CN105925268A - Soil restoring agent with heavy metal ion adsorption and immobilization functions, and preparation method thereof - Google Patents
Soil restoring agent with heavy metal ion adsorption and immobilization functions, and preparation method thereof Download PDFInfo
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- CN105925268A CN105925268A CN201610268068.7A CN201610268068A CN105925268A CN 105925268 A CN105925268 A CN 105925268A CN 201610268068 A CN201610268068 A CN 201610268068A CN 105925268 A CN105925268 A CN 105925268A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
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Abstract
The invention provides a soil restoring agent with heavy metal ion adsorption and immobilization functions, and a preparation method thereof. The raw material formula of the soil restoring agent comprises 60-80 parts of waste soil obtained after oil decolorizing and waste white clay oil extraction, 2-5 parts of a sulfur-containing compound, 8-15 parts of aluminum magnesium silicate and 10-20 parts of humic acid. The preparation method of the soil restoring agent comprises the following steps: 1, reacting the waste soil with the sulfur-containing compound at 500-700DEG C to obtain sulfenyl group-containing modified soil with an octahedral structure; and 2, mixing the modified soil with aluminum magnesium silicate and humic acid to obtain the soil restoring agent. The soil restoring agent has the advantages of recycling of the waste white clay, excellent heavy metal ion adsorption and immobilization functions, high added values, simple preparation and low cost.
Description
Technical field
The present invention relates to technical field of soil remediation, be specifically related to a kind of have absorption and the soil-repairing agent of fixing heavy metal ion.
Background technology
Soil pollution has become worldwide problem, and heavy metal pollution has become " the stealthy killer " of agricultural products in China.Chemical fertilizer is excessively used and can cause soil acidification, and then can induce the raising of soil heavy metal ion activity.Soil pH value often declines a unit, and the activity of heavy metal cadmium will promote 100 times, increases the risk of the difficult and complicated illness such as Itai-itai diseases." the maximum feature of widespread pollution from the overuse of fertilizers and pesticides in rural area is hiding, chronicity and dispersibility, is the conscious or the most conscious generation during each of agricultural production links, deals with cumbersome.According to the preliminary statistics, national contaminated arable land there are about 1 000 ten thousand hm2, organic pollution polluted agricultural land reaches 3 600 ten thousand hm2, the pesticide residues exceeding standard rate of main farm produce is up to 16%～20%；216.7 ten thousand hm that plough are polluted in sewage irrigation2, solid waste is stored up occupation of land and ruins field 13.3 ten thousand hm2.And in the situation increasingly aggravated.Soil pollution can affect the decline of Crop yield and quality, and can be by the health of the food chain harm mankind, it is also possible to causes the further deterioration of air and quality of water environment.Therefore the improvement of soil pollution is the most very urgent.
The decolouring of oils and fats mainly uses active hargil, but active hargil has also adsorbed substantial amounts of oils and fats while adsorpting pigment, by the spent bleaching clay after grease-decolor is measured, oil content reaches 20%-30%, and the hargil after decolouring loses activity, it is impossible to make decolorising agent again, if spent bleaching clay processes not in time and pollutes the environment, spent bleaching clay is all abandoned by general oil factory, and external oil factory uses landfill or the method burned, and this had not only wasted resource but also without economic benefit.
The open CN101659868A of Chinese invention patent discloses a kind of method utilizing waste bleaching clay to prepare soil conditioner, it controls 6%～8% after being extracted oil by waste bleaching clay, then, after being crushed to 60～80 mesh, make for salt-soda soil is improved as soil conditioner.Although this patented method has carried out reuse to waste bleaching clay, but the simple of waste bleaching clay is simply utilized by it, and salt-soda soil can only be improved by its prepared soil conditioner, does not possess absorption and the function of fixing heavy metal, and added value of product is low.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art to provide a kind of be possible not only to that spent bleaching clay is carried out resource reutilization and the most also there is excellent absorption and fixing heavy metal ion function, soil-repairing agent that added value is the highest and preparation method thereof.
For achieving the above object, a kind of technical scheme that the present invention takes is as follows for the present invention:
A kind of have absorption and the soil-repairing agent of fixing heavy metal ion function, in parts by weight, the composition of raw materials of this soil-repairing agent include grease-decolor spent bleaching clay carry oil after roach 60-80 part, sulfur-containing compound 2-5 part, aluminium-magnesium silicate 8-15 part and humic acids 10-20 part, soil-repairing agent is made by the steps by described raw material and obtains: 1) make described roach and sulfur-containing compound react at temperature 500-700 DEG C, it is thus achieved that the modified soil body in the octahedral structure containing sulfenyl；2) the modification soil body is mixed to get soil-repairing agent with aluminium-magnesium silicate and humic acids.
Further, described sulfur-containing compound can and the preferably a kind of or combination of two kinds in calcium polysulfide, sodium polysulphide.
Preferably, step 1) in, first roach is placed in 500-700 DEG C of roasting temperature, after the siliconoxygen bond of roach is opened, adds sulfur compound and react.
In the present invention, its oil content of roach as raw material can be 15-22%.
The another technical scheme that the present invention takes is: the preparation method of a kind of soil-repairing agent with absorption and fixing heavy metal ion function, comprising:
1) roach after making grease-decolor spent bleaching clay carry oil and sulfur-containing compound react at temperature 500-700 DEG C, it is thus achieved that the modified soil body in the octahedral structure containing sulfenyl；
2) the modification soil body is mixed to get described soil-repairing agent with aluminium-magnesium silicate and humic acids；
Wherein, the weight proportion of roach, sulfur-containing compound, aluminium-magnesium silicate and humic acids is 60-80:2-5:8-15:10-20.
Preferably, step 1) in, first roach is placed in 500-700 DEG C of roasting temperature, after the siliconoxygen bond of roach is opened, adds sulfur compound and react.
Preferably, step 1) in, roasting time is 0.5-1h, after adding sulfur compound, reacts 2-3h.
Preferably, step 1) in, the oil content of roach is 15-22wt%.
Preferably, a kind of or combination of two kinds during described sulfur-containing compound is calcium polysulfide, sodium polysulphide.
According to the present invention one is concrete and preferred aspect, step 2) in, specific operation process is: to step 1) the gained modification soil body adds aluminium-magnesium silicate and humic acids stirring mixing, finally grind to form granule or powder.
Compared with prior art, beneficial effects of the present invention is as follows:
1, the solution of the present invention is taked, hargil roach opens spent bleaching clay siliconoxygen bond after baking, react with sulfur-containing compound, sulphion substitutes oxonium ion, form the stable octahedral structure containing sulfenyl, specific surface area increases, it is greatly increased the absorption of heavy metal ion, free heavy metal (cadmium, hydrargyrum, copper, lead, zinc) in the effective stable curing soil of sulfenyl energy simultaneously, make the heavy metal ion in soil will not be by re-activation, do not adsorbed by vegetation and affect yield and the quality of crops, it is to avoid the health come by food chain harm people.
In renovation agent the most of the present invention, Magnesiumaluminumsilicate can cross the chromium in the attached soil of ion-exchange absorption, hydrargyrum, copper plasma, humic acids can be soil humic acid or water body humic acids, there is good physiologically active and absorption, complexation, the functions such as exchange, organic matter is provided in soil, heavy metal ion in activating soil, heavy metal ion can effectively be adsorbed after exciting, thus improve the adsorption rate of heavy metal ion, immobilization is stablized in the absorption being conducive to heavy metal ion, it is experimentally confirmed the ability 20%-30% to be improved of the soil-repairing agent Adsorption of Heavy Metal Ions adding humic acids.In a word, by the compounding prepared soil-repairing agent according to a certain percentage of the modified soil body, Magnesiumaluminumsilicate and the humic acids after particular modification is met the general requirement of soil remediation and has the most excellent heavy metal adsorption and crystallized ability simultaneously.
3, renovation agent of the present invention can realize the resource reutilization of spent bleaching clay, had both saved the processing cost of spent bleaching clay, alleviates again the pressure to environment, also creates high value-added product.
4, the renovation agent composition of the present invention is simple, and safety is the most harmless to soil, and meanwhile, the preparation method of renovation agent is simple, easily realizes, has good industrial applications prospect.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described in detail, and in embodiment, not marked condition is the condition that this area is conventional.When addressing consumption or the dosage of material, unless stated otherwise, refer both to weight.The oil content of roach (hereinafter referred to as roach) after the grease-decolor spent bleaching clay used in following example carries oil is 15-22wt%.
Embodiment 1
A kind of soil-repairing agent, is made by the steps and obtains:
1) roach 70 parts is placed in roasting 0.5h at 600 DEG C, adds 3 parts of calcium polysulfides, react 2h, obtain the modified soil body；
2) by step 1) the gained modification soil body and 12 parts of aluminium-magnesium silicates and 15 parts of soil humic acids stirring mixing, finally grind to form graininess, obtain soil-repairing agent.
This soil-repairing agent outward appearance is grey black granular solids, and when solid-to-liquid ratio is 1:2.5, pH is 8.20.
Embodiment 2
A kind of soil-repairing agent, is made by the steps and obtains:
1) roach 70 parts is placed in roasting 0.6h at 600 DEG C, adds 5 parts of calcium polysulfides, react 2h, obtain the modified soil body；
2) by step 1) the gained modification soil body and 8 parts of aluminium-magnesium silicates and 20 parts of soil humic acids stirring mixing, finally grind to form graininess, obtain soil-repairing agent.
This soil-repairing agent outward appearance is grey black granular solids, and when solid-to-liquid ratio is 1:2.5, pH is 8.50
Embodiment 3
A kind of soil-repairing agent, is made by the steps and obtains:
1) roach 80 parts is placed in roasting 0.5h at 600 DEG C, adds 2 parts of sodium polysulphide, reaction 2h (time), obtain the modified soil body；
2) by step 1) the gained modification soil body and 15 parts of aluminium-magnesium silicates and 10 parts of soil humic acids stirring mixing, finally grind to form graininess, obtain soil-repairing agent.
This soil-repairing agent outward appearance is grey black granular solids, and when solid-to-liquid ratio is 1:2.5, pH is 8.10.
Embodiment 4
A kind of soil-repairing agent, is made by the steps and obtains:
1) roach 70 parts is placed in roasting 1h at 700 DEG C, adds 3 parts of calcium polysulfides, react 2.5h, obtain the modified soil body；
2) by step 1) the gained modification soil body and 12 parts of aluminium-magnesium silicates and 15 parts of soil humic acids stirring mixing, finally grind to form graininess, obtain soil-repairing agent.
This soil-repairing agent outward appearance is dark gray powder shape solid, and when solid-to-liquid ratio is 1:2.5, pH is 8.20.
Embodiment 5
A kind of soil-repairing agent, is made by the steps and obtains:
1) roach 70 parts is placed in roasting 1.5h at 500 DEG C, adds 3 parts of calcium polysulfides, react 2.5h, obtain the modified soil body；
2) by step 1) the gained modification soil body and 12 parts of aluminium-magnesium silicates and 15 parts of soil humic acids stirring mixing, finally grind to form graininess, obtain soil-repairing agent.
This soil-repairing agent outward appearance is grey black granular solids, and when solid-to-liquid ratio (with the weight ratio of water) is 1:2.5, pH is 8.21.
Comparative example 1
A kind of compositions, is made by the steps and obtains: be placed at 600 DEG C after roasting 0.5h by roach 70 parts, mixes with 8 parts of aluminium-magnesium silicates and 20 parts of soil humic acid stirrings, finally grinds to form graininess.
Said composition outward appearance is grey black granular solids, and when solid-to-liquid ratio is 1:2.5, pH is 8.00.
Comparative example 2
A kind of compositions, is made by the steps and obtains: directly mix the most fired for roach 70 parts with calcium polysulfide 5 parts, then mixes with 8 parts of aluminium-magnesium silicates and 20 parts of soil humic acid stirrings, finally grinds to form graininess.
Said composition outward appearance is grey black granular solids, and when solid-to-liquid ratio is 1:2.5, pH is 8.55.
Comparative example 3
A kind of compositions, is made by the steps and obtains:
1) roach 70 parts is placed in roasting 0.6h at 600 DEG C, adds 3 parts of calcium polysulfides, react 2h, obtain the modified soil body；
2) by step 1) the gained modification soil body and the stirring mixing of 12 parts of aluminium-magnesium silicates, finally grind to form graininess.
Said composition outward appearance is grey black granular solids, and when solid-to-liquid ratio is 1:2.5, pH is 8.20.
The soil-repairing agent of embodiment 1-5 and the heavy metal adsorption of comparative example 1-3 resulting composition and crystallized ability are tested.Method of testing: soil-repairing agent uniformly mixes the surface being sprinkling upon heavy-metal contaminated soil, and every mu is 160kg, then carries out Soil tillage and makes soil-repairing agent and heavy-metal contaminated soil be sufficiently mixed uniformly, balance and complete heavy metal-polluted soil repair process in 7 days.Untreated heavy metal soil available concentration test result sees table 1, and the test result after each example soil-repairing agent processes sees table 2.
Table 1: untreated heavy metal soil available concentration
| Sequence number | pH | Cu(mg/l) | Zn(mg/l) | Pb(mg/l) | Cr(mg/l) | Cd(mg/l) | Hg(mg/l) |
| 1 | 8.00 | 0.780 | 3.020 | 1.521 | Do not detect | 0.501 | 0.081 |
Table 2: heavy metal soil available concentration after process
| Sequence number | pH | Cu(mg/l) | Zn(mg/l) | Pb(mg/l) | Cr(mg/l) | Cd(mg/l) | Hg(mg/l) |
| Embodiment 1 | 8.20 | Do not detect | 0.150 | 0.0114 | Do not detect | Do not detect | Do not detect |
| Embodiment 2 | 8.50 | 0.071 | 0.002 | Do not detect | Do not detect | Do not detect | Do not detect |
| Embodiment 3 | 8.10 | Do not detect | 0.120 | 0.003 | Do not detect | Do not detect | Do not detect |
| Embodiment 4 | 8.20 | 0.100 | Do not detect | Do not detect | Do not detect | Do not detect | 0.021 |
| Embodiment 5 | 8.21 | Do not detect | 0.023 | 0.012 | Do not detect | Do not detect | Do not detect |
| Comparative example 1 | 8.00 | 0.060 | 0.052 | Do not detect | Do not detect | 0.002 | 0.001 |
| Comparative example 2 | 8.55 | 0.012 | 0.021 | 0.002 | Do not detect | 0.012 | 0.005 |
| Comparative example 3 | 8.20 | 0.050 | 0.014 | 0.004 | Do not detect | 0.005 | 0.004 |
The data of embodiment 1 are unreasonable, please revise.
Claims (10)
1. one kind has absorption and the soil-repairing agent of fixing heavy metal ion function, it is characterised in that: with weight
Amount part meter, the composition of raw materials of described soil-repairing agent include grease-decolor spent bleaching clay carry oil after roach 60-80
Part, sulfur-containing compound 2-5 part, aluminium-magnesium silicate 8-15 part and humic acids 10-20 part, described soil is repaiied
Multiple agent is made by the steps by described raw material and obtains: 1) make described roach and sulfur-containing compound in temperature
React at 500-700 DEG C, it is thus achieved that the modified soil body in the octahedral structure containing sulfenyl；2) by described modification
The soil body is mixed to get described soil-repairing agent with aluminium-magnesium silicate and humic acids.
The most according to claim 1 have absorption and the soil-repairing agent of fixing heavy metal ion function,
It is characterized in that: described sulfur-containing compound is a kind of or combination of two kinds in calcium polysulfide, sodium polysulphide.
The soil with absorption and fixing heavy metal ion function the most according to claim 1 and 2 is repaiied
Multiple agent, it is characterised in that: step 1) in, first roach is placed in 500-700 DEG C of roasting temperature, waits to give up
After the siliconoxygen bond of soil is opened, add sulfur compound and react.
The most according to claim 1 have absorption and the soil remediation of fixing heavy metal ion function
Agent, it is characterised in that: the oil content of described roach is 15-22wt%.
5. there is a preparation method for the soil-repairing agent of absorption and fixing heavy metal ion function, its feature
It is to include:
1) grease-decolor spent bleaching clay is made to carry the roach after oil and sulfur-containing compound anti-at temperature 500-700 DEG C
Should, it is thus achieved that the modified soil body in the octahedral structure containing sulfenyl；
2) the modification soil body is mixed to get described soil-repairing agent with aluminium-magnesium silicate and humic acids；
Wherein, the weight proportion of described roach, sulfur-containing compound, aluminium-magnesium silicate and humic acids is 60-80:
2-5:8-15:10-20.
The most according to claim 5 have absorption and the soil-repairing agent of fixing heavy metal ion function
Preparation method, it is characterised in that: step 1) in, first roach is placed in 500-700 DEG C of roasting temperature,
After the siliconoxygen bond of roach is opened, add sulfur compound and react.
The most according to claim 6 have absorption and the soil-repairing agent of fixing heavy metal ion function
Preparation method, it is characterised in that: step 1) in, roasting time is 0.5-1h, adds after sulfur compound,
Reaction 2-3h.
The most according to claim 5 have absorption and the soil-repairing agent of fixing heavy metal ion function
Preparation method, it is characterised in that: step 1) in, the oil content of roach is 15-22wt%.
The most according to claim 1 have absorption and the soil-repairing agent of fixing heavy metal ion function
Preparation method, it is characterised in that: described sulfur-containing compound is the one in calcium polysulfide, sodium polysulphide
Or the combination of two kinds.
The most according to claim 5 have absorption and the soil remediation of fixing heavy metal ion function
The preparation method of agent, it is characterised in that: step 2) in, specific operation process is: to step 1) gained
The modified soil body adds aluminium-magnesium silicate and humic acids stirring mixing, finally grinds to form granule or powder.
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Cited By (5)
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| CN106635033A (en) * | 2016-12-04 | 2017-05-10 | 钦州市星火计划办公室 | Soil remediation agent and preparation method thereof |
| CN107418587A (en) * | 2017-05-17 | 2017-12-01 | 郭迎庆 | A kind of preparation method of soil heavy metal combined passivator |
| CN108101699A (en) * | 2017-12-16 | 2018-06-01 | 长沙无道工业设计有限公司 | A kind of soil-repairing agent and preparation method thereof |
| CN108405597A (en) * | 2018-03-14 | 2018-08-17 | 上海立昌环境工程股份有限公司 | A kind of heavy-metal contaminated soil renovation agent and its application |
| CN110776921A (en) * | 2019-10-31 | 2020-02-11 | 中冶南方都市环保工程技术股份有限公司 | Conditioner for repairing heavy metal chromium-polluted soil and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108405597A (en) * | 2018-03-14 | 2018-08-17 | 上海立昌环境工程股份有限公司 | A kind of heavy-metal contaminated soil renovation agent and its application |
| CN110776921A (en) * | 2019-10-31 | 2020-02-11 | 中冶南方都市环保工程技术股份有限公司 | Conditioner for repairing heavy metal chromium-polluted soil and preparation method and application thereof |
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Application publication date: 20160907 |