablet slot, and after being covered with glass cover, then be transferred to Low- temperature culture 40 in 4~10 DEG C of low temperature incubator~
60min is then transferred into constant temperature and humidity incubator 1~3h of culture under conditions of 45~55 DEG C；
(d) sample for obtaining step (c) is put into distilled water or ultra-pure water, and gel is taken out after 20~40min, and 24 is small
When it is interior change water at least 3 times, obtain the gel adsorption body；
(e) column prepared or sheet gel adsorption body are cut into the length of needs, it is spare；
(f) use heavy metal in above-mentioned gel adsorption body absorption soil and organic matter method for：Using with gel adsorption
The earth boring auger that body has similary diameter gets into the cave soil, then the gel adsorption body is directly placed into hole, after 23~25h,
Taking-up；
(g) elution process of the heavy metal on gel adsorption body and organic matter is：First use the acetonitrile of the NaCl containing 1M
The eluting rate of elution, pesticide and antibiotic is up to more than 90%, then uses volume ratio as 1：1 n-hexane and dichloromethane eluent,
The eluting rate of plasticiser, polycyclic aromatic hydrocarbon and persistence organic pollutant is up to more than 90%, then the HNO using 2M3Elution, heavy metal
Eluting rate up to 100%.
With reference to specific embodiment, the invention will be further described.
Embodiment 1
A kind of gel adsorption body, is mainly prepared by XAD18, DTPA modified material and acrylamide gel solution,
In, the weight ratio of XAD18 and DTPA modified materials is 1：The mixture of 1, XAD18 and DTPA modified materials is coagulated with acrylamide
The weight ratio of sol solution is 3：10；
The gel adsorption body further includes the volume ratio of ammonium persulfate and tetramethylethylenediamine, wherein ammonium persulfate and mixed liquor
For 3：500, the volume ratio of tetramethylethylenediamine and mixed liquor is 3： 2000.
The shape of gel adsorption body is column.
The preparation method of the gel adsorption body and heavy metal in soil and organic matter can be utilized into state efficient absorption at this
Gel adsorption body surface face, detailed process are：
(a) it is 1 according to weight ratio by XAD18 and DTPA modified materials：1 is mixed, then with acrylamide gel solution
It is 3 according to weight ratio：10 are sufficiently mixed uniformly, obtain mixed liquor；
(b) mixed liquor is ultrasonically treated 5min under the conditions of temperature is 4 DEG C, then adds in 10% persulfuric acid
The volume ratio of ammonium, ammonium persulfate and mixed liquor is 3：500, while tetramethylethylenediamine is added in, tetramethylethylenediamine and mixed liquor
Volume ratio be 3：2000, obtain suspension；
(c) by after suspension under cryogenic ultrasound 5min, then it is rapidly injected the dismountable glass with certain internal diameter
In column, and after being covered with glass cover, then Low- temperature culture 60min in 4 DEG C of low temperature incubator is transferred to, is then transferred into constant temperature
In constant humidity incubator 2h is cultivated under conditions of 50 DEG C；
(d) sample for obtaining step (c) is put into distilled water, takes out gel after 30min, and 24 interior when small change water at least 3
It is secondary, obtain the gel adsorption body；
(e) the column gel adsorption body prepared is cut into the length of needs, it is spare；
(f) use heavy metal in above-mentioned gel adsorption body absorption soil and organic matter method for：Using with gel adsorption
The earth boring auger that body has similary diameter gets into the cave soil, then the gel adsorption body is directly placed into hole, after for 24 hours, takes out
；
(g) elution process of the heavy metal on gel adsorption body and organic matter is：First use the acetonitrile of the NaCl containing 1M
The eluting rate of elution, pesticide and antibiotic is up to 90%, then uses volume ratio as 1：1 n-hexane and dichloromethane eluent, modeling
The eluting rate of agent, polycyclic aromatic hydrocarbon and persistence organic pollutant is up to 90%, then the HNO using 2M3Elution, the elution of heavy metal
Rate is up to 100%.
Embodiment 2
A kind of gel adsorption body, the present embodiment are differed only in the gel adsorption body in embodiment 1：
XAD18 is replaced with into C18.Preparation method is the same as embodiment 1.
Embodiment 3
A kind of gel adsorption body, the present embodiment are differed only in the gel adsorption body in embodiment 2：
C18 is replaced with into HLB.Preparation method is the same as embodiment 1.
Embodiment 4
A kind of gel adsorption body, the present embodiment are differed only in the gel adsorption body in embodiment 1：
XAD18 is replaced with into XAD16N.Preparation method is the same as embodiment 1.
Embodiment 5
A kind of gel adsorption body, the present embodiment are differed only in the gel adsorption body in embodiment 1：
In preparation process, dismountable glass column is replaced with into tablet slot, gel adsorption body obtained is the gel of sheet
Adsorbent.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe is described in detail the present invention with reference to foregoing embodiments, it will be understood by those of ordinary skill in the art that：Its according to
Can so modify to the technical solution recorded in foregoing embodiments either to which part or all technical characteristic into
Row equivalent substitution；And these modifications or replacement, the essence of appropriate technical solution is not made to depart from various embodiments of the present invention technology
The scope of scheme.
Claims (10)
1. a heavy metal species and organic matter adsorption gel material, which is characterized in that mainly by resin or filler, DTPA modified materials
It is prepared with acrylamide gel solution；
Wherein, the resin includes XAD18, and the filler includes C18.
2. heavy metal according to claim 1 and organic matter adsorption gel material, which is characterized in that the resin or filler
Weight ratio with DTPA modified materials is (0.5~3)：(0.5~3) is preferably (1~2)：(1~2), further preferably 1：
1；
Preferably, the resin or filler and DTPA modified materials are mixed to form mixture, and the mixture is coagulated with acrylamide
The weight ratio of sol solution is (1~4)：(8~12) are preferably (2~3)：(9~11), further preferably 3：10.
3. heavy metal according to claim 1 or 2 and organic matter adsorption gel material, which is characterized in that the resin is also
Including one or more mixtures in XAD16N, XAD1600N and XAD1180N；
The filler further includes one or more mixtures in C8, C2 and HLB.
4. a kind of gel adsorption body, which is characterized in that inhaled including claims 1 to 3 any one of them heavy metal and organic matter
Attached gel rubber material.
5. gel adsorption body according to claim 4, which is characterized in that the shape of the gel adsorption body is column, piece
Shape, bulk, strip or ring-type.
6. gel adsorption body according to claim 4 or 5, which is characterized in that further include ammonium persulfate and tetramethyl second two
Amine.
7. such as the preparation method of claim 4~6 any one of them gel adsorption body, which is characterized in that the described method includes
Following steps：
After resin or filler are mixed in proportion with DTPA modified materials, then it is fully mixed in proportion with acrylamide gel solution
It closes, obtains mixed liquor；Ammonium persulfate and tetramethylethylenediamine are added in after supersound process, obtains suspension；
The suspension is rapidly injected in supporting body, carries out Low- temperature culture and constant temperature and humidity culture successively, then takes out and is put into
It in water, is taken out after a period of time, obtains the gel adsorption body.
8. the preparation method of gel adsorption body according to claim 7, which is characterized in that the resin or filler and DTPA
The weight ratio of modified material is (0.5~3)：(0.5~3) is preferably (1~2)：(1~2), further preferably 1：1；
The resin or filler and DTPA modified materials are mixed to form mixture, the mixture and acrylamide gel solution
Weight ratio is (1~4)：(8~12) are preferably (2~3)：(9~11), further preferably 3：10；
The volume ratio of the ammonium persulfate and mixed liquor is (2~5)：(400~600) are preferably (3~4)：(450~550),
Further preferably 3：500；
The volume ratio of the tetramethylethylenediamine and mixed liquor is (2~5)：(1500~300) are preferably (3~4)：(1800~
2200) it is more preferably, 3：2000；
Preferably, the temperature of supersound process is 3~6 DEG C, and the time is 3~8min；
Preferably, the temperature of Low- temperature culture is 4~10 DEG C, and the time is 40~60min；The temperature of constant temperature and humidity culture is 45~55
DEG C, the time is 1~3min；
Preferably, described a period of time is 20~40min.
9. any one of claims 1 to 3 any one of them heavy metal and organic matter adsorption gel material or claim 4~6
Application of the gel adsorption body in terms of absorption heavy metal in soil and organic matter.
10. application according to claim 9, which is characterized in that the organic matter includes pesticide, antibiotic, plasticiser, more
Cycloaromatics and persistence organic pollutant；
Preferably, use gel adsorption body absorption soil in heavy metal and organic matter method for：First soil is got into the cave, then by institute
It states in gel adsorption body insertion hole, after 23~25h, taking-up；
Preferably, the elution process of the heavy metal on gel adsorption body and organic matter is：First use the acetonitrile of the NaCl containing 1M
The eluting rate of elution, pesticide and antibiotic is up to more than 90%, then uses volume ratio as 1：1 n-hexane and dichloromethane eluent,
The eluting rate of plasticiser, polycyclic aromatic hydrocarbon and persistence organic pollutant is up to more than 90%, then the HNO using 2M3Elution, heavy metal
Eluting rate up to 100%.
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| CN114558556A (en) * | 2022-01-11 | 2022-05-31 | 河南工程学院 | Method for jointly preparing gel filler for purifying nitrogen and phosphorus in sewage by using solid wastes |
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