CN110238185A - A kind of repair materials and its restorative procedure of heavy-metal contaminated soil - Google Patents
A kind of repair materials and its restorative procedure of heavy-metal contaminated soil Download PDFInfo
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- CN110238185A CN110238185A CN201910513683.3A CN201910513683A CN110238185A CN 110238185 A CN110238185 A CN 110238185A CN 201910513683 A CN201910513683 A CN 201910513683A CN 110238185 A CN110238185 A CN 110238185A
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- Prior art keywords
- repair materials
- heavy
- contaminated soil
- phosphate
- metal contaminated
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a kind of repair materials of heavy-metal contaminated soil and its restorative procedures.It include repair materials A and repair materials B in the repair materials, repair materials of the invention are not limited by heavy metal pollution of soil degree, good repairing effect is all had to high, medium and low contaminated soil, and, repair materials of the invention all have good repairing effect to various heavy, especially to arsenic, nickel, thallium, copper, lead, zinc, repairing effect reaches 90% or more, this has great importance for the reparation of the soil of various heavy combined pollution.Repair materials of the invention are simple and easy to get, cheap, are conducive to cost control and large-scale production.The method repaired using repair materials of the invention is simple to operation, and time-consuming short effect is good, while can carry out original position or showering, the strong operability in engineer application.
Description
Technical field
The present invention relates to the repair materials of heavy-metal contaminated soil field more particularly to a kind of heavy-metal contaminated soil and its
Restorative procedure.
Background technique
Phosphate fertilizer plant uses the mineral resources such as troilite, bauxite, phosphorus ore as a raw material for production more, these exploitation of mineral resources
And during utilizing, the heavy metal elements such as normal association nickel, chromium, zinc, copper, cadmium, thallium, arsenic, lead.China's production of phosphate fertilizer starts from 1955
Year, in the Phosphate Fertilizer Industry early stage of development, it is not perfect there are seepage control measure due to most of phosphate fertilizer plants the problems such as, production of phosphate fertilizer is processed
The heavy metal element of association is easy to migrate into soil in journey, causes the content of beary metal in soil significantly raised.By to phosphate fertilizer
Factory's resettlement ruins carry out space enrironment investigation discovery: soil heavy metal combined pollution phenomenon leaves phase in place in phosphate fertilizer plant's resettlement
When universal, there are the heavy metals exceeding standards phenomenons such as copper, nickel, lead, arsenic, zinc, thallium in most of phosphate fertilizer plants' resettlement ruins soil, but at present
The application case for leaving contaminated soil of site reparation for phosphate fertilizer plant's resettlement is less, also, place is left in most enterprises resettlement
Contaminated soil remediation case focuses primarily upon the single heavy metals contaminated sites such as chromium (sexavalence), copper, lead, nickel, for heavy metal thallium
Less with the CROSS REFERENCE of other heavy metal element combined pollutions, combined pollution reaction mechanism compared with Single Pollution is also more multiple
It is miscellaneous, it is larger to repair difficulty.Therefore, a kind of repair materials that can repair the various heavies such as arsenic, nickel, thallium, copper, lead simultaneously are developed to repair
Multiple phosphate fertilizer plant's resettlement leaves contaminated soil of site and is of great significance.
Currently, the common recovery technique of heavy-metal contaminated soil mainly has elution technique, phytoremediation technology, electronation
Method recovery technique, curing/stabilizing technology etc..Wherein, curing/stabilizing technology is since easy to operate, repairing effect is good, nothing two
Secondary pollution, the features such as economic cost is low, are widely used in heavy metal pollution site remediation engineering.Curing/stabilizing technology
It is the addition heavy metals immobilization stabilizer into soil, by the way that active form heavy metal is converted to stabilization using physical-chemical reaction
Form heavy metal, to reduce the transfer ability and biological effectiveness of heavy metal in soil.It is common in curing/stabilizing technology
Medicament mainly has cement, basic matterial etc., these medicament centerings, low concentration heavy metal have good repairing effect, and
It is only applicable to the more single place of remediating heavy metal type, but there are heavy metal types to answer since place is left in phosphate fertilizer plant's resettlement
It is miscellaneous, content is high, and be difficult to reach expected reparation containing difficult points, the above-mentioned curing and stabilizing agents such as the heavy metal thallium administered is difficult to
Effect, has a certain limitation in practical applications, thus it is necessary to develop a kind of suitable high concentration and various heavy is compound
The repair materials of pollution.
Summary of the invention
The purpose of the present invention is to provide a kind of repair materials of heavy-metal contaminated soil and its restorative procedures.
The technical solution used in the present invention is:
One of the objects of the present invention is to provide a kind of repair materials of heavy-metal contaminated soil, which includes to repair
Multiple materials A and repair materials B, wherein repair materials A includes calcium salt and phosphate, material B include silica, natural minerals and
Iron powder.
Preferably, calcium salt and phosphatic mass ratio are (0.35~2.5) in above-mentioned repair materials A: 1；Preferably (0.5
~1.5): 1；More preferably (0.8~1.2): 1.
Preferably, in above-mentioned repair materials B silica, natural minerals and iron powder mass ratio are as follows: (3~10): (1~
3): 1；More preferably (3~6): (1.5~2.5): 1.
Preferably, above-mentioned calcium salt is selected from least one of calcium oxide, calcium hydroxide.
Preferably, above-mentioned calcium salt is selected from calcium oxide and calcium hydroxide.
Preferably, the mass ratio of above-mentioned calcium oxide and calcium hydroxide is (0.15~1): 1；Preferably (0.3~0.7): 1；
More preferably (0.3~0.5): 1.
Preferably, above-mentioned phosphate is in dipotassium hydrogen phosphate, disodium hydrogen phosphate, diammonium hydrogen phosphate, potassium phosphate, sodium phosphate
At least one.
Preferably, above-mentioned phosphate is selected from dipotassium hydrogen phosphate and disodium hydrogen phosphate.
Preferably, the mass ratio of above-mentioned dipotassium hydrogen phosphate and disodium hydrogen phosphate is (0.1~1): 1；More preferably (0.3~
0.7): 1.
Preferably, above-mentioned repair materials A includes calcium oxide, calcium hydroxide, dipotassium hydrogen phosphate and disodium hydrogen phosphate.
Preferably, the mass ratio of calcium oxide, calcium hydroxide, dipotassium hydrogen phosphate and disodium hydrogen phosphate is (0.5~1): (1
~3): (0.3~1.5): (1.5~2.5)；More preferably (0.3~0.7): (1~1.5): (0.3~0.7): (1.5~2).
Preferably, above-mentioned natural minerals are selected from least one of kaolin, concave convex rod bentonite, sepiolite.
Preferably, above-mentioned calcium salt and phosphatic partial size stand alone as 120~200 mesh.
Preferably, above-mentioned silica, natural minerals, iron powder partial size stand alone as 80~120 mesh.
Another object of the present invention is to provide a kind of restorative procedures of heavy-metal contaminated soil, include the following steps:
1) repair materials A is carried out mixing maintenance with heavy-metal contaminated soil；
2) repair materials B is added and carries out maintenance reparation.
Preferably, the curing time of step 1) is 2.5~3h；More preferably 3h.
Preferably, the curing time of step 2) is 4~5h；More preferably 4.5~5h.
Preferably, the mass ratio of above-mentioned heavy-metal contaminated soil, repair materials A and repair materials B is 100:(3.3~8):
(2.5~7)；More preferably 100:(3.3~5.3): (3~4.5).
Preferably, the heavy metal in above-mentioned heavy-metal contaminated soil include arsenic, nickel, thallium, copper, mercury, lead, aluminium, in zinc extremely
Few one kind.
Preferably, the heavy metal in above-mentioned heavy-metal contaminated soil is arsenic, nickel, thallium, copper, lead, zinc.
Preferably, the partial size of above-mentioned contaminated soil is 0.5~10cm.
Preferably, the moisture content of above-mentioned contaminated soil is 10~25%.
Preferably, above-mentioned heavy-metal contaminated soil is phosphate fertilizer plant's soil.
The beneficial effects of the present invention are:
1, repair materials of the invention are not limited by heavy metal pollution of soil degree, equal to high, medium and low contaminated soil
With good repairing effect, also, repair materials of the invention all have good repairing effect to various heavy, especially
It is to arsenic, nickel, thallium, copper, lead, zinc, repairing effect reaches 90% or more, this soil for various heavy combined pollution
Reparation have great importance.
2, repair materials of the invention are simple and easy to get, cheap, are conducive to cost control and large-scale production.
3, the method repaired using repair materials of the invention is simple to operation, and time-consuming short effect is good, simultaneously
It can carry out original position or showering, the strong operability in engineer application.
Detailed description of the invention
Fig. 1 is the heavy metal in soil bio-available Zn concentration variation histogram that embodiment 3 repairs front and back.
Specific embodiment
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art are according to the present invention
Some nonessential modifications and adaptations that the principle of elaboration is made all belong to the scope of protection of the present invention.Following specific works of example
Skill parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this patent
Selection in range, and do not really want to be defined in hereafter exemplary specific data.
Embodiment 1
A kind of heavy-metal contaminated soil repair materials, including repair materials A and repair materials B, wherein repair materials A packet
Include 7.5g industrial oxidation calcium, 22.5g calcium hydroxide, 10g dipotassium hydrogen phosphate, 17.5g disodium hydrogen phosphate；Repair materials B includes
18.2g silica, 4.5g natural minerals, 2.3g iron powder.
A kind of restorative procedure of heavy-metal contaminated soil, includes the following steps:
1) phosphate fertilizer plant contaminated soil 1000g is taken, wherein the content of heavy metal arsenic is 350mg/kg, the content of copper is
4000mg/kg, lead content be 2700mg/kg, the content of nickel is 420mg/kg, the content of zinc is 6000mg/kg, the content of thallium
For 12mg/kg, and it is partial size < 100mm particle in 2L extraction flask by soil breaking, repair materials A is added, utilization is convertible
Vibrator GCC-D conserves reaction 3h with 30r/min；
2) repair materials B is added in step 1), reaction 4.5h is conserved with 30r/min using convertible vibrator GCC-D.
After reparation, according to " solid waste Leaching method level shakes method " (HJ557) to treated
Pedotheque carries out leaching process, the results showed that and the heavy metal in soil Leaching after repaired reduces 92%~98%,
Reach " groundwater quality standard (GBT-14848-2017) " IV class standard.
Embodiment 2
A kind of heavy-metal contaminated soil repair materials, including repair materials A and repair materials B, wherein repair materials A packet
Include 15g industrial oxidation calcium, 45g calcium hydroxide, 15g dipotassium hydrogen phosphate, 45g disodium hydrogen phosphate；Repair materials B includes 58.2g bis-
Silica, 14.6g natural minerals, 7.2g iron powder.
A kind of restorative procedure of heavy-metal contaminated soil, includes the following steps:
1) phosphate fertilizer plant contaminated soil 2000g is taken, wherein the content of heavy metal arsenic is 450mg/kg, the content of copper is
5700mg/kg, lead content be 3500mg/kg, the content of nickel is 500mg/kg, the content of zinc is 8300mg/kg, the content of thallium
For 22mg/kg, and it is partial size < 100mm particle in 2L extraction flask by soil breaking, repair materials A is added, utilization is convertible
Vibrator GCC-D conserves reaction 2.5h with 30r/min；
2) repair materials B is added in step 1), reaction 5h is conserved with 30r/min using convertible vibrator GCC-D.
After reparation, according to " solid waste Leaching method level shakes method " (HJ557) to treated
Pedotheque carries out leaching process, the results showed that the heavy metal in soil Leaching after repaired reduces 95%, reaches
" groundwater quality standard (GBT-14848-2017) " III class standard.
Embodiment 3
A kind of heavy-metal contaminated soil repair materials, including repair materials A and repair materials B, wherein repair materials A packet
Include 1080t industrial oxidation calcium, 3100t calcium hydroxide, 1050t dipotassium hydrogen phosphate, 3250t disodium hydrogen phosphate；Repair materials B includes
4146t silica, 1040t natural minerals, 513t iron powder.
A kind of restorative procedure of heavy-metal contaminated soil, includes the following steps:
1) certain phosphate fertilizer plant, city (95000m is chosen3), which is in Acid Rain Zone, and wherein the content of heavy metal arsenic is
490mg/kg, copper content be 6000mg/kg, the content of lead is 3300mg/kg, the content of nickel is 488mg/kg, the content of thallium
It is more than " construction land soil pollution risk management and control standard " first kind land used screening value for 25mg/kg, and utilizes crushing and screening
Equipment carries out crushing and screening to contaminated soil, and removal of impurities makes soil particle diameter between 0.5~10cm, and repair materials A, benefit is then added
Repair materials A and contaminated soil are carried out with soil remediation all-in-one machine to be sufficiently mixed maintenance 3h；
2) repair materials B, mixing maintenance 5h are added in step 1).
After reparation, according to " solid waste Leaching method level shakes method " (HJ557) to treated
Pedotheque carries out leaching process, and repairing front and back heavy metal in soil bio-available Zn concentration see the table below 1, the results showed that after repaired
Heavy metal in soil Leaching reduce 90% or more (Fig. 1), reach " groundwater quality standard (GBT-14848-
2017) " IV class standard.
Heavy metal bio-available Zn concentration before and after 1 soil remediation of table
Note: Ni is without standard value in groundwater quality standard (GBT-14848-2017), using " surface water environment quality mark
It is quasi- " value of Ni is to repair target value in GB3838-2002.
Claims (10)
1. a kind of repair materials of heavy-metal contaminated soil, it is characterised in that: the repair materials include repair materials A and reparation
Material B, wherein the repair materials A includes calcium salt and phosphate, and the material B includes silica, natural minerals and iron
Powder.
2. repair materials according to claim 1, it is characterised in that: calcium salt and phosphatic matter in the repair materials A
Amount is than being 0.35~2.5:1.
3. repair materials according to claim 1, it is characterised in that: silica, natural minerals in the repair materials B
With the mass ratio of iron powder are as follows: 3~10:1~3:1.
4. repair materials according to any one of claims 1 to 3, it is characterised in that: the calcium salt is selected from calcium oxide, hydrogen
At least one of calcium oxide；Preferably, the calcium salt is selected from calcium oxide and calcium hydroxide；Preferably, the calcium oxide and hydrogen
The mass ratio of calcium oxide is 0.15~1:1.
5. repair materials according to any one of claims 1 to 3, it is characterised in that: the phosphate is selected from phosphoric acid hydrogen
At least one of dipotassium, disodium hydrogen phosphate, diammonium hydrogen phosphate, potassium phosphate, sodium phosphate；Preferably, the phosphate is selected from phosphorus
Sour hydrogen dipotassium and disodium hydrogen phosphate；Preferably, the mass ratio of the dipotassium hydrogen phosphate and disodium hydrogen phosphate is 0.1~1:1.
6. repair materials according to any one of claims 1 to 3, it is characterised in that: the natural minerals are selected from kaolinite
At least one of soil, concave convex rod bentonite, sepiolite；Preferably, it states calcium salt and phosphatic partial size stands alone as 120~200
Mesh；Preferably, silica, natural minerals, iron powder partial size stand alone as 80~120 mesh.
7. a kind of restorative procedure of heavy-metal contaminated soil, characterized by the following steps:
1) repair materials A is carried out mixing maintenance with heavy-metal contaminated soil；
2) repair materials B is added and carries out maintenance reparation.
8. restorative procedure according to claim 7, it is characterised in that: the curing time of step 1) is 2.5~3h；It is preferred that
Ground, the curing time of step 2) are 4~5h.
9. restorative procedure according to claim 7 or 8, it is characterised in that: the heavy-metal contaminated soil, repair materials A
With the mass ratio of repair materials B are as follows: 100:3.3~8:2.5~7；Preferably, the heavy metal packet in the heavy-metal contaminated soil
Include at least one of arsenic, nickel, thallium, copper, mercury, lead, aluminium, zinc.
10. restorative procedure according to claim 7 or 8, it is characterised in that: the partial size of the heavy-metal contaminated soil is
0.5~10cm；Preferably, the moisture content of the heavy-metal contaminated soil is 10~25%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112920807A (en) * | 2021-02-03 | 2021-06-08 | 清华大学 | Heavy metal contaminated soil remediation material, preparation method thereof and remediation method of heavy metal contaminated soil |
| CN113182338A (en) * | 2021-04-25 | 2021-07-30 | 三明学院 | Method for restoring molybdenum-polluted soil by ultrasonic/oscillation-assisted chemical leaching |
| CN114106839A (en) * | 2021-12-22 | 2022-03-01 | 中电建十一局工程有限公司 | Zinc-polluted soil stabilizing material and preparation method thereof |
| CN115041128A (en) * | 2022-05-26 | 2022-09-13 | 中国地质大学（武汉） | Mineral-based heavy metal pollution repairing agent and preparation method and application thereof |
| CN115069207A (en) * | 2022-05-13 | 2022-09-20 | 中南大学 | Material with scaly pyrite nanosheets growing in situ on foamed iron and preparation method and application thereof |
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Application publication date: 20190917 |