CN108892342B - A kind of preparation method of composite material for heavy metal immobilization in water body sediment - Google Patents
A kind of preparation method of composite material for heavy metal immobilization in water body sediment Download PDFInfo
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 239000013049 sediment Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 235000014676 Phragmites communis Nutrition 0.000 claims abstract description 37
- 235000013162 Cocos nucifera Nutrition 0.000 claims abstract description 30
- 244000060011 Cocos nucifera Species 0.000 claims abstract description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000002791 soaking Methods 0.000 claims abstract description 17
- 230000007935 neutral effect Effects 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 239000004343 Calcium peroxide Substances 0.000 claims abstract description 8
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000019402 calcium peroxide Nutrition 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 4
- 230000003100 immobilizing effect Effects 0.000 claims abstract 4
- 244000273256 Phragmites communis Species 0.000 claims abstract 3
- 238000005406 washing Methods 0.000 claims description 15
- 239000012153 distilled water Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 abstract description 17
- 230000005012 migration Effects 0.000 abstract description 4
- 238000013508 migration Methods 0.000 abstract description 4
- 230000004913 activation Effects 0.000 abstract description 2
- 238000005728 strengthening Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 28
- 238000001179 sorption measurement Methods 0.000 description 25
- 150000002500 ions Chemical class 0.000 description 13
- 238000012360 testing method Methods 0.000 description 7
- 238000010000 carbonizing Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000010802 sludge Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 230000006740 morphological transformation Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000005067 remediation Methods 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000004166 bioassay Methods 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/008—Sludge treatment by fixation or solidification
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/06—Treatment of sludge; Devices therefor by oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明提供一种水体底泥重金属固定用复合材料的制备方法，步骤如下：（1）芦苇生物炭制备：将收割的芦苇用15%H3PO4浸泡，浸泡后烘干，将处理后的芦苇置于管式马弗炉中，并以200 mL/min的速度通入氮气，炭化6h，凉至室温后水洗至中性。（2）椰壳生物炭制备：将洗涤、粉碎的椰壳用30%H3PO4浸泡，浸泡烘干后，将处理后的椰壳置于管式马弗炉中，并以200 mL/min的速度通入氮气，炭化6h，凉至室温后水洗至中性。（3）复合材料的制备：将过氧化钙粉末、椰壳生物炭、芦苇生物炭进行混合，获得复合材料。该复合材料通过强化底泥中重金属活化，再通过生物炭固定，降低重金属迁移能力及其生物有效性。The present invention provides a method for preparing a composite material for immobilizing heavy metals in water body sediment. The steps are as follows: (1) Reed biochar preparation: soaking the harvested reeds with 15% H 3 PO 4 , drying after soaking, The reed was placed in a tubular muffle furnace, and nitrogen was introduced at a rate of 200 mL/min, carbonized for 6 h, cooled to room temperature, and washed with water until neutral. (2) Coconut shell biochar preparation: soak the washed and pulverized coconut shells with 30% H 3 PO 4 , soak and dry them, place the treated coconut shells in a tubular muffle furnace, and add 200 mL/ Nitrogen was introduced at the speed of min, carbonized for 6 h, cooled to room temperature and washed with water until neutral. (3) Preparation of composite material: calcium peroxide powder, coconut shell biochar, and reed biochar are mixed to obtain a composite material. The composite material reduces the migration ability and bioavailability of heavy metals by strengthening the activation of heavy metals in the sediment, and then immobilizing them by biochar.
Description
Technical Field
The invention belongs to the technical field of environmental management, and particularly relates to a preparation method of a composite material for fixing heavy metals in water body sediment.
Background
At present, although the quality of surface water body is gradually recovered along with the implementation of sewage interception and basin comprehensive control measures, sediment is the main accumulation place of pollutants and can be released under proper environmental conditions, so that the overlying water is polluted.
The method for controlling heavy metals in the sediment mainly comprises the sediment in-situ remediation technology and sediment dredging. Among them, the in-situ remediation technology of the bottom mud has become an important research direction due to its low investment, simple operation, etc., and has application examples. The in-situ chemical treatment technology is widely applied and is mainly completed by the adsorption of materials on heavy metal ions. Therefore, the technology has two cores, namely, the adsorption speed is high, and the capacity is large; secondly, the adsorbed heavy metal ions are immobilized.
At present, inorganic adsorption materials are mainly used as materials for controlling heavy metal release. The inorganic adsorption material is a natural inorganic compound with a porous structure and a large specific surface area, generally has ion exchange capacity, is characterized by wide sources, low cost and high adsorption capacity, and is generally classified into carbonaceous materials, mineral materials, metal oxides and the like. The carbonaceous adsorbent includes activated carbon, carbon nanotubes, and the like. Although the carbonaceous adsorption material has a large specific surface area and excellent adsorption performance after modification, the application of the carbonaceous adsorption material in the field of heavy metal ion adsorption is limited by high preparation and regeneration cost. The common mineral adsorbing materials include silica gel, bentonite, zeolite, etc., and are paid great attention by researchers due to wide sources, various types and low price. The mineral material has exchangeable cations, surface negative charges, surface active hydroxyl groups, larger specific surface area, pore channel structure and the like, and can be used for adsorbing heavy metal ions. Untreated mineral materials generally have a low adsorption capacity. The metal oxides such as iron oxide, aluminum oxide, manganese oxide and the like have special surface interface characteristics and reactivity and are commonly used for removing heavy metal ions in water. The surface complexation theory holds that the degree of participation of the surface hydroxyl groups of the metal oxide adsorption material in ligand exchange and complexation reactions is one of the main factors determining the adsorption performance of the material.
Although inorganic adsorption materials have many advantages in application, the typical problem still remains that these materials have good ion adsorption performance, and if they are used to cover substrate sludge so as to control the release of heavy metal ions in the substrate sludge, heavy metals of different forms in the substrate sludge need to be converted into ions to be adsorbed and fixed. Therefore, various adsorption materials are passive adsorption materials at present, and the heavy metals in the sediment cannot be actively and effectively controlled.
Disclosure of Invention
The technical problem to be solved is as follows: aiming at the defects of the existing inorganic adsorption material, the invention provides a preparation method of a composite material for fixing heavy metal in water body sediment, the prepared composite material can effectively strengthen the migration capability of heavy metal in the sediment, and strengthen the migration and fixation of the heavy metal to the adsorption material, namely, the material has the characteristics of active activation and adsorption by promoting the form transformation of the heavy metal and actively inducing the heavy metal ions to transfer to the adsorption material and be fixed, thereby improving the permanent burying capability of the heavy metal ions.
The technical scheme is as follows: a preparation method of a composite material for fixing heavy metals in water body sediment comprises the following steps:
the first step is as follows: preparing reed biochar: cutting the harvested reed into 1-2 cm long, and drying at 100 deg.C for 24 hr; then use15% H3PO4Soaking, and placing in oven at 30-40 deg.C for 12 hr; after soaking, taking out the reed, drying the reed in a drying oven at 30-40 ℃ for 24h, and taking out for later use; preheating the tubular muffle furnace for 30min, heating to 400 ℃ at the speed of 5 ℃/min, placing the treated reed in the tubular muffle furnace, introducing nitrogen at the speed of 200 mL/min, carbonizing for 6h, cooling to room temperature, and washing with distilled water until the washing liquid is neutral.
The second step is that: preparing coconut shell biochar: drying the washed and crushed coconut shells at 100 ℃ for 24 h; then using 30% H3PO4Soaking, and placing in oven at 30-40 deg.C for 12 hr; after soaking, taking out, drying in a drying oven at 30-40 ℃ for 24h, and taking out for later use; preheating a tubular muffle furnace for 30min, heating to 400 ℃ at a speed of 5 ℃/min, placing the treated coconut shell in the tubular muffle furnace, introducing nitrogen at a speed of 200 mL/min, carbonizing for 6h, cooling to room temperature, and washing with distilled water until the washing liquid is neutral.
The third step: preparing a composite material: calcium peroxide powder (purity, 75%), coconut shell biochar and reed biochar are mixed according to the mass ratio of 5: 2: 3, mixing to obtain the composite material.
Preferably, in the first step, the reaped reed is cut into 1-2 cm long and dried for 24h at 100 ℃; then using 15% H3PO4Soaking, and placing in oven at 30-40 deg.C for 12 hr; after soaking, taking out the reed, drying the reed in a drying oven at 30-40 ℃ for 24h, and taking 100g of the treated reed for later use; preheating the tubular muffle furnace for 30min, heating to 400 ℃ at the speed of 5 ℃/min, placing the treated reed in the tubular muffle furnace, introducing nitrogen at the speed of 200 mL/min, carbonizing for 6h, cooling to room temperature, and washing with distilled water until the washing liquid is neutral.
Preferably, in the second step, the washed and crushed coconut shells are dried for 24 hours at 100 ℃; then using 30% H3PO4Soaking, and placing in oven at 30-40 deg.C for 12 hr; after soaking, taking out, drying in an oven at 30-40 ℃ for 24h, and taking 100g of treated coconut shells for later use; preheating a tubular muffle furnace for 30min, heating to 400 ℃ at a speed of 5 ℃/min, and treating the coconutPlacing the shell in a tubular muffle furnace, introducing nitrogen at the speed of 200 mL/min, carbonizing for 6h, cooling to room temperature, and washing with distilled water until the washing liquid is neutral.
Has the advantages that: the preparation method of the composite material for fixing the heavy metal in the water body sediment, provided by the invention, has the following advantages:
1. the composite material for fixing the heavy metal in the water body sediment, which is prepared by the preparation method, has the characteristics of promoting the morphological transformation of the heavy metal, and actively inducing the heavy metal ions to migrate to the adsorption material and fix.
2. The covering material contains calcium peroxide, and can strengthen the generation of hydroxyl free radicals through Fenton-like reaction, promote heavy metals in the bottom mud to exist in an acid soluble state and a reducible state, and strengthen the migration capacity of heavy metal ions.
3. The preparation method has the advantages of wide material source, simple and easy preparation, and waste utilization of coconut shell and reed.
Detailed Description
Example 1
The preparation method of the composite material for fixing the heavy metal in the water body sediment comprises the following steps:
(1) preparation of reed biochar
Firstly, cutting the harvested fresh reed into 1 cm long, and drying for 24h at 100 ℃; weighing 400g of dried reed, placing in a 2L glass container, adding 1L15% H3PO4Submerging the reed, and soaking in an oven at 40 ℃ for 12 h; after soaking, taking out the reed, drying the reed in a drying oven at 40 ℃ for 24 hours, and taking out for later use; preheating the tubular muffle furnace for 30min, heating to 400 ℃ at the speed of 5 ℃/min, placing the treated reed in the tubular muffle furnace, introducing nitrogen at the speed of 200 mL/min, carbonizing for 6h, cooling to room temperature, and washing with distilled water until the washing liquid is neutral.
(2) Preparation of coconut shell biochar
Firstly, drying the washed and crushed coconut shells at 100 ℃ for 24 hours; weighing 400g of dried coconut shell, placing in a 2L glass container, adding 1L30% H3PO4Immersing coconut shell, and placing in ovenSoaking at 40 deg.C for 12 h; after soaking, taking out the coconut shells, drying the coconut shells in a drying oven at 40 ℃ for 24 hours, and taking out for later use; preheating a tubular muffle furnace for 30min, heating to 400 ℃ at a speed of 5 ℃/min, placing the treated coconut shell in the tubular muffle furnace, introducing nitrogen at a speed of 200 mL/min, carbonizing for 6h, cooling to room temperature, and washing with distilled water until the washing liquid is neutral.
(3) Preparation of composite material for fixing heavy metal in water body sediment
Mixing 500g of calcium peroxide powder, 200g of coconut shell biochar and 300g of reed biochar, and stirring and mixing for 5min in a stirrer with the rotating speed of 100rpm to obtain the composite material.
Example 2
The material obtained in example 1 was used to perform a heavy metal morphological transformation test and a heavy metal ion adsorption test, and the specific steps were as follows:
test of influence of calcium peroxide on transformation of heavy metal form
Taking black and odorous bottom mud of a certain river in Suzhou city, adding 200g of black and odorous bottom mud into 3 serum bottles respectively, adding 1g of calcium peroxide powder, uniformly mixing, and then adding 100mL of river overlying water into the mixture respectively. Standing in dark for 30 d.
Removing the water by siphonage, taking out the bottom sludge, drying, grinding, and sieving with a 100-mesh sieve for later use.
The results show that: after calcium oxide oxidation treatment, the content of the heavy metals in the bottom mud in a less stable state is obviously increased, for example, Cr is increased to 30.61%. In addition, bioavailabilities of Cr are varied, wherein bioavailabilities of Cr are increased by 1-2 times. This also indicates that calcium peroxide activates heavy metals.
The content of acid volatile sulfide in the bottom mud is 1100mg/Kg before the treatment by calcium oxide, and the acid volatile sulfide can hardly be detected after the treatment.
Adsorption of heavy metal by coconut shell charcoal and reed charcoal mixture
A constant temperature oscillator was used as the test apparatus.
The coconut shell biochar and the reed biochar are prepared according to the following steps of 2: mixing at a ratio of 3.
Respectively adding 0.5g of coconut shell biochar and reed biochar mixture and 100mLK into a series of 100mL conical flasks2Cr2O7The initial concentrations of the solution and the Cr (VI) solution are respectively 10, 20, 40, 60, 80, 100, 120, 160 and 180 mg/L, the solution is rotated at 250 rpm under the condition of (25 +/-1) DEG C, is shaken at constant temperature for 24h, is centrifuged (3500 rpm and 20 min), is filtered by 0.45 mu m, the concentration (equilibrium concentration) of Cr (VI) is measured, and the adsorption capacity of the coconut shell biochar and the reed biochar to the Cr (VI) is calculated according to the difference between the initial concentration and the equilibrium concentration.
The result shows that the maximum adsorption amount of the mixture of the coconut shell biochar and the reed biochar to Cr (VI) is up to 6780 mg/kg. The specific surface area of the material is measured to reach 1711 m2(ii)/g, pore volume 0.7757 cc/g, mesopore specific surface area 1513 m2/g。
Example 3
The composite material for fixing heavy metal in the water body sediment, which is prepared in the example 1, is used for injection test of the polluted sediment of a certain river channel in Suzhou.
The river reach water body is in a black and odorous state. The polluted bottom mud (the content of Cr (VI) in the bottom mud is 100.5 mg/kg, the content of organic matters is 24.9 percent) is dug and sent to a laboratory, and the polluted bottom mud is flatly paved at the bottoms of 2 experimental devices (0.6 m multiplied by 1.2 m) and is paved with the thickness of 50 cm. Weighing 800g of the composite material, adding the composite material into a plastic pipe with the diameter of 10cm, inserting the plastic pipe into the center of the sediment of the experimental device, slowly pulling out the plastic pipe, keeping the composite material in the sediment, and taking the other experimental device as a control test. Then, the river water was added to the river water at a depth of 50 cm.
In 10d, when no material system is injected, the content of Cr (VI) in the water body reaches 10.6 mu g/L, and then the water body is always kept in a high-position state; the injection composite material system, 50 days, the Cr (VI) in the water body is only 0.21 mu g/L, 100 days, and the Cr (VI) in the water body is only 0.35 mu g/L.
The test was completed at 100d and analysis found that the acid volatilisable sulphides in the sludge remained at a level of 1100mg/Kg without any injection of the material system, whereas the acid volatilisable sulphides in the sludge were barely detectable with the injection of the composite system. Without any material system injected, the bioassays were slightly increased. And the bioassability of the injected composite material system is obviously reduced.
While the embodiments of the present invention have been described in detail, those skilled in the art will recognize that the embodiments of the present invention can be practiced without departing from the spirit and scope of the claims.
Claims (4)
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| CN106165585A (en) * | 2016-06-16 | 2016-11-30 | 中国农业科学院农业资源与农业区划研究所 | The method utilizing charcoal preventing and treating region, Rice-rape rotation farmland phosphorus loss |
| CN106475405A (en) * | 2016-11-30 | 2017-03-08 | 中冶华天南京工程技术有限公司 | Using charcoal and the method for chelating agent fortification of plants restoration of soil polluted by heavy metal |
| CN106833657A (en) * | 2016-11-29 | 2017-06-13 | 中冶华天工程技术有限公司 | Combined contamination soil renovation agent and application process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106165585A (en) * | 2016-06-16 | 2016-11-30 | 中国农业科学院农业资源与农业区划研究所 | The method utilizing charcoal preventing and treating region, Rice-rape rotation farmland phosphorus loss |
| CN106833657A (en) * | 2016-11-29 | 2017-06-13 | 中冶华天工程技术有限公司 | Combined contamination soil renovation agent and application process |
| CN106475405A (en) * | 2016-11-30 | 2017-03-08 | 中冶华天南京工程技术有限公司 | Using charcoal and the method for chelating agent fortification of plants restoration of soil polluted by heavy metal |
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