CN110576034B - Soil in-situ remediation method - Google Patents
Soil in-situ remediation method Download PDFInfo
- Publication number
- CN110576034B CN110576034B CN201910952788.9A CN201910952788A CN110576034B CN 110576034 B CN110576034 B CN 110576034B CN 201910952788 A CN201910952788 A CN 201910952788A CN 110576034 B CN110576034 B CN 110576034B
- Authority
- CN
- China
- Prior art keywords
- soil
- sintering
- situ
- porous ceramsite
- remediation
- 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.)
- Active
Links
- 239000002689 soil Substances 0.000 title claims abstract description 90
- 238000005067 remediation Methods 0.000 title claims abstract description 61
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 33
- 230000000694 effects Effects 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000005286 illumination Methods 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims description 54
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 36
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims description 34
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 24
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 18
- 229910001940 europium oxide Inorganic materials 0.000 claims description 17
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 17
- 239000007888 film coating Substances 0.000 claims description 16
- 238000009501 film coating Methods 0.000 claims description 16
- 230000001699 photocatalysis Effects 0.000 claims description 14
- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 12
- 239000000292 calcium oxide Substances 0.000 claims description 12
- 235000012255 calcium oxide Nutrition 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 12
- 239000010802 sludge Substances 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 12
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 12
- 239000002699 waste material Substances 0.000 claims description 11
- 239000004927 clay Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000004576 sand Substances 0.000 claims description 6
- 238000004061 bleaching Methods 0.000 claims 1
- 239000000575 pesticide Substances 0.000 description 16
- 230000008439 repair process Effects 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 10
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002131 composite material Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 241000282414 Homo sapiens Species 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000005947 Dimethoate Substances 0.000 description 3
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 238000012271 agricultural production Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- NNKVPIKMPCQWCG-UHFFFAOYSA-N methamidophos Chemical compound COP(N)(=O)SC NNKVPIKMPCQWCG-UHFFFAOYSA-N 0.000 description 1
- KRTSDMXIXPKRQR-AATRIKPKSA-N monocrotophos Chemical compound CNC(=O)\C=C(/C)OP(=O)(OC)OC KRTSDMXIXPKRQR-AATRIKPKSA-N 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 239000003987 organophosphate pesticide Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- LCCNCVORNKJIRZ-UHFFFAOYSA-N parathion Chemical compound CCOP(=S)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 LCCNCVORNKJIRZ-UHFFFAOYSA-N 0.000 description 1
- RLBIQVVOMOPOHC-UHFFFAOYSA-N parathion-methyl Chemical compound COP(=S)(OC)OC1=CC=C([N+]([O-])=O)C=C1 RLBIQVVOMOPOHC-UHFFFAOYSA-N 0.000 description 1
- RGCLLPNLLBQHPF-HJWRWDBZSA-N phosphamidon Chemical compound CCN(CC)C(=O)C(\Cl)=C(/C)OP(=O)(OC)OC RGCLLPNLLBQHPF-HJWRWDBZSA-N 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000006042 reductive dechlorination reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- B01J35/39—
-
- 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
-
- 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
- C09K17/04—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only applied in a physical form other than a solution or a grout, e.g. as granules or gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
Abstract
The invention relates to a soil in-situ remediation method, which comprises the steps of mixing a prepared soil in-situ remediation agent with water and soil to be remediated under the illumination condition to remediate the soil, and measuring the soil remediation effect at intervals, wherein the dosage of the three components is determined according to the following proportion, namely the soil in-situ remediation agent: water: the soil to be restored is 1 g: 12 ml: 10 g. The soil in-situ remediation method disclosed by the invention is high in remediation efficiency, suitable for various polluted soils, wide in raw material source, low in cost and simple to operate.
Description
Technical Field
The invention relates to a soil in-situ remediation method.
Background
The pesticide is used as an important input substance for agricultural production, and makes great contribution to agricultural development and human grain supply. Investigation showed that of all the pesticides used, 60% of the chemical pesticides contained organophosphorus, and 65% of the highly toxic organophosphorus pesticides contained. On a global scale, the grain loss caused by diseases, insects and weeds accounts for about half of the total yield of the grains every year, and the use of pesticides can recover the loss. However, due to the long-term large-scale use of organophosphorus pesticides, water and soil environments are polluted, and the organophosphorus pesticides enter a food chain in a residual mode and generate an accumulation effect in an animal body, so that the organophosphorus pesticides cause teratogenesis, carcinogenesis, mutagenesis and other hazards, and pose a serious threat to the health of human beings at the top end of the food chain. Therefore, the chemical pesticide not only can protect the spirit of agriculture, but also can endanger the health of human beings and destroy the pestilence of the living environment of the human beings. With the sustainable development of agriculture and the continuous improvement of the living standard of people, the problems of pesticide pollution and food safety become the focus of people's attention, and at present, the production and sale of five high-toxicity organophosphorus pesticides such as methamidophos, parathion, methyl parathion, monocrotophos, phosphamidon and the like are limited by relevant measures in China, however, due to the long-term excessive use of the organophosphorus pesticides and the lack of understanding of farmers on national policies, the organophosphorus pesticides are still used in large quantities, so that the pollution of the organophosphorus pesticides becomes one of the most serious pollution sources in the agricultural production environment. Therefore, the treatment of the organophosphorus pesticide residue pollution becomes a serious part of the environmental pollution treatment work.
Soil remediation is a technical measure to restore normal function to contaminated soil. In the soil remediation industry, the existing soil remediation technologies can be more than one hundred, the common technologies can be more than ten, and the existing soil remediation technologies can be roughly divided into three methods, namely physical methods, chemical methods and biological methods. Since the 80 s in the 20 th century, many countries in the world, especially developed countries, have established and developed contaminated soil remediation and remediation programs, thus forming an emerging soil remediation industry.
The soil remediation method mainly comprises the following three steps: (1) performing bioremediation; (2) chemical repair; (3) and (5) physical repair. Wherein, the biological repair comprises phytoremediation, in-situ biological repair and ectopic biological repair, the chemical repair comprises in-situ chemical leaching, ectopic chemical leaching, solvent leaching technology, in-situ chemical oxidation, in-situ chemical reduction and reductive dechlorination and soil property improvement, and the physical repair comprises steam leaching technology, solidification repair technology, physical separation repair, vitrification repair, thermodynamic repair, thermal desorption repair, electrokinetic repair and soil replacement.
CN106824240B discloses a photocatalytic material for in-situ soil remediation and a preparation method thereof, wherein the material has a certain remediation capability for organic pesticides, but the soil remediation capability of the material is still difficult to meet the current ultrahigh standard requirement for soil remediation after evaluation.
Disclosure of Invention
In order to solve the problem that the soil remediation capability of a soil remediation agent in the prior art is still difficult to meet the ultrahigh standard requirement of soil remediation, the invention provides the following technical scheme:
a soil in-situ remediation method comprises the steps of mixing a prepared soil in-situ remediation agent with water and soil to be remediated under the illumination condition to remediate the soil, and measuring the soil remediation effect at intervals, wherein the dosage of the three components is determined according to the following proportion: water: the soil to be restored is 1 g: 12 ml: 10g of a mixture;
the soil in-situ remediation agent is prepared by the following method:
(1) the method comprises the following steps of (1) adopting dewatered sludge, waste clay, shale and quicklime according to the dry weight ratio of 3: 4: 9: 1, mixing, adding glass sand accounting for 2 percent of the total weight of the dry parts of the raw materials, adding water to 50 percent of the total weight of the raw materials, stirring to prepare particles with the particle size of 1-2 cm, and drying and sintering to obtain porous ceramsite;
(2) soaking the porous ceramsite obtained in the step (1) in 8% sulfuric acid, and cleaning and drying the porous ceramsite; respectively dissolving titanium sulfate, thiourea dioxide, erbium oxide and europium oxide in 0.3% dilute sulfuric acid, and uniformly stirring to prepare a modified film coating solution; mixing the ceramsite with the modified coating solution, adding urea, stirring, standing and aging; and drying to obtain the porous ceramsite coated with the photocatalytic film, wherein the weight ratio of titanium sulfate to thiourea dioxide to erbium oxide to europium oxide to the porous ceramsite to urea is 20: 10: 0.5: 0.5: 150: 60, the mass volume ratio of the porous ceramsite to the modified film coating solution is 150 g/L;
(3) and (3) sintering the porous ceramsite coated with the photocatalytic film obtained in the step (2) to obtain the soil in-situ restoration agent.
Preferably, the sintering treatment in step (1) is divided into two stages of sintering, wherein the first stage is sintered at 900 ℃ for 1h, and the second stage is sintered at 1100 ℃ for 1 h.
Preferably, the grain sizes of the dewatered sludge, the waste argil, the shale and the quick lime in the step (1) are 40-60 meshes.
Preferably, the drying temperature in step (1) is 200 ℃.
Preferably, the sulfuric acid soaking time in the step (2) is 3 h.
Preferably, the standing and aging time in the step (2) is 8 h.
Preferably, the sintering temperature in the step (3) is 700 ℃ and the sintering time is 4 h.
The technical scheme of the invention has the following beneficial effects:
(1) compared with the prior art in which a single metal element is used for doping, the light utilization effect of the material can be greatly improved by using the composite metal element for doping, so that the use effect of the soil remediation material is improved;
(2) the doped composite metal elements are not optional, and the technical effects obtained by the invention can not be obtained by doping all the composite metal elements, and a large number of experiments show that the doping combination of erbium oxide and europium oxide is more favorable for improving the light utilization effect of the material, and the effect is better than the combination of germanium oxide and europium oxide and the combination of erbium oxide and germanium oxide;
(3) preferably, compared with a single sintering system in the prior art, the sintering treatment of the porous ceramsite is performed by dividing the sintering treatment into two stages, namely sintering at 900 ℃ for 1h in the first stage and sintering at 1100 ℃ for 1h in the second stage, so that the sintering system is more beneficial to improving the structure of the porous ceramsite, further improving the film coating effect of the modified film coating solution and finally improving the using effect of the soil remediation material.
(4) The soil in-situ remediation method disclosed by the invention is high in remediation efficiency, suitable for various polluted soils, wide in raw material source, low in cost and simple to operate.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the following examples and comparative examples.
Example 1
A soil in-situ remediation method comprises the steps of mixing a prepared soil in-situ remediation agent with water and soil to be remediated under the illumination condition to remediate the soil, and measuring the soil remediation effect at intervals, wherein the dosage of the three components is determined according to the following proportion: water: the soil to be restored is 1 g: 12 ml: 10g of a mixture;
the soil in-situ remediation agent is prepared by the following method:
(1) the method comprises the following steps of (1) adopting dewatered sludge, waste clay, shale and quicklime according to the dry weight ratio of 3: 4: 9: 1, mixing, adding glass sand accounting for 2 percent of the total weight of the dry parts of the raw materials, adding water to 50 percent of the total weight of the raw materials, stirring to prepare particles with the particle size of 1-2 cm, and drying and sintering to obtain porous ceramsite;
(2) soaking the porous ceramsite obtained in the step (1) in 8% sulfuric acid, and cleaning and drying the porous ceramsite; respectively dissolving titanium sulfate, thiourea dioxide, erbium oxide and europium oxide in 0.3% dilute sulfuric acid, and uniformly stirring to prepare a modified film coating solution; mixing the ceramsite with the modified coating solution, adding urea, stirring, standing and aging; and drying to obtain the porous ceramsite coated with the photocatalytic film, wherein the weight ratio of titanium sulfate to thiourea dioxide to erbium oxide to europium oxide to the porous ceramsite to urea is 20: 10: 0.5: 0.5: 150: 60, the mass volume ratio of the porous ceramsite to the modified film coating solution is 150 g/L;
(3) and (3) sintering the porous ceramsite coated with the photocatalytic film obtained in the step (2) to obtain the soil in-situ restoration agent.
Wherein, the sintering treatment in the step (1) is divided into two stages of sintering, wherein, the first stage is sintered for 1h at 900 ℃, and the second stage is sintered for 1h at 1100 ℃; the particle sizes of the dewatered sludge, the waste argil, the shale and the quick lime in the step (1) are 40-60 meshes; in the step (1), the drying temperature is 200 ℃; the sulfuric acid soaking time in the step (2) is 3 h; standing and aging for 8 hours in the step (2); in the step (3), the sintering temperature is 700 ℃, and the sintering time is 4 h.
Example 2
A soil in-situ remediation method comprises the steps of mixing a prepared soil in-situ remediation agent with water and soil to be remediated under the illumination condition to remediate the soil, and measuring the soil remediation effect at intervals, wherein the dosage of the three components is determined according to the following proportion: water: the soil to be restored is 1 g: 12 ml: 10g of a mixture;
the soil in-situ remediation agent is prepared by the following method:
(1) the method comprises the following steps of (1) adopting dewatered sludge, waste clay, shale and quicklime according to the dry weight ratio of 3: 4: 9: 1, mixing, adding glass sand accounting for 2 percent of the total weight of the dry parts of the raw materials, adding water to 50 percent of the total weight of the raw materials, stirring to prepare particles with the particle size of 1-2 cm, and drying and sintering to obtain porous ceramsite;
(2) soaking the porous ceramsite obtained in the step (1) in 8% sulfuric acid, and cleaning and drying the porous ceramsite; respectively dissolving titanium sulfate, thiourea dioxide, erbium oxide and europium oxide in 0.3% dilute sulfuric acid, and uniformly stirring to prepare a modified film coating solution; mixing the ceramsite with the modified coating solution, adding urea, stirring, standing and aging; and drying to obtain the porous ceramsite coated with the photocatalytic film, wherein the weight ratio of titanium sulfate to thiourea dioxide to erbium oxide to europium oxide to the porous ceramsite to urea is 20: 10: 0.5: 0.5: 150: 60, the mass volume ratio of the porous ceramsite to the modified film coating solution is 150 g/L;
(3) and (3) sintering the porous ceramsite coated with the photocatalytic film obtained in the step (2) to obtain the soil in-situ restoration agent.
Wherein, the sintering treatment in the step (1) is one-stage sintering, namely sintering for 2 hours at 1000 ℃; the particle sizes of the dewatered sludge, the waste argil, the shale and the quick lime in the step (1) are 40-60 meshes; in the step (1), the drying temperature is 200 ℃; the sulfuric acid soaking time in the step (2) is 3 h; standing and aging for 8 hours in the step (2); in the step (3), the sintering temperature is 700 ℃, and the sintering time is 4 h.
Comparative example 1
A soil in-situ remediation method comprises the steps of mixing a prepared soil in-situ remediation agent with water and soil to be remediated under the illumination condition to remediate the soil, and measuring the soil remediation effect at intervals, wherein the dosage of the three components is determined according to the following proportion: water: the soil to be restored is 1 g: 12 ml: 10g of a mixture;
the soil in-situ remediation agent is prepared by the following method:
(1) the method comprises the following steps of (1) adopting dewatered sludge, waste clay, shale and quicklime according to the dry weight ratio of 3: 4: 9: 1, mixing, adding glass sand accounting for 2 percent of the total weight of the dry parts of the raw materials, adding water to 50 percent of the total weight of the raw materials, stirring to prepare particles with the particle size of 1-2 cm, and drying and sintering to obtain porous ceramsite;
(2) soaking the porous ceramsite obtained in the step (1) in 8% sulfuric acid, and cleaning and drying the porous ceramsite; respectively dissolving titanium sulfate, thiourea dioxide, germanium oxide and europium oxide in 0.3% dilute sulfuric acid, and uniformly stirring to prepare a modified film coating solution; mixing the ceramsite with the modified coating solution, adding urea, stirring, standing and aging; and drying to obtain the porous ceramsite coated with the photocatalytic film, wherein the weight ratio of titanium sulfate to thiourea dioxide to germanium oxide to europium oxide to the porous ceramsite to urea is 20: 10: 0.5: 0.5: 150: 60, the mass volume ratio of the porous ceramsite to the modified film coating solution is 150 g/L;
(3) and (3) sintering the porous ceramsite coated with the photocatalytic film obtained in the step (2) to obtain the soil in-situ restoration agent.
Wherein, the sintering treatment in the step (1) is one-stage sintering, namely sintering for 2 hours at 1000 ℃; the particle sizes of the dewatered sludge, the waste argil, the shale and the quick lime in the step (1) are 40-60 meshes; in the step (1), the drying temperature is 200 ℃; the sulfuric acid soaking time in the step (2) is 3 h; standing and aging for 8 hours in the step (2); in the step (3), the sintering temperature is 700 ℃, and the sintering time is 4 h.
Comparative example 2
A soil in-situ remediation method comprises the steps of mixing a prepared soil in-situ remediation agent with water and soil to be remediated under the illumination condition to remediate the soil, and measuring the soil remediation effect at intervals, wherein the dosage of the three components is determined according to the following proportion: water: the soil to be restored is 1 g: 12 ml: 10g of a mixture;
the soil in-situ remediation agent is prepared by the following method:
(1) the method comprises the following steps of (1) adopting dewatered sludge, waste clay, shale and quicklime according to the dry weight ratio of 3: 4: 9: 1, mixing, adding glass sand accounting for 2 percent of the total weight of the dry parts of the raw materials, adding water to 50 percent of the total weight of the raw materials, stirring to prepare particles with the particle size of 1-2 cm, and drying and sintering to obtain porous ceramsite;
(2) soaking the porous ceramsite obtained in the step (1) in 8% sulfuric acid, and cleaning and drying the porous ceramsite; respectively dissolving titanium sulfate, thiourea dioxide, erbium oxide and germanium oxide in 0.3% dilute sulfuric acid, and uniformly stirring to prepare a modified film coating solution; mixing the ceramsite with the modified coating solution, adding urea, stirring, standing and aging; and drying to obtain the porous ceramsite coated with the photocatalytic film, wherein the weight ratio of titanium sulfate to thiourea dioxide to erbium oxide to germanium oxide to the porous ceramsite to urea is 20: 10: 0.5: 0.5: 150: 60, the mass volume ratio of the porous ceramsite to the modified film coating solution is 150 g/L;
(3) and (3) sintering the porous ceramsite coated with the photocatalytic film obtained in the step (2) to obtain the soil in-situ restoration agent.
Wherein, the sintering treatment in the step (1) is one-stage sintering, namely sintering for 2 hours at 1000 ℃; the particle sizes of the dewatered sludge, the waste argil, the shale and the quick lime in the step (1) are 40-60 meshes; in the step (1), the drying temperature is 200 ℃; the sulfuric acid soaking time in the step (2) is 3 h; standing and aging for 8 hours in the step (2); in the step (3), the sintering temperature is 700 ℃, and the sintering time is 4 h.
In order to verify the technical effects of examples 1-2 and comparative examples 1-2, the soil in-situ remediation agents of examples 1-2 and comparative examples 1-2 were tested: taking 500g of 4 parts of contaminated soil sample with the dimethoate pesticide content of 4%, respectively weighing 50g of the photocatalytic materials prepared in the examples 1-2 and the comparative examples 1-2, adding 600ml of water, carrying out a photodegradation experiment under simulated illumination, wherein the experiment time is 5 hours, and the dimethoate removal rate at the end of the experiment is adopted for representation, and the results are as follows:
| numbering | Sintering process in step (1) | Doped phase | Removal rate of dimethoate |
| Example 1 | Sintering at 900 deg.C for 1h, and sintering at 1100 deg.C for 1h | Erbium oxide and europium oxide | 99.15％ |
| Example 2 | Sintering at 1000 ℃ for 2h | Erbium oxide and europium oxide | 97.54％ |
| Comparative example 1 | Sintering at 1000 ℃ for 2h | Germanium oxide and europium oxide | 95.63％ |
| Comparative example 2 | Sintering at 1000 ℃ for 2h | Erbium oxide and germanium oxide | 93.82％ |
The results show that (1) compared with the prior art (CN106824240B) in which a single metal element is used for doping, the light utilization effect of the material can be greatly improved by using the composite metal element for doping, and the use effect of the soil remediation material is further improved; (2) the doped composite metal elements are not optional, and the technical effects obtained by the invention can not be obtained by doping all the composite metal elements, and a large number of experiments show that the doping combination of erbium oxide and europium oxide is more favorable for improving the light utilization effect of the material, and the effect is better than the combination of germanium oxide and europium oxide and the combination of erbium oxide and germanium oxide; (3) preferably, compared with a single sintering system in the prior art, the sintering treatment of the porous ceramsite is divided into two stages of sintering (the first stage is sintered at 900 ℃ for 1h, and the second stage is sintered at 1100 ℃ for 1h), so that the structure of the porous ceramsite is improved, the film coating effect of the modified film coating solution is further improved, and the use effect of the soil remediation material is finally improved.
Claims (6)
1. The soil in-situ remediation method is characterized in that the prepared soil in-situ remediation agent is mixed with water and soil to be remediated to carry out soil remediation under the illumination condition, and the soil remediation effect is measured at intervals, wherein the dosage of the three components is determined according to the following proportion: water: the soil to be restored is 1 g: 12 ml: 10g of a mixture;
the soil in-situ remediation agent is prepared by the following method:
(1) the method comprises the following steps of (1) adopting dewatered sludge, waste clay, shale and quicklime according to the dry weight ratio of 3: 4: 9: 1, mixing, adding glass sand accounting for 2 percent of the total weight of the dry parts of the raw materials, adding water to 50 percent of the total weight of the raw materials, stirring to prepare particles with the particle size of 1-2 cm, and drying and sintering to obtain porous ceramsite;
(2) soaking the porous ceramsite obtained in the step (1) in 8% sulfuric acid, and cleaning and drying the porous ceramsite; respectively dissolving titanium sulfate, thiourea dioxide, erbium oxide and europium oxide in 0.3% dilute sulfuric acid, and uniformly stirring to prepare a modified film coating solution; mixing the porous ceramsite with the modified coating solution, adding urea, stirring, standing and aging; and drying to obtain the porous ceramsite coated with the photocatalytic film, wherein the weight ratio of titanium sulfate to thiourea dioxide to erbium oxide to europium oxide to the porous ceramsite to urea is 20: 10: 0.5: 0.5: 150: 60, the mass volume ratio of the porous ceramsite to the modified film coating solution is 150 g/L;
(3) sintering the porous ceramsite coated with the photocatalytic film obtained in the step (2) to obtain a soil in-situ restoration agent;
the sintering treatment in the step (1) is divided into two stages of sintering, wherein the first stage is sintered for 1h at 900 ℃, and the second stage is sintered for 1h at 1100 ℃.
2. The soil in-situ remediation method of claim 1, wherein the particle size of the dewatered sludge, spent bleaching earth, shale and quicklime in the step (1) is 40-60 meshes.
3. The soil in-situ remediation method of claim 1, wherein the drying temperature in step (1) is 200 ℃.
4. The soil in-situ remediation method of claim 1, wherein the sulfuric acid soaking time in step (2) is 3 hours.
5. The in situ soil remediation method of claim 1 wherein the standing aging time in step (2) is 8 hours.
6. The soil in-situ remediation method of claim 1, wherein the sintering temperature in step (3) is 700 ℃ and the sintering time is 4 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910952788.9A CN110576034B (en) | 2019-10-09 | 2019-10-09 | Soil in-situ remediation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910952788.9A CN110576034B (en) | 2019-10-09 | 2019-10-09 | Soil in-situ remediation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110576034A CN110576034A (en) | 2019-12-17 |
| CN110576034B true CN110576034B (en) | 2020-06-30 |
Family
ID=68814447
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910952788.9A Active CN110576034B (en) | 2019-10-09 | 2019-10-09 | Soil in-situ remediation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110576034B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1683074A (en) * | 2005-03-11 | 2005-10-19 | 南京大学 | Process for preparing visible light responding photo catalytic film layer |
| DE60024893D1 (en) * | 1999-09-07 | 2006-01-19 | Glaxosmithkline Biolog Sa | Vaccine against HPV |
| CN101003020A (en) * | 2007-01-11 | 2007-07-25 | 南京大学 | Sensitized titanium oxide and zinc sulfide visible light responsing photocalalyst, and its preparing method |
| CN101514112A (en) * | 2009-03-27 | 2009-08-26 | 贵州省建筑设计研究院 | Ceramic aggregate biological filler and preparation method thereof |
| CN101624294A (en) * | 2009-08-14 | 2010-01-13 | 准格尔旗粉煤灰煤矸石研发中心 | Porcelain granule and preparation method thereof |
| CN102204566A (en) * | 2010-03-30 | 2011-10-05 | 索尼公司 | Fungicide, photo catalytic composite material, adsorbent and depurative |
| CN102272061A (en) * | 2008-11-11 | 2011-12-07 | 莫利康普矿物有限责任公司 | Target material removal using rare earth metals |
| CN106824240A (en) * | 2016-12-30 | 2017-06-13 | 上海立昌环境工程股份有限公司 | A kind of soil in-situ repairs catalysis material and preparation method thereof |
| CN108059480A (en) * | 2017-12-22 | 2018-05-22 | 承德人和矿业有限责任公司 | A kind of illite function haydite and preparation method thereof |
-
2019
- 2019-10-09 CN CN201910952788.9A patent/CN110576034B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE60024893D1 (en) * | 1999-09-07 | 2006-01-19 | Glaxosmithkline Biolog Sa | Vaccine against HPV |
| CN1683074A (en) * | 2005-03-11 | 2005-10-19 | 南京大学 | Process for preparing visible light responding photo catalytic film layer |
| CN101003020A (en) * | 2007-01-11 | 2007-07-25 | 南京大学 | Sensitized titanium oxide and zinc sulfide visible light responsing photocalalyst, and its preparing method |
| CN102272061A (en) * | 2008-11-11 | 2011-12-07 | 莫利康普矿物有限责任公司 | Target material removal using rare earth metals |
| CN101514112A (en) * | 2009-03-27 | 2009-08-26 | 贵州省建筑设计研究院 | Ceramic aggregate biological filler and preparation method thereof |
| CN101624294A (en) * | 2009-08-14 | 2010-01-13 | 准格尔旗粉煤灰煤矸石研发中心 | Porcelain granule and preparation method thereof |
| CN102204566A (en) * | 2010-03-30 | 2011-10-05 | 索尼公司 | Fungicide, photo catalytic composite material, adsorbent and depurative |
| CN106824240A (en) * | 2016-12-30 | 2017-06-13 | 上海立昌环境工程股份有限公司 | A kind of soil in-situ repairs catalysis material and preparation method thereof |
| CN108059480A (en) * | 2017-12-22 | 2018-05-22 | 承德人和矿业有限责任公司 | A kind of illite function haydite and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110576034A (en) | 2019-12-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102764759B (en) | Remediation agent for treating arsenic contaminated soil and usage of remediation agent | |
| CN107652976A (en) | A kind of mineral base soil-repairing agent and preparation method thereof | |
| CN109731901B (en) | Stabilizing and repairing agent and repairing method for fluoride-contaminated soil | |
| CN105950165B (en) | A kind of chromium-polluted soil repairs modifying agent and its restorative procedure | |
| Liu et al. | Effects of different concentrations of mercury on accumulation of mercury by five plant species | |
| CN107297386B (en) | Mechanochemical reduction remediation method for hexavalent chromium contaminated soil | |
| CN105583222B (en) | A kind of restorative procedure of cadmium zinc heavy-metal contaminated soil | |
| Yan et al. | Evaluation of hydroxyapatite derived from flue gas desulphurization gypsum on simultaneous immobilization of lead and cadmium in contaminated soil | |
| CN106424119A (en) | Repair agent used for treating chromium-contaminated soil and use method of repair agent | |
| CN104525123A (en) | Porous composite material for removing heavy metals in soil and preparation method thereof | |
| CN104927870A (en) | Novel material for repairing heavy metal Cr-Pb-Cd polluted soil, and preparation method and application method thereof | |
| CN106903150A (en) | Heavy metal contaminated soil remediation material and application method thereof | |
| Cui et al. | Effects of hydroxyapatite on leaching of cadmium and phosphorus and their availability under simulated acid rain | |
| CN109382396A (en) | One kind is for handling antimony pollution soil remediation medicament and its application method | |
| CN109370596A (en) | A kind of in-situ passivation the reparation medicament, preparation method and application of cadmium arsenic combined pollution agricultural land soil | |
| CN106623379A (en) | Resource recycling method of construction waste and repairing agent for heavy-metal-polluted soil | |
| CN109621909A (en) | A kind of medical stone sulfydryl renovation agent and preparation method thereof for administering Soil Mercury Pollution | |
| CN109652079A (en) | A kind of flyash modified method and application for mercury pollution original position soil reparation | |
| CN104492797B (en) | A kind of restorative procedure of heavy metal pollution acid ground | |
| CN110576034B (en) | Soil in-situ remediation method | |
| CN110652980B (en) | Soil in-situ remediation agent | |
| CN111822497A (en) | Remediation device system and method for soil organic matter and heavy metal pollution | |
| CN103028598A (en) | Application of polyacrylamide in removal of soil heavy metal zinc pollution | |
| CN105855286A (en) | Oxidation removing method for polycyclic aromatic hydrocarbon in soil through Fenton reagent bag | |
| CN108620433A (en) | A kind of nickel contamination soil remediation material and the preparation method and application thereof |
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 | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20200603 Address after: Room 1111, floor 10, No. 8, Haidian North 2nd Street, Haidian District, Beijing 100080 Applicant after: BEIJING SUNWARD ECOLOGICAL ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Address before: 266000 6-5 Xiaolai Road, Hetoudian Town, Laixi City, Qingdao City, Shandong Province Applicant before: Laixi Xinhe engineering technical service center |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |