CN109943345A - Reparation medicament and its preparation method and application for handling heavy-metal contaminated soil - Google Patents
Reparation medicament and its preparation method and application for handling heavy-metal contaminated soil Download PDFInfo
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Abstract
The present invention relates to a kind of reparation medicaments and its preparation method and application for handling heavy-metal contaminated soil.The reparation medicament, in parts by weight, including following components: thio guanidine radicals formates -10-50 parts of modification biological charcoal compound stabilizer, 10-40 parts of soluble phosphate, 10-30 parts of sepiolite powder；Wherein, the thio guanidine radicals formates-modification biological charcoal compound stabilizer crosslinks to react by six thio guanidine radicals formate solutions with the modification biological charcoal is prepared.The reparation medicament has good stablizing effect to the various heavy in soil.In addition, the application the invention also includes the preparation method of the reparation medicament and in rehabilitating soil.
Description
Technical field
The present invention relates to the present invention relates to environmental protections and materials science field, more particularly to one kind to be used to handle heavy metal
Reparation medicament of contaminated soil and its preparation method and application.
Background technique
It is especially prominent with heavy metal pollution in Soil Environmental Pollution problem.Investigation display, the soil of China's heavy metal pollution
Account for about the 64.8% of the contaminated land gross area, wherein serious contaminated area accounts for about 8.4%, intermediate pollution area accounts for 9.7%, slightly
Contaminated area accounts for 46.7%.In the soil of heavy metal pollution farmland, the most serious, secondly Pb, As, Cr, Cu dirt is polluted with Cd, Hg
It is also more serious to contaminate situation.According to statistics, there are about 1.4 ten thousand hectares for the Cd contaminated land area in China.China In The Suburbs of Large And Medium Cities
The exceeding standard rate of Pb respectively reaches 38.6%, 28%, 27.6%, 41.9% and in middle veterinary antibiotics, meat and livestock products
71.1%.It is exceeded the most serious with Pb content and in 24 provinces and cities' emphasis of investigation pollution industrial and mining area, outskirts of a town.
General soil pollution problem exists simultaneously other pollutants based on a certain pollutant, i.e. combined pollution is asked
Topic.Combined contamination soil is compared with Single Pollution soil, characteristic that the physicochemical property and pollutant of soil are shown etc. meeting
Different from increases complexity to soil pollution.In general, can interact between combined pollutant, show as summing it up
Effect, antagonism and synergistic effect.There are many restorative procedure of soil, wherein chemical stabilization method is that the popular one kind of comparison is repaired
Compound method.Heavy Metal in Soil of Mining is controlled using chemical stabilizing method, prevents its contamination, at the same suitably into
Row purification and reparation are a kind of economically viable repair modes.For chemical stabilization method, the selection of renovation agent is crucial.It is real
In the application of border, stablizing effect having a certain difference property of the different stabilizers for variety classes, pollutant of different nature.And
And in the soil of combined pollutant, single stabilizer is difficult to reach reparation requirement.
Summary of the invention
The present invention acts on soil remediation single technical problem for stabilizer, proposes a kind of heavy metal-polluted for handling
Contaminate the reparation medicament and its preparation method and application of soil.
It is a kind of for handling the reparation medicament of heavy-metal contaminated soil, in parts by weight, including following components: thio
Guanidine radicals formates -10-50 parts of modification biological charcoal compound stabilizer, 10-40 parts of soluble phosphate, 10-30 parts of sepiolite powder；Its
In, the thio guanidine radicals formates-modification biological charcoal compound stabilizer passes through six thio guanidine radicals formate solutions and the modification
Charcoal crosslinks reaction and is prepared.
Preferably, described six thio guanidine radicals formates include six thio guanidine radicals potassium formates and/or six thio guanidine radicals sodium formates.
Preferably, the modification biological charcoal is impregnated through the NaOH solution that concentration is 5%-10% by charcoal and is made.
Preferably, the soluble phosphate is potassium dihydrogen phosphate, sodium dihydrogen phosphate, calcium dihydrogen phosphate, sodium phosphate, phosphoric acid
One of potassium and calcium phosphate are a variety of.
Preferably, described six thio guanidine radicals formate solutions crosslink to react with the modification biological charcoal is prepared institute
Stating thio guanidine radicals formates-modification biological charcoal compound stabilizer specific steps includes: described six thio guanidine radicals formates and institute
State modification biological charcoal in the ratio of 1:3~4 mixing after, according to solid-to-liquid ratio 1:8~10 be added water, at 40 DEG C~45 DEG C stir 2~
Carbon dioxide gas is passed through while 3h to be made.
Preferably, the partial size of the sepiolite≤200 mesh, sedimentation value >=850.
The invention also includes a kind of for handling the preparation method of the reparation medicament of heavy-metal contaminated soil, comprising steps of
1) six thio guanidine radicals formates are crosslinked to react with modification biological charcoal and thio guanidine radicals formates-modification life is made
Object charcoal compound stabilizer；
2) the thio guanidine radicals formates-modification biological charcoal compound stabilizer, soluble phosphate and sepiolite powder is pressed
It is mixed to get mixture according to proportion, is later mixed the mixture according to 1~20:100 of mass ratio with water, and stir evenly mixed
It closes, the reparation medicament is made.
Further, in step 1), the six thio guanidine radicals formate solution is crosslinked with the modification biological charcoal
It includes: by six sulphur that the specific steps of the thio guanidine radicals formates-modification biological charcoal compound stabilizer, which are prepared, in reaction
After mixing for guanidine radicals formates and the modification biological charcoal in the ratio of 1:3~4, water is added according to solid-to-liquid ratio 1:8~10, at 40 DEG C
Carbon dioxide gas is passed through while stirring 2~3h at~45 DEG C to be made.
Further, in step 1), the modification biological charcoal is 5%-10%'s by the way that charcoal is soaked in concentration
It is made in NaOH solution.Further, charcoal is soaked in concentration is to be heated to 200 DEG C in 5%-10%NaOH solution,
2h is kept, after cooling, cleaning to pH neutrality is made.
In addition, the invention also provides a kind of reparation medicaments for handling heavy-metal contaminated soil described above to repair
Application in earth backing earth, according to it is described repair medicament weight be soil weight 2%-10% by the reparation medicament with it is described
Soil blending.
The beneficial effect of the present invention compared with the prior art includes: that sepiolite is octahedra mutually by oxygen-octahedron and magnesia
The three-dimensional structure connected into has the duct through total prosperity and hole, similar to the structure of zeolite, its ratio table
Area can high 900m2/ g, therefore there is very big absorption property, since the surface of sepiolite is contained in a large amount of acid and alkalinity
The heart has stronger polarity, so the stronger substance of polarity can be first adsorbed, sepiolite counterweight Metal Ions Cd2+、Pb2+、Hg2+、
Ni2+Deng also there is special suction-operated, the heavy metal ion in adsorbable soil；Modification biological charcoal and six thio guanidine radicals formates are molten
Liquid crosslinks reaction and generates thio guanidine radicals formates-modification biological charcoal compound stabilizer, so that the hole knot of modification biological charcoal
Load has a six thio guanidine radicals formates in structure, on six thio guanidine radicals formates in contain more N, S coordination atom, be conducive to a huge sum of money
The absorption of category improves modification biological charcoal to the adsorption capacity of heavy metal.Sepiolite and thio guanidine radicals formates-modification biological charcoal
Most heavy metal in the adsorbable soil of cooperation of compound stabilizer, furthermore absorption, co-precipitation can occur for phosphate and lead
Etc. a variety of effects, using precipitation mechanism as leading role, lead produces the mineral of solubility very little, such as chlorine with phosphate in the soil
Phosphorus lead ore, hydroxyl phosphorus lead ore and fluorine phosphorus lead ore etc. further remove the relatively higher lead of heavy metal in soil content, so that
Reparation medicament proposed by the present invention has good stablizing effect to the various heavy in soil.
In addition, non-modified or functional modification charcoal has limited adsorption site, it is limited in reality
Application in heavy metal improvement.Modification biological charcoal by the soaking with sodium hydroxide of 5%-10% can change the hole of charcoal
Structure and mineral composition, and increase the oxygen-containing functional group of biological carbon surface, and the load of modification biological charcoal is made to have a sodium ion, sodium from
Son can be exchanged with the heavy metal ion in soil, realize the removal to heavy metal ions in soil.
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, below to specific reality of the invention
The mode of applying is described in detail.In the following description, numerous specific details are set forth in order to facilitate a full understanding of the present invention.But
The invention can be embodied in many other ways as described herein, and those skilled in the art can be without prejudice to this hair
Similar improvement is done in the case where bright intension, therefore the present invention is not limited to the specific embodiments disclosed below.
In following embodiment 1-3, six thio guanidine radicals formates-modification biological charcoal compound stabilizers and modification biological charcoal point
It is not prepared by the following method:
Six thio guanidine radicals formates-modification biological charcoal compound stabilizer preparation: six thio guanidine radicals formates and modified life
After object charcoal is mixed in 1:3 ratio, water is added according to solid-to-liquid ratio 1:8, after being continuously passed through carbon dioxide gas in agitating device,
2 hours are stirred in water-bath under 40 DEG C of constant temperature to get to six thio guanidine radicals formates-modification biological charcoal compound stabilizer.
The preparation of modification biological charcoal: 5g charcoal is soaked in 0.5mol/LNaOH solution, is heated to 200 DEG C, is kept
2h, after cooling, cleaning to pH neutrality.
Showed it should be noted that the in-situ immobilization in present embodiment refers in the original place of contaminated soil
Field is repaired, and showering, which refers to, excavates contaminated soil from the position polluted, and within the scope of former site or passes through
Cross the technology administered again after transport.The partial size of the sepiolite used in present embodiment≤200 mesh, sedimentation value >=
850。
Embodiment 1
The reparation medicament for being used to handle heavy-metal contaminated soil in the present embodiment, in parts by weight, including it is following
Component: six thio guanidine radicals formates -40 parts of modification biological charcoal compound stabilizer, 30 parts of soluble phosphate, inorganic mineral absorption
30 parts of material sepiolite powder；Wherein, 30 portions of soluble phosphoric acid salt include 15 parts and 15 parts of sodium phosphate of calcium dihydrogen phosphate.
Reparation medicament in the present embodiment is prepared by following steps: it carries out being mixed to get mixture by said components, it will
The mixture is mixed with water according to quality proportioning 5:100, and stirs evenly mixing, and slimy reparation medicament is made.
The present embodiment further includes the application for repairing medicament in rehabilitating soil, specific as follows:
In-situ immobilization processing is carried out to lead to be repaired, cadmium, mercury contaminated soil using the slimy reparation medicament, is pressed
The reparation medicament and the soil are blended according to 5% that the weight for repairing medicament is soil weight.
The soil to be repaired of the present embodiment soil in the place of zhuzhou,hunan chemical plant, through lead in detection soil, cadmium,
Mercury is used higher than " soil environment quality construction land soil pollution risk management and control standard (tentative) " (GB36600-2018) the second class
The standard of ground control value, lead, cadmium, mercury are according to " People's Republic of China's state environment protecting standard (HJ557-2010): solid is useless
Object Leaching leaching method horizontal vibration method " leaching concentration exceed " Groundwater Environmental Quality standard " (GB/T 14848-
2017) IV class quality standard, concrete condition are as shown in table 1.
The exceeded content of beary metal of soil in 1 zhuzhou,hunan chemical plant place of table
To the technical indicators such as the lead, cadmium, the soil types of mercury contaminated soil, physicochemical property, penetrating power, level of ground water into
After row analysis, the amount of lead, cadmium, mercury in soil to be repaired is estimated.
Medicament rehabilitating soil is repaired in the present embodiment, and specific step is as follows:
1) deep layer contaminated soil is carried out to plough deeply agitation using strong stirring heads, and grouting is installed above strong stirring heads
Injection apparatus is uniformly stirred；
2) injection apparatus is delivered directly to for medicament is repaired by hydraulic-driven, hydraulic control, is being stirred with agitating device
The negative pressure space or hydraulic-driven formed during mixing will repair medicament and spray into contaminated soil；
3) detected by being mounted on the flowmeter at conveying system valve end and repair the input speed of medicament, incorporation, make its by
It is effectively mixed according to scheduled ratio with contaminated soil；Make repair medicament it is fully penetrated to lead, cadmium, mercury contaminated soil it is whole
A region carries out repair process；
4) after conserving 5 days, soil sample is taken by professional standard, is air-dried under natural conditions, carries out Leaching Heavy Metals detection,
Testing result is shown in Table 2, it is known that maintenance 5 days, leaching concentration meets " Groundwater Environmental Quality standard " (GB/T in soil
14848-2017) IV class quality standard, by reparation medicament described in the present embodiment using in-situ immobilization treated Zhuzhou
Lead, cadmium, mercury contaminated soil in factory floor make area so that the heavy metal contaminants such as lead, cadmium, mercury spread and prevented in place
Domain ecological environment is greatly improved.
Soil remediation effect situation in 2 zhuzhou,hunan chemical plant place of table
Embodiment 2
The reparation medicament for being used to handle heavy-metal contaminated soil in the present embodiment, in parts by weight, including it is following
Component: six thio guanidine radicals formates -30 parts of modification biological charcoal compound stabilizer, 35 parts of soluble phosphate, wherein biphosphate
20 parts of calcium, 15 parts of calcium phosphate, 35 parts of inorganic mineral adsorbent material sepiolite powder；Wherein, 35 parts of soluble phosphates include phosphoric acid
20 parts and 15 parts of calcium phosphate of calcium dihydrogen.
Reparation medicament in embodiment is prepared by following steps: carrying out being mixed to get mixture by said components, by institute
It states mixture and is mixed with water according to quality proportioning 10:100, and stir evenly mixing, slimy reparation medicament is made.
The present embodiment further includes repairing application of the medicament in rehabilitating soil, specific as follows: slimy being repaired using described
Multiple medicament carries out showering processing to lead to be repaired, cadmium, mercury contaminated soil, is soil according to the weight for repairing medicament
The 8% of weight blends the reparation medicament and the soil.
The soil to be repaired of the present embodiment is from soil in liuyang hunan battery factory site, through lead, cadmium, mercury in detection soil
Higher than " soil environment quality construction land soil pollution risk management and control standard (tentative) " (GB36600-2018) the second class land used
The standard of control value, lead, cadmium, mercury are according to " People's Republic of China's state environment protecting standard (HJ557-2010): solid waste
Leaching leaching method horizontal vibration method " leaching concentration exceed " Groundwater Environmental Quality standard " (GB/T 14848-2017)
IV class quality standard, after soil is repaired in liuyang hunan battery factory site, Leaching of Heavy Metals concentration is substantially reduced, and reaches preferable
Repairing effect, concrete condition is as shown in table 3.
The exceeded content of beary metal of soil in 3 liuyang hunan battery factory site of table
To the technical indicators such as the lead, cadmium, the soil types of mercury contaminated soil, physicochemical property, penetrating power, level of ground water into
After row analysis, the amount of lead to be repaired, cadmium, mercury contaminated soil is estimated.
Specific step is as follows for reparation medicament rehabilitating soil in the present embodiment:
1) using soil breaking mixing apparatus to the broken mixing of contaminated soil, and grouting is installed above broken mixing apparatus
Injection apparatus is uniformly stirred；
2) injection apparatus is delivered directly to for medicament is repaired by hydraulic-driven, hydraulic control, is being stirred with agitating device
The negative pressure space or hydraulic-driven formed during mixing will repair medicament and spray into contaminated soil；
3) detected by being mounted on the flowmeter at conveying system valve end and repair the input speed of medicament, incorporation, make its by
It is effectively mixed according to scheduled ratio with contaminated soil；Make repair medicament it is fully penetrated to lead, cadmium, mercury contaminated soil it is whole
A region carries out repair process；
4) after conserving 7 days, soil sample is taken by professional standard, is air-dried under natural conditions, carries out Leaching Heavy Metals detection,
Testing result is shown in Table 4, it is known that maintenance 7 days, leaching concentration meets " Groundwater Environmental Quality standard " (GB/T in soil
14848-2017) IV class quality standard.
Soil remediation effect situation in 4 liuyang hunan battery factory site of table
Embodiment 3
The reparation medicament for being used to handle heavy-metal contaminated soil in the present embodiment, in parts by weight, including it is following
Component: six thio guanidine radicals formates -40 parts of modification biological charcoal compound stabilizer, 30 parts of potassium dihydrogen phosphates, inorganic mineral adsorption material
30 parts of sepiolite powder of material.
Reparation medicament in embodiment is prepared by following steps: carrying out being mixed to get mixture by said components, by institute
It states mixture and is mixed with water according to quality proportioning 10:100, and stir evenly mixing, slimy reparation medicament is made.
The present embodiment further includes repairing application of the medicament in rehabilitating soil, specific as follows: slimy being repaired using described
Multiple medicament carries out in-situ immobilization processing to lead to be repaired, cadmium, mercury contaminated soil, is soil according to the weight for repairing medicament
The 2% of weight blends the reparation medicament and the soil.
The soil to be repaired of the present embodiment be Chenzhou, Hunan Province dressing plant periphery plough (paddy field), through detection soil in lead,
Cadmium, mercury are higher than " soil environment quality farming land soil pollution risk management and control standard (tentative) " (GB 15618-2018) 5.5 < pH
The standard in≤6.5 paddy fields, lead, cadmium, mercury are according to " People's Republic of China's state environment protecting standard (HJ557-2010): solid
Waste Leaching leaching method horizontal vibration method " leaching concentration exceed " Groundwater Environmental Quality standard " (GB/T 14848-
2017) IV class quality standard, concrete condition are as shown in table 5.
5 Chenzhou, Hunan Province dressing plant periphery of the table arable land exceeded content of beary metal of (paddy field) soil
To the technical indicators such as the lead, cadmium, the soil types of mercury contaminated soil, physicochemical property, penetrating power, level of ground water into
After row analysis, the amount of lead, cadmium, mercury in contaminated soil to be repaired is estimated.
Medicament rehabilitating soil is repaired in the present embodiment, and specific step is as follows:
1) contaminated soil is stirred using rotary mixing machine, and above mixing machine installation grouting injection apparatus into
Row uniformly agitation；
2) injection apparatus is delivered directly to for medicament is repaired by hydraulic-driven, hydraulic control, is being stirred with agitating device
The negative pressure space or hydraulic-driven formed during mixing will repair medicament and spray into contaminated soil.
3) detected by being mounted on the flowmeter at conveying system valve end and repair the input speed of medicament, incorporation, make its by
It is effectively mixed according to scheduled ratio with contaminated soil；Make repair medicament it is fully penetrated to lead, cadmium, mercury contaminated soil it is whole
A region carries out repair process；
4) after conserving 3 days, soil sample is taken by professional standard, is air-dried under natural conditions, carries out Leaching Heavy Metals detection,
Testing result is shown in Table 6, it is known that maintenance 3 days, leaching concentration meets " Groundwater Environmental Quality standard " (GB/T in soil
14848-2017) IV class quality standard is selected by reparation medicament described in the present embodiment using in-situ immobilization treated Chenzhou
Mine factory periphery plough (paddy field) soil so that in farmland the heavy metal stabilizations such as lead, cadmium, mercury to lose biological effectiveness not by
Crops absorb, and ensure that the safety of food.
6 Chenzhou, Hunan Province dressing plant periphery of table arable land (paddy field) soil remediation effect situation
Reparation medicament proposed by the present invention for handling heavy-metal contaminated soil can rapidly and efficiently control heavy metal-polluted
Dye can be directed to the repairing and treating of lead, cadmium, mercury heavy-metal contaminated soil, heavy metal ion easy to migrate can be passed through absorption, network
The modes such as conjunction, precipitating are stabilized and are formed the compound of indissoluble difficulty migration, and keep preferable stability.Various ingredients it
Between mutual synergistic effect it is good, lead, cadmium, the heavy metal complete stabilityization in mercury contaminated soil can be made to lose biology
Validity removes heavy metal from soil, and repairing effect is good.Application of the soil-repairing agent in rehabilitating soil shows steady
It is good, quick and without secondary pollution to determine effect.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Each technical characteristic of embodiment described above can carry out arbitrarily
Combination, for simplicity of description, it is not all possible to each technical characteristic in above-described embodiment combination be all described, so
And as long as there is no contradiction in the combination of these technical features, it all should be considered as described in this specification.
Claims (10)
1. a kind of for handling the reparation medicament of heavy-metal contaminated soil, which is characterized in that in parts by weight, including it is following
Component: thio guanidine radicals formates -10-50 parts of modification biological charcoal compound stabilizer, 10-40 parts of soluble phosphate, sepiolite powder
10-30 parts；Wherein, the thio guanidine radicals formates-modification biological charcoal compound stabilizer passes through six thio guanidine radicals formate solutions
It crosslinks to react with the modification biological charcoal and be prepared.
2. according to claim 1 for handling the reparation medicament of heavy-metal contaminated soil, which is characterized in that six sulphur
It include six thio guanidine radicals potassium formates and/or six thio guanidine radicals sodium formates for guanidine radicals formates.
3. according to claim 1 for handling the reparation medicament of heavy-metal contaminated soil, which is characterized in that the modification
Charcoal, which is impregnated by charcoal through the NaOH solution that concentration is 5%-10%, to be made.
4. according to claim 1 for handling the reparation medicament of heavy-metal contaminated soil, which is characterized in that described solvable
Acid phosphate is one of potassium dihydrogen phosphate, sodium dihydrogen phosphate, calcium dihydrogen phosphate, sodium phosphate, potassium phosphate and calcium phosphate or more
Kind.
5. according to claim 1 for handling the reparation medicament of heavy-metal contaminated soil, which is characterized in that six sulphur
It crosslinks to react with the modification biological charcoal for guanidine radicals formate solution and the thio guanidine radicals formates-modification life is prepared
The specific steps of object charcoal compound stabilizer include: by described six thio guanidine radicals formates and the modification biological charcoal by the ratio of 1:3~4
After example mixing, water is added according to solid-to-liquid ratio 1:8~10, is passed through carbon dioxide gas while 2~3h is stirred at 40 DEG C~45 DEG C
Body is made.
6. according to claim 1 for handling the reparation medicament of heavy-metal contaminated soil, which is characterized in that the Hai Pao
The partial size of stone≤200 mesh, sedimentation value >=850.
7. it is a kind of described in any one of claims 1-6 for handling the preparation method of the reparation medicament of heavy-metal contaminated soil,
Characterized by comprising the following steps:
1) six thio guanidine radicals formates are crosslinked to react with modification biological charcoal and thio guanidine radicals formates-modification biological charcoal is made
Compound stabilizer；
2) by the thio guanidine radicals formates-modification biological charcoal compound stabilizer, soluble phosphate and sepiolite powder according to matching
Than being mixed to get mixture, the mixture is mixed with water according to 1~20:100 of mass ratio later, and stir evenly mixing,
The reparation medicament is made.
8. preparation method according to claim 7, which is characterized in that in step 1), the six thio guanidine radicals formates
Solution, which crosslinks to react with the modification biological charcoal, is prepared the thio guanidine radicals formates-modification biological charcoal stable composition
The specific steps of agent include: after mixing described six thio guanidine radicals formates and the modification biological charcoal in the ratio of 1:3~4, to press
Water is added according to solid-to-liquid ratio 1:8~10, is passed through carbon dioxide gas while 2~3h is stirred at 40 DEG C~45 DEG C and is made.
9. preparation method according to claim 7, which is characterized in that in step 1), the modification biological charcoal pass through by
Charcoal is soaked in the NaOH solution that concentration is 5%-10% and is made.
10. a kind of reparation medicament described in any one of claims 1-6 for handling heavy-metal contaminated soil is in rehabilitating soil
In application, which is characterized in that according to the weight for repairing medicament be the 2%-10% of soil weight by the reparation medicament
It is blended with the soil.
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