CN117004394A - Arsenic-antimony contaminated soil restoration agent and preparation method and application thereof - Google Patents
Arsenic-antimony contaminated soil restoration agent and preparation method and application thereof Download PDFInfo
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- CN117004394A CN117004394A CN202310876071.7A CN202310876071A CN117004394A CN 117004394 A CN117004394 A CN 117004394A CN 202310876071 A CN202310876071 A CN 202310876071A CN 117004394 A CN117004394 A CN 117004394A
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- 239000002689 soil Substances 0.000 title claims abstract description 119
- 238000002360 preparation method Methods 0.000 title claims abstract description 95
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 58
- DLISVFCFLGSHAB-UHFFFAOYSA-N antimony arsenic Chemical compound [As].[Sb] DLISVFCFLGSHAB-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000000197 pyrolysis Methods 0.000 claims abstract description 86
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000011282 treatment Methods 0.000 claims abstract description 46
- 239000002734 clay mineral Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 32
- 150000007524 organic acids Chemical class 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 13
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 13
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 238000005067 remediation Methods 0.000 claims description 18
- 239000005995 Aluminium silicate Substances 0.000 claims description 13
- 239000004113 Sepiolite Substances 0.000 claims description 13
- 235000012211 aluminium silicate Nutrition 0.000 claims description 13
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052624 sepiolite Inorganic materials 0.000 claims description 13
- 235000019355 sepiolite Nutrition 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 238000001764 infiltration Methods 0.000 claims description 2
- 230000008595 infiltration Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 230000006641 stabilisation Effects 0.000 description 11
- 238000011105 stabilization Methods 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 230000007774 longterm Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 238000003900 soil pollution Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000003281 allosteric effect Effects 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001687 destabilization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000005838 radical anions Chemical class 0.000 description 1
- 239000002681 soil colloid Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 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
- C09K17/08—Aluminium compounds, e.g. aluminium hydroxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
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)
- Processing Of Solid Wastes (AREA)
Abstract
The application relates to an arsenic-antimony contaminated soil restoration agent, and a preparation method and application thereof, wherein the method comprises the following steps: carrying out first pyrolysis treatment on clay minerals to obtain a first pyrolysis product; and mixing the first pyrolysis product with birnessite type manganese dioxide, and performing a second pyrolysis treatment on the mixture under the action of organic acid to obtain a second pyrolysis product. The arsenic-antimony contaminated soil restoration agent obtained by the method has long-acting and stable restoration effects on arsenic single contaminated soil, antimony single contaminated soil or arsenic-antimony combined contaminated soil.
Description
Technical Field
The application relates to the technical field of soil remediation and environmental functional materials, in particular to an arsenic-antimony contaminated soil remediation agent, a preparation method and application thereof.
Background
At present, inorganic soil pollution represented by heavy metals is serious. The national soil pollution condition investigation publication jointly issued by the environmental protection department and the national soil resource department in 2014 shows that the national soil pollution point position exceeds the standard rate by 16.1 percent, and the inorganic pollution accounts for 82.8 percent in the exceeding standard point position. Stabilization is the most common repair technique for heavy metal pollution of soil, and the adoption rate of the technique is as high as 48.5% in 2018. However, conventional stabilizing materials fail in practical applications due to crack development, acid leaching, and the like. In addition, compared with positively charged cationic heavy metals (such as cadmium, lead and copper), the metalloid arsenic and antimony exist in the soil in the form of oxyacid radical anions, have the same electrical properties as the soil colloid, have stronger mobility than cations, and are more difficult to realize stabilization.
Therefore, it is necessary to provide a stable soil restoration material capable of realizing long-term restoration aiming at arsenic-antimony pollution.
Disclosure of Invention
Based on the above, the application provides the repair agent for the arsenic-antimony contaminated soil, and the preparation method and the application thereof, which can realize the long-acting stable repair of the arsenic-antimony composite contaminated soil.
The application provides a preparation method of an arsenic-antimony contaminated soil restoration agent, which comprises the following steps:
carrying out first pyrolysis treatment on clay minerals to obtain a first pyrolysis product; and
and mixing the first pyrolysis product with birnessite type manganese dioxide, and performing a second pyrolysis treatment on the mixture under the action of organic acid to obtain a second pyrolysis product.
In some of these embodiments, the clay mineral comprises kaolin and sepiolite, optionally in a mass ratio of 1: (2-4).
In some of these embodiments, the mass ratio of the first pyrolysis product to the birnessite-type manganese dioxide is (6-8): 1.
in some embodiments, the temperature of the first pyrolysis treatment is 400-500 ℃, and the time of the first pyrolysis treatment is 2-3 h.
In some embodiments, the temperature of the second pyrolysis treatment is 600-800 ℃, and the temperature of the second pyrolysis treatment is 4-6 h.
In some of these embodiments, the method of subjecting the mixture to a second pyrolysis treatment with an aqueous solution of an organic acid includes the step of immersing the mixture of the first pyrolysis product and the birnessite-type manganese dioxide in the aqueous solution of the organic acid.
In some embodiments, the concentration of the organic acid in the aqueous solution of the organic acid is 0.1mol/L to 0.5mol/L, and the infiltration time is 1 to 3 hours.
In some of these embodiments, the organic acid comprises one or more of citric acid, malic acid, oxalic acid, and tartaric acid, optionally citric acid.
In some embodiments, the subjecting the clay mineral to a first pyrolysis treatment step further comprises: and (3) carrying out acid washing on the clay mineral.
In some of these embodiments, the acid wash step uses H in the acid solution + The concentration of the clay mineral is 1mol/L to 5mol/L, and the solid-liquid ratio of the clay mineral to the acid liquid is 1: (5-20), wherein the unit is g/mL, and the action time of the acid liquor is 1-3 h.
In a second aspect, the application provides an arsenic-antimony contaminated soil restoration agent prepared by the method of the first aspect.
In a third aspect, the application provides the use of the arsenic-antimony contaminated soil restoration agent of the second aspect of the application in soil restoration.
In some of these embodiments, the soil is arsenic single contaminated soil, antimony single contaminated soil, or arsenic-antimony combined contaminated soil.
According to a fourth aspect of the application, there is provided a soil remediation method comprising the step of adding the arsenic-antimony contaminated soil remediation agent according to the second aspect of the application to soil to be remediated, wherein the addition amount of the arsenic-antimony contaminated soil remediation agent is 1% -5% of the mass of the soil to be remediated.
In some embodiments, the soil remediation method further comprises adding water to the soil to be remediated for maintenance after adding the arsenic-antimony contaminated soil remediation agent, wherein the maintenance time is 5-7 days, and the water adding amount is 25% -40% of the mass of the soil to be remediated.
Compared with the prior art, the application has at least the following beneficial effects:
according to the preparation method of the arsenic-antimony contaminated soil restoration agent, the birnessite type manganese dioxide is adopted to modify clay minerals, and the arsenic-antimony contaminated soil restoration agent is obtained by combining two pyrolysis treatments. The arsenic-antimony contaminated soil restoration agent obtained by the preparation method has long-acting and stable restoration effects on arsenic single contaminated soil, antimony single contaminated soil or arsenic-antimony combined contaminated soil.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present application, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of a preparation method of an arsenic-antimony contaminated soil remediation agent according to an embodiment of the application;
fig. 2 is a schematic flow chart of a preparation method of an arsenic-antimony contaminated soil restoration agent according to another embodiment of the application.
Detailed Description
In order that the application may be readily understood, a more complete description of the application will be rendered by reference to the appended drawings. Preferred embodiments of the present application are shown in the drawings. This application may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
In the application, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.
In the present application, "one or more" means any one, any two or more of the listed items.
In the present application, the numerical ranges are referred to as continuous, and include the minimum and maximum values of the ranges, and each value between the minimum and maximum values, unless otherwise specified. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
All embodiments of the application and alternative embodiments may be combined with each other to form new solutions, unless otherwise specified.
All technical features and optional technical features of the application may be combined with each other to form new technical solutions, unless specified otherwise.
All steps of the present application may be performed sequentially or randomly unless otherwise specified. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, or may comprise steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), may include steps (a), (c) and (b), may include steps (c), (a) and (b), and the like.
The terms "comprising" and "including" as used herein mean open ended or closed ended, unless otherwise noted. For example, the terms "comprising" and "comprises" may mean that other components not listed may be included or included, or that only listed components may be included or included.
The term "or" is inclusive in this application, unless otherwise specified. For example, the phrase "a or B" means "a, B, or both a and B. More specifically, either of the following conditions satisfies the condition "a or B": a is true (or present) and B is false (or absent); a is false (or absent) and B is true (or present); or both A and B are true (or present).
Referring to fig. 1, in a first aspect of the present application, a method for preparing an arsenic-antimony contaminated soil restoration agent is provided, which includes the following steps:
s10, performing first pyrolysis treatment on clay minerals to obtain a first pyrolysis product; and
s20, mixing the first pyrolysis product and birnessite type manganese dioxide, and performing a second pyrolysis treatment on the mixture under the action of organic acid to obtain a second pyrolysis product.
According to the preparation method of the arsenic-antimony contaminated soil restoration agent, the birnessite type manganese dioxide is adopted to modify clay minerals, and the arsenic-antimony contaminated soil restoration agent is obtained by combining two pyrolysis treatments. The clay mineral is modified by the birnessite type manganese dioxide, so that the repairing agent has physical adsorptivity and chemical adsorptivity at the same time, water adsorbed between clay mineral layers is removed by first pyrolysis treatment, and lattice conversion is realized by second pyrolysis treatment under the action of organic acid. Without being limited by any theory, the arsenic-antimony contaminated soil restoration agent obtained by the preparation method has long-acting and stable restoration effect on arsenic-single contaminated soil, antimony-single contaminated soil or arsenic-antimony combined contaminated soil.
The clay mineral can be a single component or a combination of a plurality of components, the clay mineral of the plurality of components can also be called as a compound clay mineral, and the plurality of components play a role in synergy. In some embodiments, the clay minerals include kaolin and sepiolite. Alternatively, in some embodiments, the mass ratio of kaolin to sepiolite is 1: (2-4), e.g. 1:2.5, 1:3. 1:3.5, etc., and any ratio therebetween. The mass ratio of kaolin to sepiolite in this range is more favorable for the adsorptivity and stability of the soil restoration agent. The mass ratio of the kaolin is too high, and the total surface adsorption point number of the arsenic-antimony polluted soil restoration agent is reduced; the sepiolite has excessive mass ratio, and the soil restoration agent polluted by arsenic and antimony has good ductility, easy destabilization and unstable crystal lattice after being added.
The mesh number of each of the individual component or the components of the clay mineral may be selected to be 80 to 120 mesh, for example, 85 mesh, 90 mesh, 95 mesh, 100 mesh, 105 mesh, 110 mesh, 115 mesh, and any value therebetween.
In some embodiments, the temperature of the first pyrolysis treatment is 400 ℃ to 500 ℃, such as 410 ℃, 420 ℃, 430 ℃, 440 ℃, 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃, and any value therebetween. The temperature of the first pyrolysis treatment is in the range, which is more favorable for the long-term stability of the soil restoration agent polluted by arsenic and antimony. The temperature of the first pyrolysis treatment is too low, interlayer adsorption water of clay minerals cannot be completely removed, and the adsorption capacity of the arsenic-antimony polluted soil restoration agent cannot be well excited; the temperature of the first pyrolysis treatment is too high, and the crystal lattice is thermally destructively unstable.
In some embodiments, the time of the first pyrolysis treatment is from 2h to 3h, such as 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h, 2.9h, and any value therebetween.
In some embodiments, the temperature of the second pyrolysis treatment is 600 ℃ to 800 ℃, such as 620 ℃, 640 ℃, 660 ℃, 680 ℃, 700 ℃, 720 ℃, 740 ℃, 760 ℃, 780 ℃, and any value therebetween. The temperature of the second pyrolysis treatment is in the range more favorable for the recombination of the clay minerals and birnessite to form new crystal lattices.
In some embodiments, the second pyrolysis treatment is for a period of time ranging from 4 hours to 6 hours, such as 4.2 hours, 4.4 hours, 4.6 hours, 4.8 hours, 5 hours, 5.2 hours, 5.4 hours, 5.6 hours, 5.8 hours, and any value therebetween.
In some embodiments, the mass ratio of the first pyrolysis product to the birnessite type manganese dioxide is (6-8): 1, e.g., 6:1, 6.5:1, 7:1, 7.5:1, and any value therebetween. The clay mineral mainly plays a role in physical adsorption, and the birnessite manganese dioxide plays a role in modifying the clay mineral to have a chemical adsorption effect, so that the ratio of the birnessite manganese dioxide to the birnessite manganese dioxide has a better adsorption and restoration effect on arsenic and antimony in polluted soil.
The first pyrolysis treatment and the second pyrolysis treatment are both performed under an inert atmosphere, for example, a nitrogen atmosphere.
The second pyrolysis treatment mentioned above requires that the mixture is subjected to an organic acid, i.e., the organic acid is present in the mixture of the first pyrolysis product and birnessite type manganese dioxide during the second pyrolysis treatment. The organic acid provides an acidic environment for the second pyrolysis, is favorable for pyrolysis allosteric recombination, and enables clay minerals and birnessite type manganese dioxide to form new crystal lattices.
In some embodiments, the method of subjecting the mixture to a second pyrolysis treatment with an organic acid comprises immersing the mixture of the first pyrolysis product and birnessite-type manganese dioxide in an aqueous solution of the organic acid. It should be further noted that the infiltrated mixture was not rinsed and the second pyrolysis treatment was performed in the presence of an organic acid in the mixture of the first pyrolysis product and birnessite type manganese dioxide. In still other embodiments, the infiltrated mixture is not subjected to a drying process. The drying treatment can reduce the stabilizing and repairing effects of the soil repairing agent.
The aqueous solution of the organic acid mainly provides an acidic environment for the second pyrolysis treatment, is favorable for the pyrolysis allosteric recombination of the second pyrolysis, and allows the clay mineral and the birnessite manganese dioxide to recombine to form a new crystal lattice. In some embodiments, the concentration of the organic acid in the aqueous solution of the organic acid is from 0.1mol/L to 0.5mol/L. Optionally, the organic acid comprises one or more of citric acid, malic acid, oxalic acid and tartaric acid. Further alternatively, the organic acid is citric acid.
In some embodiments, the first pyrolysis product and birnessite-type manganese dioxide mixture is immersed in the aqueous solution of the organic acid for a period of time ranging from 1h to 3h.
Referring to fig. 2, in some embodiments, in step S10, before the clay mineral is subjected to the first pyrolysis treatment step, S00 is further included: and (3) carrying out acid washing on the clay mineral. The purpose of the acid washing is to remove clay mineral impurities.
In some embodiments, the acid solution used in the acid wash step is H + The acid solution used in the acid washing step may be one or more of hydrochloric acid, sulfuric acid and nitric acid, for example, in a concentration of 1mol/L to 5mol/L, and may be 2mol/L, 3mol/L and 4 mol/L.
In some embodiments, the solid to liquid ratio of clay mineral to acid solution is 1: (5-20) (g/mL), for example, may also be 1:6 (g/mL), 1:8 (g/mL), 1:10 (g/mL), 1:12 (g/mL), 1:14 (g/mL), 1:16 (g/mL), 1:18 (g/mL).
In some embodiments, the acid solution is applied for 1h to 3h, for example, 1.2h, 1.4h, 1.6h, 1.8h, 2h, 2.2h, 2.4h, 2.6h, 2.8h.
In a second aspect of the embodiment of the application, there is provided an arsenic-antimony contaminated soil restoration agent prepared by the method of the first aspect of the embodiment of the application.
In a third aspect of the embodiment of the present application, there is provided the use of the arsenic-antimony contaminated soil restoration agent according to the second aspect of the application for soil restoration. In some embodiments, the soil is arsenic single contaminated soil, antimony single contaminated soil, or arsenic-antimony combined contaminated soil.
According to a fourth aspect of the embodiment of the application, a soil remediation method is provided, which comprises the steps of adding the arsenic-antimony contaminated soil remediation agent according to the second aspect of the application into soil to be remediated, wherein the addition amount of the arsenic-antimony contaminated soil remediation agent is 1% -5% of the mass of the soil to be remediated.
In some embodiments, the soil remediation method further comprises adding water to the soil to be remediated for maintenance after adding the arsenic-antimony contaminated soil remediation agent, wherein the maintenance time is 5-7 days, and the water addition amount is 25% -40% of the mass of the soil to be remediated.
The following are specific examples. The present application is further described in detail to assist those skilled in the art and researchers in further understanding the present application, and the technical conditions and the like are not to be construed as limiting the present application in any way. Any modification made within the scope of the claims of the present application is within the scope of the claims of the present application.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods. The apparatus is a routine choice in the art. The experimental methods without specific conditions noted in the examples were carried out according to conventional conditions, such as those described in the literature, books, or recommended by the manufacturer.
Preparation example 1
1. Mixing kaolin (100 meshes) and sepiolite (100 meshes) according to a mass ratio of 1:2, soaking for 1h (solid-to-liquid ratio of 1:10 g/mL) by using 2mol/L hydrochloric acid, and then flushing with deionized water until the pH of an eluent is unchanged, so as to obtain the compound clay mineral powder.
2. And (3) carrying out first pyrolysis on the compound clay mineral powder, and placing the compound clay mineral powder in a muffle furnace for pyrolysis for 2 hours in a nitrogen atmosphere at 500 ℃ to obtain a first pyrolysis product.
3. The first pyrolysis product and birnessite type manganese dioxide (100 meshes) are mixed in a mass ratio of 8:1, ball-milled for 1h at 300rpm, then placed in 0.2mol/L citric acid for soaking for 2h, then the wet soaked product is subjected to second pyrolysis, and placed in a muffle furnace for pyrolysis for 5h under the nitrogen atmosphere at 700 ℃.
Preparation example 2
The preparation method of preparation example 2 was substantially the same as that of preparation example 1, except that: the mass ratio of kaolin to sepiolite was replaced with 1:1.
Preparation example 3
The preparation method of preparation example 3 was substantially the same as that of preparation example 1, except that: the mass ratio of kaolin to sepiolite was replaced with 1:4.
Preparation example 4
The preparation method of preparation example 4 was substantially the same as that of preparation example 1, except that: the mass ratio of kaolin to sepiolite was replaced with 1:5.
Preparation example 5
The preparation method of preparation example 5 was substantially the same as that of preparation example 1, except that: and (3) replacing the temperature of the first pyrolysis of the compound clay mineral powder in the step (2) in a muffle furnace with 300 ℃.
Preparation example 6
The preparation method of preparation example 6 was substantially the same as that of preparation example 1, except that: and (3) replacing the temperature of the first pyrolysis of the compound clay mineral powder in the step (2) in a muffle furnace with 400 ℃.
Preparation example 7
The preparation method of preparation example 7 was substantially the same as that of preparation example 1, except that: and (3) replacing the temperature of the first pyrolysis of the compound clay mineral powder in the step (2) in a muffle furnace with 600 ℃.
Preparation example 8
The preparation method of preparation example 8 was substantially the same as that of preparation example 1, except that: the temperature of the second pyrolysis was replaced with 600 ℃.
Preparation example 9
The preparation method of preparation example 9 was substantially the same as that of preparation example 1, except that: the temperature of the second pyrolysis was replaced with 800 ℃.
Preparation example 10
The preparation method of preparation example 10 was substantially the same as that of preparation example 1, except that: the temperature of the second pyrolysis was replaced with 500 ℃.
Preparation example 11
The preparation method of preparation example 11 was substantially the same as that of preparation example 1, except that: the temperature of the second pyrolysis was replaced with 900 ℃.
Preparation example 12
The preparation method of preparation example 12 was substantially the same as that of preparation example 1, except that: the mass ratio of the first pyrolysis product to birnessite type manganese dioxide is replaced with 5:1.
Preparation example 13
The preparation method of preparation example 13 was substantially the same as that of preparation example 1, except that: the mass ratio of the first pyrolysis product to birnessite type manganese dioxide is replaced by 9:1.
Preparation example 14
The preparation method of preparation example 14 was substantially the same as that of preparation example 1, except that: the mass ratio of the first pyrolysis product to birnessite type manganese dioxide is replaced with 6:1.
Preparation example 15
The preparation method of preparation example 15 was substantially the same as that of preparation example 1, except that: the mass ratio of the first pyrolysis product to birnessite type manganese dioxide is replaced with 7:1.
Preparation example 16
The preparation method of preparation example 16 was substantially the same as that of preparation example 1, except that: in the step 3, the wet soaked matter is dried before the second pyrolysis.
Preparation example 17
The preparation method of preparation example 16 was substantially the same as that of preparation example 1, except that: the acid washing treatment in the step 1 is omitted, and the mixture of the kaolin and the sepiolite is directly subjected to the first pyrolysis treatment.
Preparation of comparative example 1
The preparation method of preparation comparative example 1 was substantially the same as that of preparation example 1, except that: and omitting the citric acid soaking step, and directly carrying out secondary pyrolysis on the first pyrolysis product and the birnessite type manganese dioxide ball-milling mixture.
Preparation of comparative example 2
The preparation method of preparation comparative example 2 was substantially the same as that of preparation example 1, except that: the clay mineral was not modified, and only the compound clay mineral was subjected to acid washing treatment, that is, only step 1 in production example 1 was performed.
Example 1
Taking the soil of a non-ferrous metal mining and selecting site in the southwest of China as target soil to be repaired, and adding a soil repairing agent into the soil of the site to perform stabilization treatment. The site soil has arsenic and antimony combined pollution, the arsenic concentration of the soil is 294.5+/-15.3 mg/kg, the antimony concentration is 449.2 +/-37.5 mg/kg, and the soil particle size is less than 2mm. The soil restoration agent prepared in preparation example 1 was added to the soil at a mass ratio of 3% (the soil restoration agent accounts for the mass of the dry soil), and was cultured with 30% of water (the water addition amount accounts for the mass of the dry soil) for 7 days.
Examples 2 to 15
Examples 2 to 15 are substantially similar to example 1, except that the soil restoration agents prepared in preparation example 1 are replaced with the soil restoration agents prepared in preparation examples 2 to 2, respectively.
Comparative examples 1 to 2
Comparative examples 1 to 2 are substantially similar to example 1 except that: the soil restoration agents prepared in preparation example 1 were replaced with the soil restoration agents prepared in preparation comparative examples 1 to 2, respectively.
Comparative examples 3 to 5
Comparative examples 3 to 5 are substantially similar to example 1 except that: the soil restoration agent prepared in preparation example 1 was replaced with kaolin, sepiolite, and birnessite type manganese dioxide, respectively.
The process parameters in the preparation methods of preparation examples 1 to 15 are listed in table 1 below:
TABLE 1
The soil after the repair of examples 1 to 15 and comparative examples 1 to 8 was subjected to short-term and long-term repair effect test, respectively, as follows:
1. short-term repair effect test method
Leaching heavy metals in soil by a horizontal oscillation method, and testing arsenic leaching concentration C before and after stabilization by adopting inductively coupled plasma mass spectrometry (ICP-MS) 0 And C t1 Antimony leach concentration C 'before and after stabilization' 0 And C' t1 . Calculating the stabilization rate eta of short-term repair As 1 ＝(C 0 -C t1 )/C 0 *100%, short-term repair of Sb stabilization rate eta 2 ＝(C' 0 -C' t1 )/C' 0 *100％。
2. Long-term repair effect test method
The stabilized soil is subjected to aging treatment for 20 times, and the arsenic leaching concentration C before and after aging is tested by adopting the same method or standard as the short-term restoration effect test method t1 And C t2 Antimony leach concentration C 'before and after aging' t1 And C' t2 . Calculating the stabilization rate eta of the long-term repair As 3 ＝(C t1 -C t2 )/C t1 *100%, short-term repair of Sb stabilization rate eta 4 ＝(C' t1 -C' t2 )/C' t1 *100％。
The test results are shown in Table 2:
TABLE 2
Therefore, the soil restoration agent prepared by the preparation method of the arsenic-antimony contaminated soil restoration agent provided by the application has a longer-acting and stable restoration effect on the arsenic-antimony contaminated soil. In comparative example 1, the short-term repair stabilization rate η was set to be equal to 1 、η 2 All higher, but long-term repair stabilization rate eta 3 、η 4 Very low, indicating that the long-acting stability of the restorative prepared without the action of organic acid is poor.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples merely represent a few embodiments of the present application, which facilitate a specific and detailed understanding of the technical solutions of the present application, but are not to be construed as limiting the scope of the application. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. It should be understood that, based on the technical solutions provided by the present application, those skilled in the art may obtain technical solutions through logical analysis, reasoning or limited experiments, which are all within the scope of protection of the appended claims. The scope of the patent is therefore intended to be covered by the appended claims, and the description and drawings may be interpreted as illustrative of the contents of the claims.
Claims (15)
1. The preparation method of the arsenic-antimony contaminated soil restoration agent is characterized by comprising the following steps of:
carrying out first pyrolysis treatment on clay minerals to obtain a first pyrolysis product; and
and mixing the first pyrolysis product with birnessite type manganese dioxide, and performing a second pyrolysis treatment on the mixture under the action of organic acid to obtain a second pyrolysis product.
2. The method for producing an arsenic-antimony contaminated soil restoration agent according to claim 1, wherein the clay mineral comprises kaolin and sepiolite, optionally, the mass ratio of the kaolin to the sepiolite is 1: (2-4).
3. The method for preparing an arsenic-antimony contaminated soil restoration agent according to claim 1, wherein the mass ratio of the first pyrolysis product to the birnessite type manganese dioxide is (6 to 8): 1.
4. the method for preparing an arsenic-antimony contaminated soil restoration agent according to claim 1, wherein the temperature of the first pyrolysis treatment is 400-500 ℃, and the time of the first pyrolysis treatment is 2-3 hours.
5. The method for preparing an arsenic-antimony contaminated soil restoration agent according to claim 1, wherein the temperature of the second pyrolysis treatment is 600-800 ℃, and the time of the second pyrolysis treatment is 4-6 h.
6. The method for preparing the arsenic-antimony contaminated soil restoration agent according to claim 1, wherein the method for subjecting the mixture to a second pyrolysis treatment under the action of an organic acid comprises: and placing the mixture of the first pyrolysis product and the birnessite type manganese dioxide in the aqueous solution of the organic acid for soaking.
7. The method for preparing an arsenic-antimony contaminated soil restoration agent according to claim 6, wherein the concentration of the organic acid in the aqueous solution of the organic acid is 0.1mol/L to 0.5mol/L, and the infiltration time is 1 to 3 hours.
8. The method for producing an arsenic-antimony contaminated soil restoration agent according to claim 6 or 7, wherein the organic acid is citric acid.
9. The method for producing an arsenic-antimony contaminated soil restoration agent according to any one of claims 1 to 8, wherein before the clay mineral is subjected to the first pyrolysis treatment step, further comprising: and (3) carrying out acid washing on the clay mineral.
10. The method for preparing an arsenic-antimony contaminated soil restoration agent according to claim 9, wherein the acid liquid used in the acid washing step is H + The concentration of the clay mineral is 1mol/L to 5mol/L, and the solid-liquid ratio of the clay mineral to the acid liquid is 1: (5-20), wherein the unit is g/mL, and the action time of the acid liquor is 1-3 h.
11. An arsenic-antimony contaminated soil restoration agent prepared by the method of any one of claims 1 to 10.
12. Use of the arsenic-antimony contaminated soil restoration agent according to claim 11 in soil restoration.
13. The use according to claim 12, wherein the soil is arsenic single contaminated soil, antimony single contaminated soil or arsenic-antimony combined contaminated soil.
14. A soil remediation method, which is characterized by comprising the step of adding the arsenic-antimony contaminated soil remediation agent according to claim 11 into soil to be remediated, wherein the addition amount of the arsenic-antimony contaminated soil remediation agent is 1% -5% of the mass of the soil to be remediated.
15. The soil remediation method of claim 14 further comprising adding water to the soil to be remediated for a period of 5 to 7 days after adding the arsenic-antimony contaminated soil remediation agent, the added water being 25 to 40% of the mass of the soil to be remediated.
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