CN109692673A - A kind of porous adsorption resin material and preparation method thereof and application method - Google Patents
A kind of porous adsorption resin material and preparation method thereof and application method Download PDFInfo
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- CN109692673A CN109692673A CN201910106590.9A CN201910106590A CN109692673A CN 109692673 A CN109692673 A CN 109692673A CN 201910106590 A CN201910106590 A CN 201910106590A CN 109692673 A CN109692673 A CN 109692673A
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- 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
- B01J20/22—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
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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
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- C09K17/00—Soil-conditioning materials or soil-stabilising materials
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- 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 discloses a kind of porous adsorption resin material and preparation method thereof and application methods, are related to remediation of heavy metal-contaminated soil field.A kind of porous adsorption resin provided by the invention and preparation method thereof and application method, it is applied to after heavy-metal contaminated soil for Crosslinked Polyaminated acid type heavy metal ion bonding agent and is difficult to recycle, the technical issues of easily causing secondary pollution, using crosslinked polyamino acid and sulfur-containing compound, adhesive prepares porous adsorption resin material, realizing crosslinked polyamino acid in porous adsorption resin material to the good complex performance of heavy metal ions in soil simultaneously, realize effective withdrawal to crosslinked polyamino acid, it avoids crosslinked polyamino acid from being degraded by microorganisms and dissolves out heavy metal again, Crosslinked Polyaminated acid type heavy metal ion bonding agent is solved to be difficult to recycle, the technical issues of easily causing soil secondary pollution, realize effective recycling to Crosslinked Polyaminated acid type heavy metal ion bonding agent, avoid the technical effect of soil secondary pollution.
Description
Technical field
The present invention relates to remediation of heavy metal-contaminated soil field, in particular to a kind of porous adsorption resin material and its
Preparation method and application method.
Background technique
The heavy metal of contaminated soil mainly has the significant element of the bio-toxicities such as mercury, lead, chromium, cadmium and metalloid arsenic, and
There are the elements such as the copper, zinc and nickel of certain toxicity.Heavy metal contaminants in the soil are not microbial degradation, by food chain into
It after entering human body, is not easy to be excreted by human body, when accumulation will directly affect human health to a certain extent.According to statistics, the whole nation by
Up to 300,000,000 mu, serious contaminated land is more than 10,000,000 mu in heavy metal pollution soil, wherein 2,000,000 mu of soils are due to cadmium content is exceeded
It is forced no longer cultivated.It is estimated that the whole nation every year because the grain of heavy metal pollution is up to 12,000,000 tons, caused by direct economic loss be more than
20000000000 yuan.
The existing processing method to heavy-metal contaminated soil is usually to throw by heavy metal ion contaminated soil surface
Heavy metal ion bonding agent is spilt, the heavy metal in heavy-metal contaminated soil is carried out by absorption combination with this, to restore soil fertilizer
Power.For example, China, which applies for a patent CN106832265A, discloses a kind of Crosslinked Polyaminated acid type metal absorbent, preparation and its suction
Attached metal process, the patent are filtered or are inhaled to the polluted-water containing heavy metal ion by Crosslinked Polyaminated acid hydrogel
Attached work finally collects and combines the hydrogel of heavy metal ion and be further processed.
In the implementation of the present invention, inventor find the relevant technologies the prior art has at least the following problems:
When occurrence of large-area heavy metal pollution of soil event, Crosslinked Polyaminated acid type heavy metal ion bonding agent is shed to soil
After earth, combine the heavy metal ion bonding agent of heavy metal ion usually still long-term existence in soil and being difficult to recycle, by
Belong to degradable substance in crosslinked polyamino acid class, Crosslinked Polyaminated acid type heavy metal ion bonding agent is dropped in long-term microorganism
In solution preocess, adsorbed heavy metal ion is very easy to be precipitated again, causes soil again by heavy metal pollution.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, the present invention provides a kind of porous adsorption resin material and its preparation sides
Method and application method are prepared porous by the way that crosslinked polyamino acid and high molecular polymer are bonded together sinter molding
Resin material is adsorbed, which not only has good heavy metal adsorption performance, and adsorbs heavy metal ion
It is convenient for recycling and reusing afterwards.Technical scheme is as follows:
First aspect according to an embodiment of the present invention provides a kind of porous adsorption resin material, which is characterized in that described porous
Absorption resin material constituent include:
1wt% ~ 99wt% crosslinked polyamino acid；
0wt% ~ 50wt% sulfur-containing compound；
1wt% ~ 30wt% adhesive；
The sum of dosage of the crosslinked polyamino acid, sulfur-containing compound and adhesive is 100%.
In a preferred embodiment, the crosslinked polyamino acid is cross-linked polylysine, crosslinking polyglutamic acid, crosslinking
At least one of poly-aspartate, the poly- cysteine of crosslinking, crosslinking polyglutamine or crosslinking polyhistidyl.
In a preferred embodiment, the sulfur-containing compound is trithiocyanuric acid, thiocarbamide, NaHS or three polysulfides
At least one of cyanic acid sodium salt.
In a preferred embodiment, described adhesive is polyethylene, polylactic acid, polystyrene, polycaprolactone, polychlorostyrene
At least one of ethylene, polypropylene, epoxy resin or polyurethane.
The second aspect according to an embodiment of the present invention provides a kind of preparation method of above-mentioned porous adsorption resin material,
It is characterized in that, which comprises
1wt% ~ 99wt% crosslinked polyamino acid, 0wt% ~ 50wt% sulfur-containing compound and 1wt% ~ 30wt% adhesive are uniformly mixed
Afterwards, it is placed in cold stamping die and is cold-pressed to obtain cold base；
After the cold base merging heating device is sintered, taking-up is cooled to room temperature, and obtains porous adsorption resin material.
In a preferred embodiment, the cold pressing pressure that cold pressing process uses is 0 ~ 20Mpa, the burning of sintering process use
Junction temperature is 50 ~ 300oC.
In a preferred embodiment, the shape of the porous adsorption resin material is cylindrical body or cuboid.
In terms of third according to an embodiment of the present invention, a kind of application method of above-mentioned porous adsorption resin material is provided,
It is characterized in that, which comprises
The porous adsorption resin material is inserted in the absorption that target soil carries out heavy metal ion, the porous adsorption resin
The depth that material is inserted into target soil is 0 ~ 200cm, and spacing is 0 ~ 3m；
Every other day water to the target soil for being inserted with the porous adsorption resin material；
After preset duration, the porous adsorption resin material is withdrawn from target soil, is added in competitive solution and carries out
Contact is impregnated, the porous adsorption resin material desorption is made to realize adsorbent reactivation, the temperature for impregnating contact is -80-80oC, leaching
The when a length of 1min-3h of bubble contact.
In a preferred embodiment, the competitive solution be in strong acid and the small molecule being complexed by force with metal extremely
Few one kind, the pH value of the strong acid is less than 2.0.
In a preferred embodiment, the strong acid include hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, in sulfonic acid extremely
Few one kind, the small molecule that the metal is complexed by force are ethylenediamine tetra-acetic acid.
Compared with prior art, a kind of porous adsorption resin provided by the invention and preparation method thereof and application method have
Following advantages:
A kind of porous adsorption resin provided by the invention and preparation method thereof and application method, for a Crosslinked Polyaminated acid type huge sum of money
Belong to after ions binding agent is applied to heavy-metal contaminated soil and be difficult to the technical issues of recycling, easily causing secondary pollution, using crosslinking
Polyaminoacid and sulfur-containing compound, adhesive prepare porous adsorption resin material jointly, so that handing in porous adsorption resin material
Join polyaminoacid while realizing complex performance good to heavy metal ions in soil, realizes to the effective of crosslinked polyamino acid
It withdraws, avoidable crosslinked polyamino acid is degraded by microorganisms and dissolves out heavy metal again, solves a Crosslinked Polyaminated acid type huge sum of money
Belong to the technical issues of ions binding agent is difficult to recycle, easily causes soil secondary pollution, realizes to Crosslinked Polyaminated acid type weight
Effective recycling of metal ion bonding agent, avoids the technical effect of soil secondary pollution.
Detailed description of the invention
The drawings herein are incorporated into the specification and forms part of this specification, and shows and meets implementation of the invention
Example, and be used to explain the principle of the present invention together with specification.
Fig. 1 is a kind of method flow of the preparation method of porous adsorption resin material shown according to an exemplary embodiment
Figure.
Fig. 2 is a kind of method flow of the application method of porous adsorption resin material shown according to an exemplary embodiment
Figure.
Fig. 3 is a kind of macro morphology figure of porous adsorption resin material shown according to an exemplary embodiment.
Fig. 4 is a kind of microscopic appearance figure of porous adsorption resin material shown according to an exemplary embodiment.
Specific embodiment
To describe the technical solutions in the embodiments of the present invention more clearly, make required in being described below to embodiment
Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for
For those of ordinary skill in the art, without creative efforts, it can also be obtained according to these attached drawings other
Attached drawing.
The present invention is prepared porous by the way that crosslinked polyamino acid and high molecular polymer are bonded together sinter molding
Resin material is adsorbed, which not only has good heavy metal adsorption performance, and adsorbs heavy metal ion
It is convenient for recycling and reusing afterwards, the invention is realized by the following technical scheme:
Fig. 1 is a kind of method flow diagram of the preparation method of porous adsorption resin material shown according to an exemplary embodiment,
As shown in Figure 1, this method comprises:
Step 101: 1wt% ~ 99wt% crosslinked polyamino acid, 0wt% ~ 50wt% sulfur-containing compound and 1wt% ~ 30wt% adhesive is mixed
After closing uniformly, it is placed in cold stamping die and is cold-pressed to obtain cold base.
It is furthermore preferred that the content of the crosslinked polyamino acid is 50wt% ~ 90wt%, the content of the sulfur-containing compound is
10wt% ~ 30wt%, the content of described adhesive are 10wt% ~ 30wt%.
Wherein, in each constituent mix proportion scheme, the sum of crosslinked polyamino acid, sulfur-containing compound and dosage of adhesive
It is 100%.
In a preferred embodiment, the crosslinked polyamino acid is cross-linked polylysine, crosslinking polyglutamic acid, crosslinking
At least one of poly-aspartate, the poly- cysteine of crosslinking, crosslinking polyglutamine or crosslinking polyhistidyl.It is furthermore preferred that
The crosslinked polyamino acid is at least one of cross-linked polylysine, crosslinking polyglutamic acid and crosslinking polyhistidyl.
In a preferred embodiment, the sulfur-containing compound is trithiocyanuric acid, thiocarbamide, NaHS or three polysulfides
At least one of cyanic acid sodium salt.It is furthermore preferred that the sulfur-containing compound is trithiocyanuric acid, thiocarbamide and trithiocyanuric acid sodium salt
At least one of.
In a preferred embodiment, described adhesive is polyethylene, polylactic acid, polystyrene, polycaprolactone, polychlorostyrene
At least one of ethylene, polypropylene, epoxy resin or polyurethane.It is furthermore preferred that described adhesive is polyethylene, polyphenyl second
At least one of alkene, polypropylene and polyurethane.
It should be noted that the present invention can be increased by using a small amount of sulfur-containing compound in adsorbent material significantly
The ability of strong cross-linking polyaminoacid combination heavy metal ion, forms more stable heavy metal conjugate.In crosslinked polyamino acid
Under the synergistic effect of sulfur-containing compound, it is poly- that the porous adsorption resin that the present invention obtains compares crosslinking to the adsorption effect of heavy metal
The simple superposition effect that amino acid and sulfur-containing compound use respectively is more outstanding, especially when water body and heavy metal in soil from
Effect is more significant when sub- concentration is higher.
In a preferred embodiment, the cold pressing pressure that cold pressing process uses is 0 ~ 20Mpa, the burning of sintering process use
Junction temperature is 50 ~ 300 DEG C.It is furthermore preferred that the cold pressing pressure that cold pressing process uses is 1 ~ 5 MPa, the sintering that sintering process uses
Temperature is 100 ~ 180 DEG C.
In a preferred embodiment, the shape of the porous adsorption resin material is cylindrical body or cuboid.
For example, the shape of porous adsorption resin material is cylindrical body, wherein a length of the 10 of porous adsorption resin material ~
50cm, diameter are 5 ~ 10cm.
For another example, the shape of porous adsorption resin material is cuboid, wherein a length of the 5 of porous adsorption resin material ~
20cm, width are 5 ~ 10cm, a height of 10 ~ 50cm.
The porous adsorption resin material that embodiment provides in order to better illustrate the present invention, shows one kind as shown in Figure 2
The method flow diagram of the application method of porous adsorption resin material, as shown in Figure 2, which comprises
Step 201: porous adsorption resin material is inserted in the absorption that target soil carries out heavy metal ion, porous adsorption resin
The depth that material is inserted into target soil is 0 ~ 200cm, and spacing is 0 ~ 3m.
It is furthermore preferred that the depth of porous adsorption resin material insertion target soil is 0 ~ 30cm, spacing is 0 ~ 1m.
Step 202: every other day watering to the target soil for being inserted with porous adsorption resin material.
Step 203: after preset duration, porous adsorption resin material being withdrawn from target soil, be added to competitive molten
Immersion contact is carried out in liquid, porous adsorption resin material desorption is made to realize adsorbent reactivation, and the temperature for impregnating contact is -80-80o
C impregnates the when a length of 1min-3h of contact.
It is furthermore preferred that the temperature for impregnating contact is 0-80oC.
In a preferred embodiment, the competitive solution be in strong acid and the small molecule being complexed by force with metal extremely
Few one kind, the pH value of the strong acid is less than 2.0.
In a preferred embodiment, the strong acid include hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, in sulfonic acid extremely
Few one kind, the small molecule that the metal is complexed by force are ethylenediamine tetra-acetic acid.
It is furthermore preferred that the strong acid is hydrochloric acid or acetic acid.
It should be noted that when strong acid and when mixing with the small molecule that metal is complexed by force, strong acid and it is complexed by force with metal
The proportionate relationship of small molecule is without specifically limited.
In porous adsorption resin material provided by the invention, crosslinked polyamino acid is obtained by biomass material amino acid
Arrive, possess a large amount of amino, hydroxyl, carboxyl, sulfydryl, guanidine radicals, amide groups etc. can with the functional group of metal complex, meanwhile,
A large amount of micropore is produced during the machine-shaping of porous adsorption resin material, porous adsorption resin material is gathered around
There is very big specific surface area, this will greatly improve the contact probability of adsorption functional group and heavy metal ion in crosslinked polyamino acid,
So as to improve the absorption property and recovery efficiency of porous adsorption resin material.Therefore, porous adsorption resin provided by the invention
The advantages that material possesses that absorption property is good, recovery efficiency is high and is easy to use.
Wherein, the macro morphology figure of porous adsorption resin material provided by the invention is as shown in figure 3, porous adsorption resin material
The microscopic appearance figure of material is as shown in Figure 4.It can be arrived by Fig. 3, Fig. 4 with clear view, the surface of porous adsorption resin material and interior
Part is furnished with a large amount of pore structures, so that porous adsorption resin material can be realized sufficiently connecing to target soil or target water body
Touching, so that heavy metal element is efficiently adsorbed and be recycled.
The beneficial effect for the porous adsorption resin material that embodiment provides in order to better illustrate the present invention, the present invention are also logical
Embodiment 1-6 is crossed to be illustrated.
Embodiment 1
The preparation of porous adsorption resin material: by the poly- second of 75wt% cross-linked polylysine, the trithiocyanuric acid of 5wt% and 20wt%
Alkene is uniformly mixed after being ground to 60 mesh, is placed in long 30cm, is cold-pressed to obtain cold base in the column cold stamping die of diameter 5cm,
In, the cold pressing pressure that cold pressing process uses for 5Mpa, when cold pressing a length of 20min；The cold base merging heating device is burnt
After knot, taking-up is cooled to room temperature, and obtains porous adsorption resin material, wherein the sintering temperature that sintering process uses for 180 DEG C,
A length of 10min when sintering.
The reparation of target soil: the porous adsorption resin material being prepared is inserted in the target soil of cadmium metal pollution
The absorption of heavy metal ion is carried out, the depth that porous adsorption resin material is inserted into target soil is 30cm, spacing 0.5m；Every
10% moisture for spilling soil quality is poured to the target soil for being inserted with porous adsorption resin material within one day, to promote cadmium ion and more
Macroporous adsorbent resin material comes into full contact with；After 4 weeks, porous adsorption resin material is withdrawn from target soil, be added to containing
In the hydrochloric acid solution of the 0.1M of 0.2% ethylenediamine tetra-acetic acid, 30 minutes are stood, is taken out, clear water rinses；It is then added to unsaturated carbonate
It impregnates 10 minutes, takes out in sodium solution, clear water rinses, and is detected by ICP and does not contain cadmium element in porous adsorption resin material, said
The bright present invention can be realized the De contamination of absorption resin.
It repairs change of heavy metal in the target soil of front and back: being measured near porous adsorbing material by hac buffer method
The toxicity leaching content of cadmium is reduced to 0.41 mg/kg from 3.8 mg/kg in soil, and reduction ratio reaches 89.2%.
Embodiment 2
The preparation of porous adsorption resin material: 70wt% is crosslinked polyglutamic acid, the NaHS of 8wt% and the polylactic acid of 20wt%
It is uniformly mixed after being ground to 100 mesh, is placed in long 10cm, is cold-pressed to obtain cold base in the column cold stamping die of diameter 2cm,
In, the cold pressing pressure that cold pressing process uses for 2Mpa, when cold pressing a length of 30min；The cold base merging heating device is burnt
After knot, taking-up is cooled to room temperature, and obtains porous adsorption resin material, wherein the sintering temperature that sintering process uses for 190 DEG C,
A length of 10min when sintering.
The reparation of target soil: the porous adsorption resin material being prepared is inserted in the target of mercury and lead metal pollution
Soil carries out the absorption of heavy metal ion, and the depth that porous adsorption resin material is inserted into target soil is 10cm, spacing 0.5m；
20% moisture for spilling soil quality is every other day poured to the target soil for being inserted with porous adsorption resin material, with promote mercury and lead from
Son comes into full contact with porous adsorption resin material；After 2 weeks, porous adsorption resin material is withdrawn from target soil, is added
Into the hydrochloric acid solution of the 0.1M containing 0.2% ethylenediamine tetra-acetic acid, 30 minutes are stood, is taken out, clear water rinses；It is then added to full
It impregnates 10 minutes, takes out in sodium carbonate liquor, clear water rinses, and is detected by ICP and does not contain mercury in porous adsorption resin material
And lead element, illustrate that the present invention can be realized the De contamination of absorption resin.
It repairs change of heavy metal in the target soil of front and back: being measured near porous adsorbing material by hac buffer method
The toxicity leaching content of mercury in soils is reduced to 0.88 mg/kg from 4.1 mg/kg, and reduction ratio reaches 78.5%；The toxicity of lead is soaked
Output is reduced to 0.73 mg/kg from 3.5 mg/kg, and reduction ratio reaches 79.1%.
Embodiment 3
The preparation of porous adsorption resin material: the 60wt% polypropylene for being crosslinked polyhistidyl, the thiocarbamide of 10wt% and 30wt% is ground
It is uniformly mixed after to 80 mesh, is placed in long 50cm, is cold-pressed to obtain cold base in the column cold stamping die of diameter 10cm, wherein cold
The cold pressing pressure that uses of pressure process for 10Mpa, when cold pressing a length of 20min；After the cold base merging heating device is sintered,
Taking-up is cooled to room temperature, and obtains porous adsorption resin material, wherein the sintering temperature that sintering process uses is 180 DEG C, sintering
Shi Changwei 25min.
The reparation of target soil: the porous adsorption resin material being prepared is inserted in mercury, cadmium, lead and chromium metallic pollution
Target soil carry out heavy metal ion absorption, porous adsorption resin material be inserted into target soil depth be 50cm, spacing
For 0.5m；10% moisture for spilling soil quality is poured, to the target soil for being inserted with porous adsorption resin material every other day to promote
Mercury, cadmium, lead and chromium ion come into full contact with porous adsorption resin material；It is after 6 weeks, porous adsorption resin material is native from target
It is withdrawn in earth, porous adsorption resin material is withdrawn from target soil, be added to the 0.1M containing 0.2% ethylenediamine tetra-acetic acid
Hydrochloric acid solution in, stand 30 minutes, take out, clear water rinse；It is then added in saturated sodium carbonate solution and impregnates 10 minutes, take
Out, clear water rinses, and is detected by ICP and does not contain mercury, cadmium, lead and chromium in porous adsorption resin material, illustrates energy of the present invention
Enough De contaminations for realizing absorption resin.
It repairs change of heavy metal in the target soil of front and back: being measured near porous adsorbing material by hac buffer method
The toxicity leaching content of mercury in soils is reduced to 0.47 mg/kg from 5.8 mg/kg, and reduction ratio reaches 91.8%；The toxicity of cadmium is soaked
Output is reduced to 0.50 mg/kg from 4.6 mg/kg, and reduction ratio reaches 89.1%；The toxicity leaching content of lead is from 10.8 mg/kg
1.30 mg/kg are reduced to, reduction ratio reaches 87.9%；The toxicity leaching content of chromium is reduced to 0.78 mg/ from 12.5 mg/kg
Kg, reduction ratio reach 93.7%.
Embodiment 4
The preparation of porous adsorption resin material: by the poly- second of 70wt% cross-linked polylysine, the trithiocyanuric acid of 5wt% and 25wt%
Alkene is uniformly mixed after being ground to 70 mesh, is placed in long 80cm, is cold-pressed to obtain cold base in the column cold stamping die of diameter 15cm,
In, the cold pressing pressure that cold pressing process uses for 5Mpa, when cold pressing a length of 20min；The cold base merging heating device is burnt
After knot, taking-up is cooled to room temperature, and obtains porous adsorption resin material, wherein the sintering temperature that sintering process uses for 180 DEG C,
A length of 10min when sintering.
The reparation of target soil: the porous adsorption resin material being prepared is inserted in the target soil of cadmium metal pollution
The absorption of heavy metal ion is carried out, the depth that porous adsorption resin material is inserted into target soil is 30cm, spacing 0.5m；Every
10% moisture for spilling soil quality is poured to the target soil for being inserted with porous adsorption resin material within one day, with promote cadmium ion with it is porous
Absorption resin material comes into full contact with；After 1 week, porous adsorption resin material is withdrawn from target soil, be added to containing
In the hydrochloric acid solution of the 0.1M of 0.2% ethylenediamine tetra-acetic acid, 30 minutes are stood, is taken out, clear water rinses；It is then added to unsaturated carbonate
It impregnates 10 minutes, takes out in sodium solution, clear water rinses, and is detected by ICP and does not contain cadmium element in porous adsorption resin material, said
The bright present invention can be realized the De contamination of absorption resin.
It repairs change of heavy metal in the target soil of front and back: being measured near porous adsorbing material by hac buffer method
The toxicity leaching content of cadmium is reduced to 0.58 mg/kg from 4.6 mg/kg in soil, and reduction ratio reaches 87.4%.
Embodiment 5
The preparation of porous adsorption resin material: by the cross-linked poly-aspartic acid of 50wt%, 20wt% trithiocyanuric acid sodium salt and
The polycaprolactone of 30wt% is ground to after 50 mesh and is uniformly mixed, and is placed in long 8cm, in the cuboid cold stamping die of wide 5cm, high 30cm
Be cold-pressed to obtain cold base, wherein the cold pressing pressure that cold pressing process uses for 20Mpa, when cold pressing a length of 20min；It will be described cold
After base merging heating device is sintered, taking-up is cooled to room temperature, and obtains porous adsorption resin material, wherein sintering process is adopted
Sintering temperature is 180 DEG C, when sintering a length of 25min.
The reparation of target soil: the porous adsorption resin material being prepared is inserted in mercury, cadmium, lead and chromium metallic pollution
Target soil carry out heavy metal ion absorption, porous adsorption resin material be inserted into target soil depth be 30cm, spacing
For 0.5m；10% moisture for spilling soil quality is poured, to the target soil for being inserted with porous adsorption resin material every other day to promote
Mercury, cadmium, lead and chromium ion come into full contact with porous adsorption resin material；After 12 weeks, by porous adsorption resin material from target
It withdraws, is added in the hydrochloric acid solution of the 0.1M containing 0.2% ethylenediamine tetra-acetic acid in soil, stand 30 minutes, take out, clear water
It rinses；It is then added in saturated sodium carbonate solution and impregnates 10 minutes, take out, clear water rinses, and detects porous adsorption resin by ICP
Mercury, cadmium, lead and chromium are not contained in material, illustrate that the present invention can be realized the De contamination of absorption resin.
It repairs change of heavy metal in the target soil of front and back: being measured near porous adsorbing material by hac buffer method
The toxicity leaching content of mercury in soils is reduced to 0.45 mg/kg from 5.8 mg/kg, and reduction ratio reaches 92.2%；The toxicity of cadmium is soaked
Output is reduced to 0.21 mg/kg from 4.6 mg/kg, and reduction ratio reaches 95.4%；The toxicity leaching content of lead is from 10.8 mg/kg
It is reduced to 0.43 mg/kg, reduction ratio reaches 96.0%；The toxicity leaching content of chromium is reduced to 0.38 mg/ from 12.5 mg/kg
Kg, reduction ratio reach 96.9%.
Embodiment 6
The preparation of porous adsorption resin material: by the crosslinking polyglutamine of 65wt%, the trithiocyanuric acid of 15wt% and 20wt%
Polyurethane is uniformly mixed after being ground to 85 mesh, is placed in long 10cm, is cold-pressed in the cuboid cold stamping die of wide 8cm, high 45cm
Obtain cold base, wherein the cold pressing pressure that cold pressing process uses for 20Mpa, when cold pressing a length of 20min；The cold base merging is added
After thermal is sintered, taking-up is cooled to room temperature, and obtains porous adsorption resin material, wherein the sintering that sintering process uses
Temperature is 200 DEG C, when sintering a length of 25min.
The reparation of target soil: the porous adsorption resin material being prepared is inserted in the target soil of mercury metallic pollution
The absorption of heavy metal ion is carried out, the depth that porous adsorption resin material is inserted into target soil is 45cm, spacing 0.5m；Every
10% moisture for spilling soil quality is poured to the target soil for being inserted with porous adsorption resin material within one day, with promote mercury ion with it is porous
Absorption resin material comes into full contact with；After 36 weeks, porous adsorption resin material is withdrawn from target soil, be added to containing
In the hydrochloric acid solution of the 0.1M of 0.2% ethylenediamine tetra-acetic acid, 30 minutes are stood, is taken out, clear water rinses；It is then added to unsaturated carbonate
It impregnates 10 minutes, takes out in sodium solution, clear water rinses, and is detected by ICP and does not contain mercury element in porous adsorption resin material, said
The bright present invention can be realized the De contamination of absorption resin.
It repairs change of heavy metal in the target soil of front and back: being measured near porous adsorbing material by hac buffer method
The toxicity leaching content of mercury in soils is reduced to 0.25 mg/kg from 9.4 mg/kg, and reduction ratio reaches 97.3%.
In conclusion a kind of porous adsorption resin provided by the invention and preparation method thereof and application method, for crosslinking
Polyaminoacid type heavy metal ion bonding agent is difficult to recycle after being applied to heavy-metal contaminated soil, easily causes the technology of secondary pollution
Problem prepares porous adsorption resin material using crosslinked polyamino acid and sulfur-containing compound, adhesive, so that porous absorption jointly
Crosslinked polyamino acid is realized poly- to crosslinking while realizing complex performance good to heavy metal ions in soil in resin material
Effective withdrawal of amino acid, avoidable crosslinked polyamino acid are degraded by microorganisms and dissolve out heavy metal again, and it is poly- to solve crosslinking
The technical issues of amino acid pattern heavy metal ion bonding agent is difficult to recycle, easily causes soil secondary pollution is realized to crosslinking
Effective recycling of polyaminoacid type heavy metal ion bonding agent, avoids the technical effect of soil secondary pollution.
Although having used general explanation, specific embodiment and test above, the present invention is described in detail,
But on the basis of the present invention, it can be modified or be improved, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, fall within the scope of the claimed invention without departing from theon the basis of the spirit of the present invention.
Those skilled in the art will readily occur to of the invention other after considering specification and practice invention here
Embodiment.The present invention is directed to cover any variations, uses, or adaptations of the invention, these modifications, purposes or
Adaptive change follow general principle of the invention and including the undocumented common knowledge in the art of the present invention or
Conventional techniques.It should be understood that the invention is not limited to the accurate knots for being described above and being shown in the accompanying drawings
Structure, and various modifications and changes may be made without departing from the scope thereof.
Claims (10)
1. a kind of porous adsorption resin material, which is characterized in that the constituent of the porous adsorption resin material includes:
1wt% ~ 99wt% crosslinked polyamino acid；
0wt% ~ 50wt% sulfur-containing compound；
1wt% ~ 30wt% adhesive；
The sum of dosage of the crosslinked polyamino acid, sulfur-containing compound and adhesive is 100%.
2. porous adsorption resin material according to claim 1, which is characterized in that the crosslinked polyamino acid is that crosslinking is poly-
Lysine, crosslinking polyglutamic acid, cross-linked poly-aspartic acid, the poly- cysteine of crosslinking, crosslinking polyglutamine or crosslinking poly group ammonia
At least one of acid.
3. porous adsorption resin material according to claim 1, which is characterized in that the sulfur-containing compound is three polysulfide cyanogen
At least one of acid, thiocarbamide, NaHS or trithiocyanuric acid sodium salt.
4. porous adsorption resin material according to claim 1, which is characterized in that described adhesive is polyethylene, poly- cream
At least one of acid, polystyrene, polycaprolactone, polyvinyl chloride, polypropylene, epoxy resin or polyurethane.
5. a kind of preparation method of porous adsorption resin material according to claim 1, which is characterized in that the method packet
It includes:
1wt% ~ 99wt% crosslinked polyamino acid, 0wt% ~ 50wt% sulfur-containing compound and 1wt% ~ 30wt% adhesive are uniformly mixed
Afterwards, it is placed in cold stamping die and is cold-pressed to obtain cold base；
After the cold base merging heating device is sintered, taking-up is cooled to room temperature, and obtains porous adsorption resin material.
6. a kind of preparation method of porous adsorption resin material according to claim 5, which is characterized in that cold pressing process is adopted
Cold pressing pressure is 0 ~ 20 Mpa, and the sintering temperature that sintering process uses is 50 ~ 300oC.
7. a kind of preparation method of porous adsorption resin material according to claim 5, which is characterized in that the porous suction
The shape of attached resin material is cylindrical body or cuboid.
8. a kind of application method of porous adsorption resin material according to claim 1, which is characterized in that the method packet
It includes:
The porous adsorption resin material is inserted in the absorption that target soil carries out heavy metal ion, the porous adsorption resin
The depth that material is inserted into target soil is 0 ~ 200cm, and spacing is 0 ~ 3m；
Every other day water to the target soil for being inserted with the porous adsorption resin material；
After preset duration, the porous adsorption resin material is withdrawn from target soil, is added in competitive solution and carries out
Contact to be impregnated, the porous adsorption resin material desorption is made to realize adsorbent reactivation, the temperature for impregnating contact is -80-80 oC,
Impregnate the when a length of 1min-3h of contact.
9. a kind of application method of porous adsorption resin material according to claim 8, which is characterized in that the competitiveness
Solution is strong acid and at least one of the small molecule being complexed by force with metal, and the pH value of the strong acid is less than 2.0.
10. a kind of application method of porous adsorption resin material according to claim 8, which is characterized in that the strong acid
Including at least one of hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, sulfonic acid, the small molecule that the metal is complexed by force is ethylenediamine
Tetraacethyl.
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| CN110976507A (en) * | 2019-12-27 | 2020-04-10 | 湖北群盛环境科技发展有限公司 | Electric field assisted adsorption extraction method for in-situ remediation of heavy metal contaminated soil |
| CN111793499A (en) * | 2020-05-22 | 2020-10-20 | 中国环境科学研究院 | Application of biodegradable high molecular material in improving soil property and improving plant growth performance |
| CN115926404A (en) * | 2022-12-14 | 2023-04-07 | 安徽正欣生物科技有限公司 | Heat-resistant polylactic acid fiber prepared by crosslinking modified polylactic acid and yarn |
| CN116283426A (en) * | 2023-05-23 | 2023-06-23 | 北京助天科技集团有限公司 | Novel hierarchical porous composite material, resin containing same and application of hierarchical porous composite material in soil improvement |
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