CN104307858A - Ecological bag for in situ curing and removing of soil heavy mental and application method - Google Patents

Ecological bag for in situ curing and removing of soil heavy mental and application method Download PDF

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Publication number
CN104307858A
CN104307858A CN201410611997.4A CN201410611997A CN104307858A CN 104307858 A CN104307858 A CN 104307858A CN 201410611997 A CN201410611997 A CN 201410611997A CN 104307858 A CN104307858 A CN 104307858A
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soil
rhodamine
bag
heavy metal
biomass
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CN201410611997.4A
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CN104307858B (en
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李坤权
王效华
潘根兴
徐恩兵
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Nanjing Agricultural University
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Nanjing Agricultural University
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Abstract

The invention provides an ecological bag for in situ curing and removing of soil heavy mental lead, cadmium and chromium. The ecological bag comprises two layers of packaging bags, wherein rhodamine 6G modified biomass charcoal high polymer material is contained in the inner layer polypropylene fiber geotechnical cloth bag; the inner and outer layers of packaging bags are respectively made of polypropylene fiber geotechnical cloth and dacron geotechnical cloth; the outer layer dacron geotechnical cloth covers the inner layer polypropylene fiber geotechnical cloth; a high polymer material contained in the inner layer takes biomass straws and rhodamine 6G as a precursor; the ecological bag is prepared through steps of carbonization, oxidation, glycidyl and polymerization, is rich in pore structures and polyamine molecule, and has high adsorptive property to lead, cadmium and chromium ion. The ecological bag overcomes the defects that the traditional in situ curing and passivating technology only reduces the bioavailability of heavy metal, but the heavy metal still exists in soil, and the risk of secondary pollution exists; materials for preparation come from biomass; the ecological bag is green and environmental-friendly, simple in technology, and high in efficiency of removal of lead, cadmium and chromium in the soil, meets development requirements of circular economy, and has scale production and application prospects.

Description

A kind of in-situ solidifying removes ecology bag and the application process of heavy metal-polluted soil
Technical field
The invention belongs to safety of soil environment and resource reutilization technical field, relate to a kind of in-situ solidifying-remove heavy metal-polluted soil lead, cadmium, the ecology bag of chromium and application process.
Background technology
Soil is one of mankind's Main Natural Resources of depending on for existence, but along with the continuous expansion of China's industrial and agricultural production scale, heavy metal pollution of soil is day by day serious.Heavy metal pollution of soil has disguise, cumulative bad and transitivity, causes multiple harm to health, economical production, ecological environment etc., has become the key factor of restriction China's sustainable development and construction of harmonious society.Have investigation display, China has reached 2,000 ten thousand hectares by the cultivated area of heavy metal pollution, accounts for 1/6 of national total area under cultivation.Wherein, by mining area contaminated land 2,000,000 hectares, about 5,000,000 hectares, oil pollution soil, solid waste is stacked and is polluted about 50,000 hectares, and " three industrial wastes " pollute and plough nearly 1,000 ten thousand hectares, and polluted agricultural land area reaches more than 330 ten thousand hectares.For this reason, research remediation of heavy metal-contaminated soil, effectively administers heavy metal pollution of soil, ensures the sustainable use of soil resource, becomes problem demanding prompt solution.
At present, the heavy metal pollution of soil original position Treatment process that exceeds standard mainly fixes passivating technique and microorganism remediation technology.Soil fixing technology points in soil to add fixative, regulates and change the chemical form of heavy metal contaminants in soil and occurrence status, thus reduce biological effectiveness and the animal migration of heavy metal, reduce the absorption of plant heavy metal.In view of heavy metal pollution of soil, usually to relate to area very large, the high cost of various engineering reclamation activities, and original position soil immobilization technology has the features such as economical and efficient, easy to operate, effect is quick, there is in soil controlling area-source pollution field unique advantage, meet the needs of China's sustainable agriculture development, be just used widely in contaminated soil is administered.But no matter use which kind of fixative, finally by absorption passivation heavy metal all stay in soil, and may along with the change of environmental condition not, biological effectiveness may be recovered again, causes soil secondary pollution.
The in-situ solidifying that the present invention proposes removes the bag that is made up of the polypropylene spunbond non-woven fabrics of outer field terylene geotextiles, internal layer of ecology bag of heavy metal-polluted soil lead, cadmium, chromium, and the rhodamine 6G modified biomass based high molecular material be loaded in internal layer polypropylene spunbond non-woven fabrics forms jointly.Be loaded on biomass carbon macromolecular material in cloth bag with agricultural biomass stalk and rhodamine 6G for presoma, obtained by step preparations such as charing, activation, carboxylated and rhodamine 6G amination modifyings, be rich in pore structure and polyamine molecule, there is stronger absorption property to lead ion, effectively can adsorb heavy metal lead, cadmium, chromium in fixing soil.Bag outer field terylene geotextiles has certain uv-resistant performance, imposes in soil the ecological time limit that can reach and need to use.
A kind of in-situ solidifying that the present invention proposes removes heavy metal-polluted soil lead, cadmium, the ecology bag of chromium and application process, it is characterized in that:
A), in-situ solidifying removes the composition of ecology bag of heavy metal-polluted soil lead, cadmium, chromium: comprise bag and the rhodamine 6G modified biomass based high molecular material be loaded in bag is formed jointly.Bag is covered on polypropylene spunbond non-woven fabrics by the terylene geotextiles of anti-U V corrosive nature and is made; Rhodamine 6G modified biomass based high molecular material is loaded in the polypropylene spunbond non-woven fabrics in bag.
B), the preparation process of rhodamine 6G modified biomass based high molecular material: ripe agricultural biomass powder of straw is added the multiporous biological matter charcoal that phosphoric acid heat-activated in blanket of nitrogen prepares the oxygen-containing functional groups such as rich surface hydroxyl, carboxylic acid group, get 5 grams of above-mentioned biomass carbons add 10 ~ 50% of 100 ~ 500ml nitric acid stir 1 ~ 10 hour, after after completion of the reaction product washing and filtering being dried, be distributed in 50 ~ 200ml toluene and 0.5 ~ 2.0g rhodamine 6G, stir, add 5 grams of N, N '-dicyclohexylcarbodiimide, back flow reaction 8 ~ 48 hours.Filter product, clean, dry and to obtain novel rhodamine 6G modified biomass base charcoal macromolecular material.
C), the in-situ solidifying of heavy metal-polluted soil: the ecology bag that rhodamine 6G modified biomass charcoal is housed is applied in mild or moderate heavy metals exceeding standard soil by plum blossom, chessboard, grid, snakelike method, places 15 ~ 180 days.Wherein heavy metal is one or more in lead, cadmium, chromium, the ecology bag that 500g rhodamine 6G modified biomass charcoal is housed is imbedded 10 ~ 20cm in upland field soil, or directly system is fixed on paddy field soil on the surface, ecology bag amount of application is 20/every mu (each ecology bag includes 500g rhodamine 6G modified biomass charcoal), soil moisture content is not less than 20%, and soil pH value is 5 ~ 9.
D), the removing of heavy metal-polluted soil: the rhodamine 6G modified biomass charcoal ecology bag of Adsorption of Heavy Metals is taken out from soil, completes heavy metal-polluted soil in-situ solidifying-remove.
Excellent results of the present invention is as follows:
(1) easy to use: only need by the ecology bag of in-built rhodamine 6G modified biomass based high molecular material during use, execute and be distributed in heavy metal lead, cadmium, chromium exceeds standard in soil, through after a period of time, again the ecology bag of the saturated heavy metal of absorption is taken out from soil, complete the in-situ solidifying of heavy metal-polluted soil-remove;
(2) environmental protection: overcome traditional fixation in situ-passivating technique and only reduce bioavailability of heavy metals, but heavy metal still resides in soil, and there is the deficiency of secondary pollution risk; Raw materials derives from agricultural biomass stalk, widely distributed in farmland, inexpensive, the preparation method of the biomass carbon adopted is ripe, cost is low, polymerisation grafting polyamine method technique is simple, effective, biomass carbon extensively exists in soil, green non-poisonous, pollution-free in the process preparing active carbon, not welding.
(3) repairing effect is good: rhodamine 6G modified biomass based high molecular material to the lead in soil, cadmium, chromium ion adsorption capacity is large, the rate of adsorption is fast, can effectively remove micro heavy lead, cadmium, chromium, to lead, cadmium, chromium, there is good Selective adsorption, little by the Environmental Factors such as soil acidity or alkalinity, PK, purification efficiency is high, and removal effect is good;
(4) simple, the economy of preparation technology of the present invention, environmental protection, meet the needs of recycling economy development, have large-scale production and application prospect.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, but be not limited thereto.
Example 1:
By the bagasse powder after clean oven dry and phosphoric acid with 1: 1 mass ratio soak 12 hours; bagasse powder after soaking is placed in 60 DEG C of baking ovens; pre-carbonization 10 hours; put into microwave reactor; under the protection of the nitrogen stream of 50ml/min, under the condition of 900W, constant temperature activates 22 minutes and obtains bagasse biomass carbon.By above-mentioned 5g biomass carbon mass fraction be 10% HCl solution stir purifying 5 hours at 60 DEG C, then the nitric acid biological powdered carbon after purifying being added 32.5% of 300ml stirs 5 hours, take the powdered carbon 5g after above-mentioned nitric acid oxidation, add toluene and 1 gram of rhodamine 6G of 100ml, after agitating heating is even, add 5 grams of N, N '-dicyclohexylcarbodiimide, back flow reaction 48 hours.Rhodamine 6G modification bagasse base charcoal polymer composite is obtained by after dry for product washing oven dry.
Loaded in the bag be made by two layers of cloth inside and outside polypropylene spunbond non-woven fabrics and terylene geotextiles by 500g rhodamine 6G modification bagasse base charcoal polymer composite, obtained in-situ solidifying removes the ecology bag of heavy metal-polluted soil.Above-mentioned 5 ecology bags to be exceeded standard 5cm under rice test water in field with the heavy metal cadmium that gridding method is fixed on 20 square meters, places 30 days (be selected from Jiangsu for examination paddy soil, belong to subacidity soil, pH value is 5.8, total cadmium content 5mg/kg in soil).Taken out from soil by the rhodamine 6G modified biomass charcoal ecology bag of Adsorption of Heavy Metals after 30 days, complete the in-situ solidifying of heavy metal-polluted soil lead-remove, in ecology bag, rhodamine 6G modified biomass charcoal macromolecular material is 32.6mg/g. to the adsorbance of lead
Example 2:
Get rhodamine 6G modification bagasse base charcoal polymer composite 250g obtained in example 1 to load in the bag be made by two layers of cloth inside and outside polypropylene spunbond non-woven fabrics and terylene geotextiles, obtained in-situ solidifying removes the ecology bag of heavy metal-polluted soil.Above-mentioned 5 ecology bags to be exceeded standard 5cm under rice test water in field with the heavy metal cadmium that gridding method is fixed on 20 square meters, places 30 days (be selected from Jiangsu for examination paddy soil, belong to subacidity soil, pH value is 5.8, total cadmium content 50mg/kg in soil).Taken out from soil by the rhodamine 6G modified biomass charcoal ecology bag of Adsorption of Heavy Metals after 30 days, complete the in-situ solidifying of soil heavy metal cadmium-remove, in ecology bag, rhodamine 6G modified biomass charcoal macromolecular material is 19.2mg/g. to the adsorbance of cadmium
Example 3:
Get rhodamine 6G modification bagasse base charcoal polymer composite 500g obtained in example 1 to load in the bag be made by two layers of cloth inside and outside polypropylene spunbond non-woven fabrics and terylene geotextiles, obtained in-situ solidifying removes the ecology bag of heavy metal-polluted soil.Above-mentioned 10 ecology bags to be exceeded standard 5cm under rice test water in field with the heavy metal lead that gridding method is fixed on 20 square meters, places 20 days (for examination paddy soil from Jiangsu, belong to subacidity soil, pH value is 5.8, total chromium content in soil content 600mg/kg).Taken out from soil by the rhodamine 6G modified biomass charcoal ecology bag of Adsorption of Heavy Metals after 30 days, complete the in-situ solidifying of heavy metal-polluted soil lead-remove, in ecology bag, rhodamine 6G modified biomass charcoal macromolecular material is 33.8mg/g. to the adsorbance of chromium
Example 4:
Corn stem after clean oven dry is pulverized; with mass concentration be 30% phosphoric acid with 2: 1 mass ratio soak 12 hours; insert in tube furnace after paddy rice cane powder after immersion is dried; under the protection of the nitrogen stream of 50ml/min; 450 DEG C are warmed up to 10 DEG C/min; and constant temperature carbonizes 2.0 hours at such a temperature, being washed till PH with distilled water after cooling is 7.0.Then, clean product is put into baking oven with 105 DEG C of oven dry.Stirred 5 hours at 60 DEG C by above-mentioned for 10g biomass carbon powder 200ml10%HCl solution, the nitric acid that purified charcoal powder adds 32.5% of 300ml again stirs 3 hours, then it is washed till neutral oven dry.Take the powdered carbon 5g after above-mentioned nitric acid oxidation, add toluene and 1.5 grams of rhodamine 6Gs of 150ml, after agitating heating is even, add 5 grams of N, N '-dicyclohexylcarbodiimide, back flow reaction 24 hours.Rhodamine 6G modification paddy rice based biomass charcoal polymer composite is obtained by after dry for product washing oven dry.
Loaded in the bag be made by two layers of cloth inside and outside polypropylene spunbond non-woven fabrics and terylene geotextiles by above-mentioned for 500g corn straw modification based biomass charcoal polymer composite, obtained in-situ solidifying removes the ecology bag of heavy metal-polluted soil.Above-mentioned 5 ecology bags to be exceeded standard 10cm under upland field soil with the heavy metal lead that gridding method is fixed on 20 square meters, place and (be selected from experiment field, Nan Nong Pukou for examination dryland soil in 30 days, pH value is 7.6, keeps soil water-containing to be 60% of field capacity, total lead content 200mg/kg in soil).Taken out from soil by the modified biomass charcoal base ecology bag of Adsorption of Heavy Metals lead after 30 days, complete the in-situ solidifying of heavy metal-polluted soil lead-remove, in ecology bag, rhodamine 6G modified biomass charcoal macromolecular material is 21.2mg/g to the adsorbance of lead.
Example 5:
Get rhodamine 6G corn straw modification based biomass charcoal polymer composite 250g obtained in example 2 to load in the bag be made by two layers of cloth inside and outside polypropylene spunbond non-woven fabrics and terylene geotextiles, obtained in-situ solidifying removes the ecology bag of heavy metal-polluted soil.Above-mentioned 5 ecology bags to be exceeded standard 10cm under upland field soil with the heavy metal lead that chessboard method is fixed on 20 square meters, place and (be selected from experiment field, Nan Nong Pukou for examination dryland soil in 30 days, pH value is 7.6, keeps soil water-containing to be 60% of field capacity, total lead content 200mg/kg in soil).Taken out from soil by the rhodamine 6G modified biomass charcoal ecology bag of Adsorption of Heavy Metals after 30 days, complete the in-situ solidifying of soil heavy metal cadmium-remove, in ecology bag, rhodamine 6G modified biomass charcoal macromolecular material is 16.7mg/g. to the adsorbance of cadmium
Example 6:
Get rhodamine 6G modification bagasse base charcoal polymer composite 250g obtained in example 1 to load in the bag be made by two layers of cloth inside and outside polypropylene spunbond non-woven fabrics and terylene geotextiles, obtained in-situ solidifying removes the ecology bag of heavy metal-polluted soil.Above-mentioned 10 ecology bags to be exceeded standard 10cm under upland field soil with the heavy metal lead that gridding method is fixed on 20 square meters, place and (be selected from experiment field, Nan Nong Pukou for examination dryland soil in 30 days, pH value is 7.6, soil moisture content is kept to be 60% of field capacity, total lead content 200mg/kg in soil).Taken out from soil by the rhodamine 6G modified biomass charcoal ecology bag of Adsorption of Heavy Metals after 30 days, complete the in-situ solidifying of heavy metal-polluted soil lead-remove, in ecology bag, rhodamine 6G modified biomass charcoal macromolecular material is 33.2mg/g to the adsorbance of chromium.

Claims (1)

1. a kind of in-situ solidifying that the present invention proposes removes heavy metal-polluted soil lead, cadmium, the ecology bag of chromium and application process, it is characterized in that:
1), in-situ solidifying removes the composition of ecology bag of heavy metal-polluted soil lead, cadmium, chromium: comprise bag and the biomass-based macromolecular material of rhodamine 6G modification that is loaded in bag is formed jointly.Bag is covered on polypropylene spunbond non-woven fabrics by the terylene geotextiles of uv blocking corrosive nature and is made; Rhodamine 6G modified biomass based high molecular material is loaded in the polypropylene spunbond nonwoven layer in bag internal layer.
2), the preparation process of rhodamine 6G modified biomass based high molecular material: ripe agricultural biomass powder of straw is added the multiporous biological matter charcoal that phosphoric acid heat-activated in blanket of nitrogen prepares the oxygen-containing functional groups such as rich surface hydroxyl, carboxylic acid group, get 5 grams of above-mentioned biomass carbons add 10 ~ 50% of 100 ~ 500ml nitric acid stir 1 ~ 10 hour, after after completion of the reaction product washing and filtering being dried, be distributed in 50 ~ 200ml toluene and 0.5 ~ 2.0g rhodamine 6G, stir, add 5 grams of N, N '-dicyclohexylcarbodiimide, back flow reaction 8 ~ 48 hours.Filter product, clean, dry and to obtain novel rhodamine 6G modified biomass base charcoal macromolecular material.Wherein agricultural biomass stalk comprises bagasse, maize straw, wheat stalk, soybean stalk and cotton stalk etc.
3), the in-situ solidifying of heavy metal-polluted soil: the ecology bag that rhodamine 6G modified biomass based high molecular material is housed is applied in mild or moderate heavy metals exceeding standard soil with plum blossom, chessboard, grid, snakelike method, places 15 ~ 180 days.Wherein heavy metal is one or more in lead, cadmium, chromium, the ecology bag that 500g rhodamine 6G modified biomass charcoal is housed is imbedded 10 ~ 20cm in upland field soil, or be directly fixed on paddy field soil on the surface, ecology bag amount of application is 10 ~ 20/every mu (each ecology bag includes 100 ~ 500g rhodamine 6G modified biomass charcoal), soil moisture content is not less than 20%, and soil pH value is 5 ~ 9.
4), the removing of heavy metal-polluted soil: the ecology bag of Adsorption of Heavy Metals is taken out from soil, completes heavy metal-polluted soil in-situ solidifying-remove.
CN201410611997.4A 2014-10-30 2014-10-30 A kind of in-situ solidifying removes ecology bag and the application process of heavy metal-polluted soil Expired - Fee Related CN104307858B (en)

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CN104941996A (en) * 2015-06-09 2015-09-30 北京市环境保护科学研究院 Remediation method for chromium-contaminated soil
CN105032912A (en) * 2015-07-17 2015-11-11 中国科学院武汉岩土力学研究所 In-situ repair method for shallow-buried heavy metal pollution site
CN105268738A (en) * 2015-11-25 2016-01-27 武汉科技大学 Method for stabilizing chromium pollution soil in chromium salt factory through nitric acid modified activated carbon
CN105950180A (en) * 2016-06-27 2016-09-21 安徽金联地矿科技有限公司 Remediation agent for soil polluted by heavy metals and remediation method thereof
CN107052034A (en) * 2017-05-23 2017-08-18 中国水稻研究所 A kind of plunger-type heavy metal-polluted soil of suitable pot rice removes device and application
CN107552027A (en) * 2017-09-11 2018-01-09 湖南农业大学 A kind of application that the method for carbon material and its carbon material of preparation are prepared using biomass dead meal
CN107931322A (en) * 2017-11-23 2018-04-20 成都新柯力化工科技有限公司 A kind of method using zeroth order Nanoscale Iron original position continuous repair soil
CN109622592A (en) * 2018-11-23 2019-04-16 山西大学 A kind of heavy metal-polluted soil removing method based on modification biological charcoal
CN109821876A (en) * 2019-01-24 2019-05-31 湖州师范学院 A kind of technique for administering heavy metal pollution of soil
CN110076191A (en) * 2019-05-23 2019-08-02 山东师范大学 A kind of heavy metal that passivator can be removed from soil passivation restorative procedure
CN112090950A (en) * 2020-05-23 2020-12-18 北京博泰至淳生物科技有限公司 Paddy field heavy metal pollution remediation material and processing method and remediation method thereof

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Cited By (14)

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Publication number Priority date Publication date Assignee Title
CN104673321B (en) * 2015-02-11 2019-05-31 博天环境集团股份有限公司 A kind of heavy metals immobilization stabilizer and preparation method thereof and application method
CN104673321A (en) * 2015-02-11 2015-06-03 博天环境集团股份有限公司 Heavy metal immobilization stabilizer as well as preparation method and application method of stabilizer
CN104941996A (en) * 2015-06-09 2015-09-30 北京市环境保护科学研究院 Remediation method for chromium-contaminated soil
CN105032912A (en) * 2015-07-17 2015-11-11 中国科学院武汉岩土力学研究所 In-situ repair method for shallow-buried heavy metal pollution site
CN105268738A (en) * 2015-11-25 2016-01-27 武汉科技大学 Method for stabilizing chromium pollution soil in chromium salt factory through nitric acid modified activated carbon
CN105950180A (en) * 2016-06-27 2016-09-21 安徽金联地矿科技有限公司 Remediation agent for soil polluted by heavy metals and remediation method thereof
CN107052034A (en) * 2017-05-23 2017-08-18 中国水稻研究所 A kind of plunger-type heavy metal-polluted soil of suitable pot rice removes device and application
CN107552027A (en) * 2017-09-11 2018-01-09 湖南农业大学 A kind of application that the method for carbon material and its carbon material of preparation are prepared using biomass dead meal
CN107931322B (en) * 2017-11-23 2019-03-01 浙江一龙环保科技有限公司 A method of utilizing zeroth order Nanoscale Iron original position continuous repair soil
CN107931322A (en) * 2017-11-23 2018-04-20 成都新柯力化工科技有限公司 A kind of method using zeroth order Nanoscale Iron original position continuous repair soil
CN109622592A (en) * 2018-11-23 2019-04-16 山西大学 A kind of heavy metal-polluted soil removing method based on modification biological charcoal
CN109821876A (en) * 2019-01-24 2019-05-31 湖州师范学院 A kind of technique for administering heavy metal pollution of soil
CN110076191A (en) * 2019-05-23 2019-08-02 山东师范大学 A kind of heavy metal that passivator can be removed from soil passivation restorative procedure
CN112090950A (en) * 2020-05-23 2020-12-18 北京博泰至淳生物科技有限公司 Paddy field heavy metal pollution remediation material and processing method and remediation method thereof

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