CN114702962A - Iron-based modified nano hydroxyapatite material, preparation method thereof and application thereof in Cd-contaminated soil remediation - Google Patents
Iron-based modified nano hydroxyapatite material, preparation method thereof and application thereof in Cd-contaminated soil remediation Download PDFInfo
- Publication number
- CN114702962A CN114702962A CN202210435552.XA CN202210435552A CN114702962A CN 114702962 A CN114702962 A CN 114702962A CN 202210435552 A CN202210435552 A CN 202210435552A CN 114702962 A CN114702962 A CN 114702962A
- Authority
- CN
- China
- Prior art keywords
- iron
- modified nano
- solution
- based modified
- hydroxyapatite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 239000000463 material Substances 0.000 title claims abstract description 80
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 77
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 61
- 239000002689 soil Substances 0.000 title claims abstract description 48
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000005067 remediation Methods 0.000 title abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910001868 water Inorganic materials 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000839 emulsion Substances 0.000 claims abstract description 15
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 9
- 239000010452 phosphate Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- 239000011575 calcium Substances 0.000 claims description 13
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 12
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 11
- 150000002505 iron Chemical class 0.000 claims description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 20
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- 238000005342 ion exchange Methods 0.000 abstract description 3
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- 238000010668 complexation reaction Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 17
- 238000011160 research Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 description 6
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 238000002161 passivation Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
- C09K17/06—Calcium compounds, e.g. lime
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
-
- C—CHEMISTRY; METALLURGY
- 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
- C09K2101/00—Agricultural use
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to the technical field of heavy metal adsorption materials and soil remediation, and particularly discloses an iron-based modified nano hydroxyapatite material, a preparation method thereof and application thereof in remediation of Cd-polluted soil. The preparation method of the iron-based modified nano hydroxyapatite material comprises the following steps: dissolving phosphate in water, and adjusting the pH value to 10-11 to obtain a solution A; dissolving calcium salt and ferric salt in water, and adjusting the pH value to 10-11 to obtain a solution B; mixing the solution A and the solution B to obtain a milky solution; and then heating the emulsion solution for reaction, and washing and drying the product after the reaction is finished to obtain the iron-based modified nano hydroxyapatite material. The iron-based modified nano hydroxyapatite material prepared by the method has excellent ion exchange capacity, surface area, surface complexation and coprecipitation; the method has an excellent repairing effect on Cd-polluted soil.
Description
Technical Field
The invention relates to the technical field of heavy metal adsorption materials and soil remediation, in particular to an iron-based modified nano hydroxyapatite material, a preparation method thereof and application thereof in remediation of Cd-polluted soil.
Background
The soil heavy metal pollution refers to the phenomenon that the content of heavy metals in soil is obviously higher than the background value of the heavy metals in local soil due to the fact that the heavy metals enter the soil through the activities of human beings, and the existing or potential soil degradation and soil ecological and environmental deterioration can be caused. Heavy metal pollution of soil can cause the yield and quality of crops to be reduced, so that agriculture and rural economy suffer huge losses. Once entering the soil, heavy metals such as cadmium, lead, mercury, arsenic and the like can be absorbed by crops, so that the heavy metals remain in agricultural products and endanger the health of livestock and poultry, and finally pose a threat to the health of human beings through a food chain.
The hydroxyapatite is slightly water-soluble alkalescent calcium phosphate, has large specific surface area, can not only be subjected to precipitation reaction with heavy metal, but also can adsorb heavy metal through the huge specific surface areaThe metal ions can reduce the activity of the heavy metal, and can also generate ion exchange effect with different functional groups or heavy metal ions, thereby becoming one of hot materials for environmental remediation research. However, Ca in the hydroxyapatite lattice prepared by different methods2+The positions of (a) and (b) are different, as are the valency and radius; therefore, the hydroxyapatite prepared by different methods has different passivation adsorption capacities on different heavy metals.
The research on the adsorption of heavy metals by nano hydroxyapatite materials mainly focuses on water environment and atmospheric environment, and the research on the passivation adsorption of heavy metal ions on soil is relatively less. The soil is a complex system, a plurality of heavy metal ions exist in the soil, competitive adsorption exists among the heavy metal ions, and the determining factors such as the pH value, the organic matter content and the cation exchange amount in the soil environment are complex. However, what effect of the nano-hydroxyapatite material on the passivation and adsorption of various heavy metal ions in the soil is, the nano-hydroxyapatite material prepared by any method aiming at the soil polluted by specific heavy metals has excellent heavy metal passivation and adsorption effect, and these needs further intensive research by the technicians in this field.
Therefore, on the basis of the prior art, the development of the nano hydroxyapatite material with good repairing effect on the Cd-polluted soil has important application value.
Disclosure of Invention
In order to overcome at least one technical problem in the prior art, the invention provides a preparation method of an iron-based modified nano hydroxyapatite material; research shows that the iron-based modified nano-hydroxyapatite material prepared by the method has excellent repairing effect on Cd-polluted soil; and the repairing effect of the material on Cd-polluted soil is obviously higher than that of an unmodified nano hydroxyapatite material.
The technical scheme for solving the technical problems is as follows:
a preparation method of an iron-based modified nano hydroxyapatite material comprises the following steps:
dissolving phosphate in water, and adjusting the pH value to 10-11 to obtain a solution A;
dissolving calcium salt and ferric salt in water, and adjusting the pH value to 10-11 to obtain a solution B;
mixing the solution A and the solution B to obtain a milky solution; and then heating the emulsion solution for reaction, and washing and drying the product after the reaction is finished to obtain the iron-based modified nano hydroxyapatite material.
The invention is surprisingly found in the research that: the iron-based modified nano hydroxyapatite material prepared by the method has a repairing effect on Cd-polluted soil which is obviously higher than that of an unmodified nano hydroxyapatite material.
Preferably, the phosphate is (NH)4)2HPO4。
Preferably, the dosage ratio of the phosphate to the water is 30-50 mmol: 100-200 mL.
Most preferably, the ratio of phosphate to water is 40mmol:150 mL.
Preferably, the calcium salt is Ca (NO)3)2·4H2O; the iron salt is FeCl3·6H2O。
Preferably, Ca (NO)3)2·4H2O、FeCl3·6H2The dosage ratio of O to water is 60-70 mmol: 6-7 mmol: 100-150 mL.
Most preferably, Ca (NO)3)2·4H2O、FeCl3·6H2The dosage ratio of O to water was 60.03mmol:6.67mmol:120 mL.
Preferably, the volume ratio of the solution A to the solution B is 1-1.5: 1.
Preferably, the heating reaction is carried out at 85-95 ℃ for 40-90 min.
Preferably, the heating reaction is carried out at 40-45 ℃ for 15-20 min; then reacting for 15-20 min at 75-80 ℃; and then reacting for 20-50 min at 85-95 ℃.
Most preferably, the heating reaction is carried out at 43 ℃ for 15 min; then reacting for 20min at 75 ℃; finally, the reaction is carried out at 90 ℃ for 40 min.
The inventor further discovers in the research; in the process of preparing the iron-based modified nano-hydroxyapatite material by using the raw materials, the heating reaction temperature plays an important role in determining whether the prepared iron-based modified nano-hydroxyapatite material has an excellent repairing effect on Cd-polluted soil; the iron-based modified nano-hydroxyapatite material prepared at different reaction temperatures has excellent repairing effect on Cd-polluted soil, and the difference is great. A great deal of experimental research shows that the iron-based modified nano-hydroxyapatite material prepared under the three-stage heating reaction condition has a far higher repairing effect on Cd-polluted soil than the iron-based modified nano-hydroxyapatite material prepared under a single temperature condition.
Preferably, NaOH and NH are selected for use in the invention3.H2O or urea to adjust the pH.
The invention also provides the iron-based modified nano hydroxyapatite material prepared by the preparation method.
The invention also provides an application of the iron-based modified nano hydroxyapatite material in repairing Cd-polluted soil.
Has the advantages that: the invention provides a brand new preparation method of an iron-based modified nano-hydroxyapatite material, and the iron-based modified nano-hydroxyapatite material prepared by the method has excellent ion exchange capacity, surface area, surface complexation and coprecipitation; experiments and researches show that the remediation of Cd-polluted soil is obviously higher than that of unmodified nano hydroxyapatite materials.
Detailed Description
The present invention is further explained below with reference to specific examples, which are not intended to limit the present invention in any way.
Example 1 preparation of iron-based modified nano-hydroxyapatite Material
(1) Take 40mmol (NH)4)2HPO4Dissolved in 150ml of water and then NH is added3·H2O regulating solution acid-baseObtaining solution A when the temperature is 11 ℃;
(2) 60.03mmol of Ca (NO) was taken3)2·4H2O (calcium nitrate tetrahydrate) and 6.67mmol FeCl3·6H2O was dissolved in 120ml of water, and NH was then added3·H2Regulating the pH value of the solution to 11 to obtain a solution B;
(3) under the condition of room temperature, dropwise adding the solution B into the solution A while stirring, and obtaining an emulsion solution after dropwise adding; then reacting the emulsion solution at 90 ℃ for 60 min; and (3) after the reaction is finished, washing the product to be neutral by using distilled water, and drying at 110 ℃ to obtain the iron-based modified nano hydroxyapatite material.
Example 2 preparation of iron-based modified nano-hydroxyapatite Material
(1) Take 40mmol (NH)4)2HPO4Dissolved in 150ml of water and then NH is added3·H2Adjusting the pH value of the solution to 11 to obtain a solution A;
(2) 60.03mmol of Ca (NO) was taken3)2·4H2O (calcium nitrate tetrahydrate) and 6.67mmol FeCl3·6H2O was dissolved in 120ml of water, and NH was then added3·H2Regulating the pH value of the solution to 11 to obtain a solution B;
(3) under the condition of room temperature, dropwise adding the solution B into the solution A while stirring, and obtaining an emulsion solution after dropwise adding; then the emulsion solution is firstly reacted for 15min at 43 ℃; then reacting for 20min at 75 ℃; finally reacting for 40min at 90 ℃; and (3) after the reaction is finished, washing the product to be neutral by using distilled water, and drying at 110 ℃ to obtain the iron-based modified nano hydroxyapatite material.
Comparative example 1 preparation of nano hydroxyapatite Material
(1) Take 40mmol (NH)4)2HPO4Dissolved in 150ml of water and then NH is added3·H2Regulating the pH value of the solution to 11 to obtain a solution A;
(2) 60.03mmol of Ca (NO) was taken3)2·4H2O (calcium nitrate tetrahydrate) was dissolved in 120ml of water, and NH was added3·H2Regulating the pH value of the solution to 11 to obtain a solution B;
(3) under the condition of room temperature, dropwise adding the solution B into the solution A while stirring, and obtaining an emulsion solution after dropwise adding; then reacting the emulsion solution at 90 ℃ for 60 min; and after the reaction is finished, washing the product to be neutral by using distilled water, and drying at 110 ℃ to obtain the nano hydroxyapatite material.
Comparative example 1 differs from example 1 in that comparative example 1 does not add FeCl3Only preparing nano hydroxyapatite material; in example 1, FeCl was added during the preparation3And preparing the iron-based modified nano hydroxyapatite material.
Comparative example 2 preparation of iron-based modified nano-hydroxyapatite Material
(1) Take 40mmol (NH)4)2HPO4Dissolved in 150ml of water and then NH is added3·H2Regulating the pH value of the solution to 11 to obtain a solution A;
(2) 60.03mmol of Ca (NO) was taken3)2·4H2O (calcium nitrate tetrahydrate) and 6.67mmol FeCl3·6H2O was dissolved in 120ml of water, and NH was then added3·H2Regulating the pH value of the solution to 11 to obtain a solution B;
(3) under the condition of room temperature, dropwise adding the solution B into the solution A while stirring, and obtaining an emulsion solution after dropwise adding; then the emulsion solution is firstly reacted for 35min at 75 ℃; then reacting for 40min at 90 ℃; and (3) after the reaction is finished, washing the product to be neutral by using distilled water, and drying at 110 ℃ to obtain the iron-based modified nano hydroxyapatite material.
The difference between the comparative example 2 and the example 2 is that the heating reaction in the comparative example 2 adopts two-stage heating reaction, namely, the reaction is firstly carried out for 35min at 75 ℃; then reacted at 90 ℃ for 40 min. In the embodiment 2, three-stage heating reaction is adopted, namely, the reaction is firstly carried out for 15min at 43 ℃; then reacting for 20min at 75 ℃; finally, the reaction is carried out at 90 ℃ for 40 min.
Comparative example 3 preparation of iron-based modified nano-hydroxyapatite Material
(1) Take 40mmol (NH)4)2HPO4Dissolved in 150ml of water and thenAddition of NH3·H2Regulating the pH value of the solution to 11 to obtain a solution A;
(2) 60.03mmol of Ca (NO) was taken3)2·4H2O (calcium nitrate tetrahydrate) and 6.67mmol FeCl3·6H2O was dissolved in 120ml of water, and NH was then added3·H2Regulating the pH value of the solution to 11 to obtain a solution B;
(3) under the condition of room temperature, dropwise adding the solution B into the solution A while stirring, and obtaining an emulsion solution after dropwise adding; then the emulsion solution is firstly reacted for 15min at 50 ℃; then reacting for 20min at 70 ℃; finally reacting for 40min at 90 ℃; and (3) after the reaction is finished, washing the product to be neutral by using distilled water, and drying at 110 ℃ to obtain the iron-based modified nano hydroxyapatite material.
Comparative example 3 is different from example 2 in that, in comparative example 3, although the three-stage heating reaction was used, the conditions of the three-stage heating reaction were different; comparative example 3 the reaction was first carried out at 50 ℃ for 15 min; then reacting for 20min at 70 ℃; finally, the reaction is carried out at 90 ℃ for 40 min. In example 2, the reaction is carried out for 15min at 43 ℃; then reacting for 20min at 75 ℃; finally, the reaction is carried out at 90 ℃ for 40 min.
Comparative example 4 preparation of iron-based modified nano-hydroxyapatite Material
(1) Take 40mmol (NH)4)2HPO4Dissolved in 150ml of water and then NH is added3·H2Regulating the pH value of the solution to 11 to obtain a solution A;
(2) 60.03mmol of Ca (NO) was taken3)2·4H2O (calcium nitrate tetrahydrate) and 6.67mmol FeCl3·6H2O was dissolved in 120ml of water, and NH was then added3·H2Regulating the pH value of the solution to 11 to obtain a solution B;
(3) under the condition of room temperature, dropwise adding the solution B into the solution A while stirring, and obtaining an emulsion solution after dropwise adding; then the emulsion solution is firstly reacted for 20min at 35 ℃; then reacting for 20min at 80 ℃; finally reacting for 35min at 95 ℃; and (3) after the reaction is finished, washing the product to be neutral by using distilled water, and drying at 110 ℃ to obtain the iron-based modified nano hydroxyapatite material.
Comparative example 4 is different from example 2 in that, in comparative example 4, although the three-stage heating reaction was used, the conditions of the three-stage heating reaction were different; comparative example 4 reaction at 35 ℃ for 20 min; then reacting for 20min at 80 ℃; finally, the reaction was carried out at 95 ℃ for 35 min. In example 2, the reaction is carried out for 15min at 43 ℃; then reacting for 20min at 75 ℃; finally, the reaction is carried out at 90 ℃ for 40 min.
Examples of the experiments
The soil to be tested is selected from farmland soil of Dong Pond villages and towns of Renzhi county of Shaoguan city, is naturally air-dried, is crushed after sundries are removed, is sieved by a nylon sieve with the diameter of 2mm, and is uniformly mixed for later use; then dividing into 7 parts, and placing each 100g part into a 100ml conical flask; dividing the materials into a control group and an experimental group, wherein the control group is not added with any adsorbing material, and the experimental group is respectively added with the iron-based modified nano hydroxyapatite materials prepared in the embodiment 1 or 2 or the control groups 1-4 according to the addition amount of 0.5% by weight; the iron-based modified nano hydroxyapatite material is uniformly mixed with soil, and then deionized water is used for ensuring that the cultivation soil is just infiltrated (the water content is maintained at about 30 percent and is not more than 40 percent), and the cultivation reaction is carried out for 15 days in a constant-temperature incubator at the temperature of 25 +/-0.5 ℃. After the cultivation reaction is finished, respectively weighing 6.00g of dry soil of a control group or each experimental group into a 50mL centrifuge tube, adding 15mL of DTPA solution, oscillating for 2h at normal temperature, centrifuging at 4000r/min, then retaining supernatant, and determining the content of heavy metal by adopting an atomic absorption instrument; the lower the content of Cd in the DTPA extracted state of the experimental soil is, the better the restoration effect of the iron-based modified nano hydroxyapatite material on Cd-polluted soil can be reflected.
Table 1. DTPA extracted Cd content determination result of experimental soil
As can be seen from the experimental results in table 1, the content of Cd in the DTPA extracted state of the iron-based modified nano-hydroxyapatite material prepared in example 1 to the experimental soil is significantly lower than that of the nano-hydroxyapatite material prepared in comparative example 1; this indicates that: the iron-based modified nano hydroxyapatite material prepared by the method has a repairing effect on Cd-polluted soil which is obviously higher than that of an unmodified nano hydroxyapatite material.
It can be seen from the experimental results in table 1 that the content of Cd in the DTPA extracted state of the experimental soil in the iron-based modified nano-hydroxyapatite material prepared in example 2 is further significantly lower than that in the iron-based modified nano-hydroxyapatite material prepared in example 1; and is also far lower than the nano hydroxyapatite material prepared in the comparative example 1. Meanwhile, compared with the example 1, the content of Cd in the DTPA extracted state of the experimental soil in the iron-based modified nano-hydroxyapatite material prepared in the comparative examples 2-4 is not reduced or greatly reduced. This indicates that: in the process of preparing the iron-based modified nano-hydroxyapatite material by using the raw materials, the heating reaction temperature plays an important role in determining whether the prepared iron-based modified nano-hydroxyapatite material has an excellent repairing effect on Cd-polluted soil; the iron-based modified nano-hydroxyapatite material prepared at different reaction temperatures has excellent repairing effect on Cd-polluted soil, and the difference is great. The above experimental results show that: the iron-based modified nano-hydroxyapatite material prepared under the three-stage heating reaction condition (namely, the iron-based modified nano-hydroxyapatite material is firstly reacted at 40-45 ℃ for 15-20 min, then reacted at 75-80 ℃ for 15-20 min, and finally reacted at 85-95 ℃ for 20-50 min) has a far higher repairing effect on Cd-polluted soil than the iron-based modified nano-hydroxyapatite material prepared under a single temperature condition; the repairing effect of the iron-based modified nano-hydroxyapatite material prepared under the three-stage heating reaction condition on Cd-polluted soil is far higher than that of the iron-based modified nano-hydroxyapatite material prepared under a single temperature condition; however, the iron-based modified nano-hydroxyapatite material prepared under other three-stage heating reaction conditions or two-stage heating reaction conditions has a repairing effect on Cd-polluted soil which is not higher or far higher than that of the iron-based modified nano-hydroxyapatite material prepared under a single temperature condition.
Claims (10)
1. A preparation method of an iron-based modified nano hydroxyapatite material is characterized by comprising the following steps:
dissolving phosphate in water, and adjusting the pH value to 10-11 to obtain a solution A;
dissolving calcium salt and ferric salt in water, and adjusting the pH value to 10-11 to obtain a solution B;
mixing the solution A and the solution B to obtain a milky solution; and then heating the emulsion solution for reaction, and washing and drying the product after the reaction is finished to obtain the iron-based modified nano hydroxyapatite material.
2. The method for preparing the iron-based modified nano hydroxyapatite material according to claim 1, wherein the phosphate is (NH)4)2HPO4。
3. The preparation method of the iron-based modified nano hydroxyapatite material according to claim 1, wherein the use amount ratio of phosphate to water is 30-50 mmol: 100-200 mL;
most preferably, the ratio of phosphate to water is 40mmol:150 mL.
4. The method for preparing iron-based modified nano hydroxyapatite material according to claim 1, wherein the calcium salt is Ca (NO)3)2·4H2O; the iron salt is FeCl3·6H2O。
5. The method for preparing the iron-based modified nano hydroxyapatite material according to claim 1, wherein Ca (NO) is added3)2·4H2O、FeCl3·6H2The dosage ratio of O to water is 60-70 mmol: 6-7 mmol: 100-150 mL;
most preferably, Ca (NO)3)2·4H2O、FeCl3·6H2The dosage ratio of O to water was 60.03mmol:6.67mmol:120 mL.
6. The method for preparing the iron-based modified nano hydroxyapatite material according to claim 1, wherein the volume ratio of the solution A to the solution B is 1-1.5: 1.
7. The method for preparing the iron-based modified nano hydroxyapatite material according to claim 1, wherein the heating reaction is carried out at 85-95 ℃ for 40-90 min.
8. The method for preparing the iron-based modified nano hydroxyapatite material according to claim 1, wherein the heating reaction is carried out at 40-45 ℃ for 15-20 min; then reacting for 15-20 min at 75-80 ℃; and finally reacting for 20-50 min at 85-95 ℃.
9. The iron-based modified nano hydroxyapatite material prepared by the preparation method of any one of claims 1 to 8.
10. The application of the iron-based modified nano hydroxyapatite material of claim 9 in repairing Cd-contaminated soil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210435552.XA CN114702962B (en) | 2022-04-24 | 2022-04-24 | Iron-based modified nano hydroxyapatite material, preparation method thereof and application thereof in restoring Cd-polluted soil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210435552.XA CN114702962B (en) | 2022-04-24 | 2022-04-24 | Iron-based modified nano hydroxyapatite material, preparation method thereof and application thereof in restoring Cd-polluted soil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114702962A true CN114702962A (en) | 2022-07-05 |
| CN114702962B CN114702962B (en) | 2023-11-03 |
Family
ID=82175255
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210435552.XA Active CN114702962B (en) | 2022-04-24 | 2022-04-24 | Iron-based modified nano hydroxyapatite material, preparation method thereof and application thereof in restoring Cd-polluted soil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114702962B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115318259A (en) * | 2022-07-08 | 2022-11-11 | 南方科技大学 | Preparation method and application of iron-doped hydroxyapatite nano slow-release compound |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005131574A (en) * | 2003-10-31 | 2005-05-26 | Sumikon Serutekku Kk | Insolubilization method of heavy metal contaminated soil |
| CN101407316A (en) * | 2007-10-12 | 2009-04-15 | 西南交通大学 | Method for preparing high dispersibility nano-hydroxyapatite |
| CN101486452A (en) * | 2009-02-16 | 2009-07-22 | 重庆大学 | Preparation of nano hydroxylapatite powder |
| CN101734635A (en) * | 2009-12-31 | 2010-06-16 | 四川大学 | Method for preparing nano hydroxyapatite powder |
| KR20120016888A (en) * | 2010-08-17 | 2012-02-27 | 경북대학교 산학협력단 | A method of adsorbing and immobillizing heavy metals in contaminated soil using modified clays and phosphates |
| CN106044734A (en) * | 2016-06-23 | 2016-10-26 | 宝钢发展有限公司 | Method for preparing nano-hydroxyapatite |
| CN109679659A (en) * | 2018-12-27 | 2019-04-26 | 广东开源环境科技有限公司 | A kind of renovation agent of restoration of soil polluted by heavy metal and its preparation method and application |
| CN110653248A (en) * | 2019-10-09 | 2020-01-07 | 安徽省农业科学院土壤肥料研究所 | Composite passivation material suitable for arsenic, cadmium and lead polluted rice field and application thereof |
| CN111701562A (en) * | 2020-06-23 | 2020-09-25 | 中南大学 | Hydroxyapatite-loaded nano zero-valent iron composite material and preparation and application methods thereof |
| CN113429975A (en) * | 2021-08-10 | 2021-09-24 | 中南大学 | Soil passivator for repairing lead-cadmium-arsenic combined pollution and preparation method and application thereof |
| WO2023061203A1 (en) * | 2021-10-14 | 2023-04-20 | 江西农业大学 | Method for reducing greenhouse gas emissions from heavy metal polluted soil |
-
2022
- 2022-04-24 CN CN202210435552.XA patent/CN114702962B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005131574A (en) * | 2003-10-31 | 2005-05-26 | Sumikon Serutekku Kk | Insolubilization method of heavy metal contaminated soil |
| CN101407316A (en) * | 2007-10-12 | 2009-04-15 | 西南交通大学 | Method for preparing high dispersibility nano-hydroxyapatite |
| CN101486452A (en) * | 2009-02-16 | 2009-07-22 | 重庆大学 | Preparation of nano hydroxylapatite powder |
| CN101734635A (en) * | 2009-12-31 | 2010-06-16 | 四川大学 | Method for preparing nano hydroxyapatite powder |
| KR20120016888A (en) * | 2010-08-17 | 2012-02-27 | 경북대학교 산학협력단 | A method of adsorbing and immobillizing heavy metals in contaminated soil using modified clays and phosphates |
| CN106044734A (en) * | 2016-06-23 | 2016-10-26 | 宝钢发展有限公司 | Method for preparing nano-hydroxyapatite |
| CN109679659A (en) * | 2018-12-27 | 2019-04-26 | 广东开源环境科技有限公司 | A kind of renovation agent of restoration of soil polluted by heavy metal and its preparation method and application |
| CN110653248A (en) * | 2019-10-09 | 2020-01-07 | 安徽省农业科学院土壤肥料研究所 | Composite passivation material suitable for arsenic, cadmium and lead polluted rice field and application thereof |
| CN111701562A (en) * | 2020-06-23 | 2020-09-25 | 中南大学 | Hydroxyapatite-loaded nano zero-valent iron composite material and preparation and application methods thereof |
| CN113429975A (en) * | 2021-08-10 | 2021-09-24 | 中南大学 | Soil passivator for repairing lead-cadmium-arsenic combined pollution and preparation method and application thereof |
| WO2023061203A1 (en) * | 2021-10-14 | 2023-04-20 | 江西农业大学 | Method for reducing greenhouse gas emissions from heavy metal polluted soil |
Non-Patent Citations (3)
| Title |
|---|
| 张维丽;王臻;李荣先;张欣宇;: "利用液相合成方法制备纳米羟基磷灰石", 新技术新工艺, no. 02 * |
| 杨辉;王栋;蔡日强;: "共沉淀法制备高纯度纳米羟基磷灰石的研究", 精细化工, no. 01 * |
| 莫利蓉;李玉宝;吕国玉;李吉东;杨维虎;: "不同条件下合成的纳米羟基磷灰石晶体的性能研究", 化学研究与应用, no. 03 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115318259A (en) * | 2022-07-08 | 2022-11-11 | 南方科技大学 | Preparation method and application of iron-doped hydroxyapatite nano slow-release compound |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114702962B (en) | 2023-11-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Research progress and mechanism of nanomaterials-mediated in-situ remediation of cadmium-contaminated soil: A critical review | |
| Ashworth et al. | Complexation of copper by sewage sludge-derived dissolved organic matter: Effects on soil sorption behaviour and plant uptake | |
| Anastopoulos et al. | Composts as biosorbents for decontamination of various pollutants: a review | |
| Tang et al. | Removal of lead ions from aqueous solution by the dried aquatic plant, Lemna perpusilla Torr. | |
| Singh et al. | Microwave induced poly (acrylic acid) modification of Cassia javanica seed gum for efficient Hg (II) removal from solution | |
| Chatterjee et al. | Fractions, uptake and fixation capacity of phosphorus and potassium in three contrasting soil orders | |
| Salama et al. | Synthesis of an eco-friendly nanocomposite fertilizer for common bean based on carbon nanoparticles from agricultural waste biochar | |
| CN109678626B (en) | Soil conditioner for mercury-polluted farmland remediation and preparation method and application thereof | |
| Wu et al. | Magnetic biochar reduces phosphorus uptake by Phragmites australis during heavy metal remediation | |
| CN107502362B (en) | Method for preparing acid soil conditioner from papermaking black liquor and application thereof | |
| Coelho et al. | Removal of Cd (II), Pb (II) and Cr (III) from water using modified residues of Anacardium occidentale L. | |
| CN114702962A (en) | Iron-based modified nano hydroxyapatite material, preparation method thereof and application thereof in Cd-contaminated soil remediation | |
| Nacke et al. | Removal of Cd (II) from water using the waste of jatropha fruit (Jatropha curcas L.) | |
| Liu et al. | Effects of mercury binding by humic acid and humic acid resistance on mercury stress in rice plants under high Hg/humic acid concentration ratios | |
| CN110653248A (en) | Composite passivation material suitable for arsenic, cadmium and lead polluted rice field and application thereof | |
| Huang et al. | Enhanced fluoride adsorption of aluminum humate and its resistance on fluoride accumulation in tea leaves | |
| Wang et al. | Risk assessment of Artemia egg shell-Mg-P composites as a slow-release phosphorus fertilizer during its formation and application in typical heavy metals contaminated environment | |
| CN114751389B (en) | Selenium-based modified nano hydroxyapatite material, preparation method thereof and application thereof in restoring Cd-polluted soil | |
| Leite et al. | Activated ZnCl2 biochar and humic acid as additives in monoammonium phosphate fertilizer: Physicochemical characterization and agronomic effectiveness | |
| Qian et al. | Effect of culturing temperatures on cadmium phytotoxicity alleviation by biochar | |
| Pan et al. | Rhizosphere environmental factors regulated the cadmium adsorption by vermicompost: Influence of pH and low-molecular-weight organic acids | |
| An et al. | Recovery of ammonia nitrogen and phosphate from livestock farm wastewater by iron-magnesium oxide coupled lignite and its potential for resource utilization | |
| Nigro et al. | Optimising heavy metal adsorbance by dried seaweeds | |
| EP2498927A2 (en) | Method for sequestering organic carbon in soil | |
| Rezaei-Aghdam et al. | Synthesis of a Nanocomposite Containing CTAB-stabilized Fe3O4 Magnetic Nanoparticles and a Comparison between the Adsorption Behavior of Cobalt ions on the Nanocomposite and Typha latifolia L. |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |