CN108905961A - A kind of restorative procedure in cadmium zinc pollution river - Google Patents
A kind of restorative procedure in cadmium zinc pollution river Download PDFInfo
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- B01J20/16—Alumino-silicates
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- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
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Abstract
A kind of restorative procedure in cadmium zinc pollution river, includes the following steps：（1）Prepare the absorption stabilizing and curing agent based on Zeolite modifying, 1. zeolite, 2. by particulate zeolites high-temperature process, is 3. placed in NaOH solution and handles by clinoptilolite is broken, grinding and screening, 4. zeolite is placed in zirconyl chloride solution processing, the absorption stabilizing and curing agent based on Zeolite modifying is 5. obtained；（2）Improvement reparation is carried out to Cd, Zn polluted river channel using the absorption stabilizing and curing agent based on Zeolite modifying, 1. the absorption of polluted river water is administered, dredging and curing process 2. are carried out to polluted river channel bed mud, pollution by dredging bed mud is 3. repaired by ecological slope protection.This method is high temperature modified to natural zeolite progress, NaOH is modified and the processing such as zirconium oxychloride is modified, prepare the absorption stabilizing and curing agent based on Zeolite modifying, comprehensive improvement is carried out together in combination with Channel slope regulation and River Landscape transformation, regulation effect is good, easy to operate, being compatible with the environment property is good, and removal is accurate.
Description
Technical field
The present invention relates to a kind of restorative procedures for cadmium zinc pollution river, belong to Heavy Metal Pollution Control technical field.
Background technique
Traditional river Heavy Metal Pollution Control technology mainly first investigates Heavy Metal Pollution in Sediments situation, in cutting external source
In the case that heavy metal inputs, bed mud heavy metal is repaired.Major technique type has peripheral doses, chemical remediation and biological prosthetic three
Kind.Peripheral doses project amount is big, and Dredged bed mud still needs to one processing disposition of progress.Chemical remediation needs to put into a large amount of medicaments, cost
Height, reaction condition are not easy to control, and the medicament being not efficiently used can cause secondary pollution to environment, and cannot fundamentally by
Except heavy metal removing river arrives in river bottom mud.
The processing method in the river containing heavy metal disclosed in Chinese patent literature CN201710812098.4, bed mud is placed in super
Concussion processing is carried out in sound wave shock instrument, makes its emulsification, in the practical harnessing project of river bottom mud, can not be implemented on a large scale.
A kind of ecological treatment method in heavy metal pollution river, need to add flocculant and gold into river disclosed in 201711473810.9
Belong to the heavy metal ion in trapping agent removal river, secondary pollution is caused to river, heavy metal in river can not thoroughly be gone
It removes.
Due to comprehensive, the complexity of heavy metal pollution river regulation, improvement is big, the period is long, and regulation effect is good, grasps
Making restorative procedure simple, that being compatible with the environment property is good is always that people inquire into and urgent need to resolve.
Summary of the invention
The present invention provides a kind of simple process, practical for deficiency existing for existing waterway Heavy Metal Pollution Control technology
The cadmium zinc pollution river (cadmium pollution river, zinc pollution river and or the common polluted river channel of cadmium zinc) that property is strong, regulation effect is good
Restorative procedure.
The restorative procedure in cadmium zinc pollution of the present invention river, includes the following steps：
(1) the absorption stabilizing and curing agent based on Zeolite modifying is prepared:
1. clinoptilolite crosses 18-5 mesh after broken, screening and grinding, after being rinsed well with deionized water, obtain
Partial size is the zeolite of 1.0-4.0mm；
2. the particulate zeolites for taking step 1. to obtain 450-550 DEG C of roasting in Muffle furnace, removes and deposits in its hole and hole
Impurity and hydrone (active zeolite, make its internal surface area increase, improve the adsorption capacity of zeolite), roasting 2-4 hours after,
It is cooled to room temperature；
3. the modified zeolite for taking step 2. to obtain in mass ratio 1:The ratio of 20-30 is placed in concentration 1.0-3.0mol/L's
(increase the pore volume of zeolite, enhance the adsorption capacity to heavy metal cation) in NaOH solution, 90-105 DEG C of heating water bath
2.5-3.5 hours, 220-260 revs/min isothermal vibration 9-11 hours, be sufficiently mixed zeolite with NaOH solution, by supernatant
It pours out, is cleaned with deionized water, 105 DEG C drying 2-4 hours in baking oven；
4. the modified zeolite for taking step 3. to obtain in mass ratio 1:The ratio of 5-15 is placed in the oxygen of concentration 0.1-0.2mol/L
Zirconium chloride (ZrOCl2) twice-modified, (inner passage of dredging zeolite, improve the adsorption capacity of zeolite) is carried out in solution.It is placed in
The magnetic agitation instrument that revolving speed is 1600-1800 revs/min stirs 3-5 hours, and modified zeolite is made to be in suspended state.
5. 4. mixed solution that step is obtained is adjusted to pH 9-11 (with concentration 2mol/L NaOH solution), then carry out
After separation of solid and liquid, using deionized water cleaning solid to supernatant pH 6.5-7.5, then solid is placed in 105 DEG C of baking oven
It dries to get the absorption stabilizing and curing agent of modified zeolite is arrived；
(2) improvement reparation is carried out to Cd and Zn polluted river channel using the absorption stabilizing and curing agent based on Zeolite modifying：
1. the absorption to polluted river water is administered：
Absorption stabilizing and curing agent is fitted into mesh bag, in the two sides approximately level setting gabion slope protection of polluted river channel, gabion
Upper layer and lower layer filler is set, and lower layer is block stone (playing the role of slope protection), and upper layer is the mesh bag equipped with absorption stabilizing and curing agent, is used
Heavy metal Cd and Zn pollutant in adsorbed water body；
The partial size of the absorption stabilizing and curing agent is 1.0-4.0mm, and mesh bag perforation size is 50-140 mesh.
The mesh bag is having a size of 10-50cm × 10-50cm × 10-50cm.
The gabion is mild steel wire outsourcing PVC material, and size of mesh opening is 3-10cm × 3-10cm.
The thickness proportion of upper layer filler and lower layer's filler is 1 in the gabion:1-3.
Net door is set at the top of the gabion, when zeolite adsorbed water body heavy metal ion especially Cd and Zn ion reaches saturation
Afterwards, net door is opened, mesh bag is replaced.
2. carrying out dredging and curing process to polluted river channel bed mud：
Strand is utilized in the case where preventing polluted bed mud from suspending and diffusion for river heavy metal Cd and Zn polluted bed mud
Absorbing dredge boat, which will twist polluted bed mud, to be inhaled and is pumped into the bed mud of river bank and temporarily solidify place, temporarily solidify place bottom and
Surrounding carries out Anti-seeping technology, and after temporarily Dredged bed mud is carried out screening process by solidification place, the sandstone for removing 2-5mm or more is miscellaneous
The lower bed mud of sieve in beta site desiccation to moisture content is 20-30% by object.
If Cd concentration is less than 10mg/kg in the bed mud under sieve, and Zn pollution concentration is less than 1000mg/kg, into bed mud
The absorption stabilizing and curing agent based on Zeolite modifying is added by the weight ratio of 10-14%, and stirs and is sufficiently mixed, is solidified 7-10 days
It is used for the planting soil of subsequent river channel ecology slope protection afterwards.If Cd concentration is polluted in 10mg/kg or more or Zn in the bed mud under sieve
Concentration then carries out the leach toxicity test of heavy metal in 1000mg/kg or more to it, if exceeding leaching characteristic identification mark
Quasi- value (foundation《Hazardous waste judging standard leaching characteristic identification》(GB 5085.3-2007)), it is carried out at processing by hazardous waste
It sets；If adding the absorption based on Zeolite modifying without departing from the standard by the weight ratio of 15-20% into bed mud and stablizing admittedly
Agent, and stir and be sufficiently mixed, the planting soil of subsequent river channel ecology slope protection is used for after solidifying 7-10 days；
The occurrence patterns of heavy metal Cd and Zn change in bed mud after curing process, turn from labile state to stable state
Become, wherein the residual form ratio of Cd increases 43-48%, in bed mud the Cd of 32-36% with Acid extractable and can reduction-state exist
It is converted into relatively stable residual form；The residual form ratio of Zn increases 16-20%, and the Zn of 18-22% is extractable with acid in bed mud
State and can reduction-state exist be converted into relatively stable oxidable state and residual form, effectively reduce heavy metal Cd and Zn to environment
Harm.As planting soil, the migration of interior heavy metal Cd and Zn die down curing process bed mud, can effectively prevent or reduce because
Heavy metal imports the risk in river with precipitation again in slope protection soil, and this Cd and Zn pollution planting soil is suitable for taking water plant
Further ecology enrichment is repaired, and solves the handling problems of polluted bed mud after current bed mud ecological, environmental protective dredging.
3. repairing pollution by dredging bed mud by ecological slope protection：
Under the premise of not influencing river water conservancy trade culture, Channel slope is rebuild, will temporarily be solidified at the solidification in place
Bed mud is managed as river channel ecology slope protection planting soil, is meeting suitable season, the plant of plantation enrichment Cd and Zn, plant on slope protection
By plant harvesting before withered, burning disposal is carried out after drying.
The curing process bed mud is 20-40m as the cladding thickness of planting soil.
The plant of the plantation enrichment Cd and Zn, is to sow penny cress in late March, type of seeding uses drilling, line-spacing
15-20cm is sowed, shallow ridges depth 1.5-2.5cm is opened, uniformly seed is sowed in ditch；Polygonum aubertii is being transplanted around Clear and Bright, is being chosen to
Ripe branch, by distance between rows and hills 15cm × 5cm insertion slope protection planting soil.Penny cress and Polygonum aubertii are enterprising in the different plot of slope protection
Row intersects plantation, and wheel is carried out on same plot and grows plantation (rotation in 1 year).
The root system of enriching plant can will solidify the heavy metal Cd in bed mud and Zn and gradually shift enrichment to groups such as plant stem-leafs
In knitting.Before plant is withered, by heavy metal accumulation plant harvesting, dry after, carry out burning disposal, and carry out flying dust trapping and remaining
Bottom ash disposing task, to be processed and disposition amount have greatly reduced compared to Dredged bed mud.According to weight in flying dust and remaining bottom ash
The leach toxicity test of metal and《Hazardous waste judging standard leaching characteristic identification》(GB 5085.3-2007), such as beyond danger
The judging standard value of waste carries out processing disposition by hazardous waste；To the flying dust that does not reach hazardous waste judging standard value and residual
Remaining bottom ash, is pressed《General industry waste storage, disposal site contamination control standard》(GB18599-2001) it is handled and is disposed.
The present invention is used as substrate using extensive, the cheap zeolite of material source, by suitably modified, provides its absorption and surely
The performance for determining heavy metal carries out comprehensive treatment to heavy metal Cd and Zn polluted river channel in conjunction with river channel ecology slope protection etc., and this method can
Carry out comprehensive improvement together in conjunction with Channel slope regulation and River Landscape transformation, regulation effect is good, it is easy to operate, be compatible with the environment
Property is good.
The present invention carries out that high temperature modified, NaOH is modified to natural zeolite and processing, the preparation such as rare earth modified zirconia are based on zeolite
Modified absorption stabilizing and curing agent, the height for heavy metal Cd and Zn in the high-efficiency adsorbent and bed mud of heavy metal in water Cd and Zn
Imitate stabilizing and curing agent.For the river that heavy metal Cd and Zn pollute, river water body pollution control, river bottom mud environmental dredging are taken
Curing process, pollution by dredging bed mud ecological slope protection three kinds of methods of reparation reach to the comprehensive comprehensive of heavy metal Cd and Zn polluted river channel
It closes and administers.
The invention has the characteristics that：
1. preparing modified particles zeolite as substrate using clinoptilolite adsorbs stabilizing and curing agent, raw material is easy to get, cheap.
2. repairing cadmium zinc pollution river using modified particles zeolite, river water quality can be purified and repair river bottom mud,
Littoral landscape can also be improved, it is easy to operate, it is applied widely.
3. can be realized the accurate removal to cadmium zinc in polluted river channel.
Detailed description of the invention
Fig. 1 gives the suction of absorption stabilizing and curing agent adsorbed water body cadmium and zinc ion in embodiment 1 based on Zeolite modifying
Attached isollaothermic chart, wherein (a) is cadmium sorption isollaothermic chart, it is (b) zinc ion adsorption isotherm map.
Fig. 2 gives the fractions distribution that Cd and Zn in bed mud under stabilizing and curing agent different administration ratio is adsorbed in embodiment 1
Variation diagram, wherein (a) is the fractions distribution variation diagram of Cd in bed mud under different administration ratio, it is (b) different administration ratio bottom
The fractions distribution variation diagram of Zn in mud.
Fig. 3 gives the electron microscope in embodiment 2 before Zeolite modifying.
Fig. 4 gives in embodiment 2 (the absorption stabilizing and curing agent 2 based on Zeolite modifying after Zeolite modifying#) electron microscope.
Fig. 5 provides the figure of the FTIR in the present embodiment 2 before and after Zeolite modifying, wherein upper solid line is natural zeolite；Middle solid line：It is high
The modified zeolite of temperature；Lower solid line：Zeolite (the absorption stabilizing and curing agent based on Zeolite modifying after high temperature, NaOH and modified zirconia
2#)
Specific embodiment
Embodiment 1
1. preparing the absorption stabilizing and curing agent 1 based on Zeolite modifying#
(1) clinoptilolite crosses 18 meshes after broken, screening and grinding, after being rinsed well with deionized water, obtains grain
Diameter is the zeolite of 1.0mm.
(2) particulate zeolites for taking step (1) to obtain 450 DEG C of roastings in Muffle furnace, remove and exist in its hole and hole
Impurity and hydrone, roasting 2 hours after, be cooled to room temperature.
(3) modified zeolite in mass ratio 1 for taking step (2) to obtain:The NaOH that 20 ratio is placed in concentration 1.0mol/L is molten
In liquid, 90 DEG C heating water bath 2.5 hours, 220 revs/min isothermal vibration 9 hours, be sufficiently mixed zeolite with NaOH solution.It will
Supernatant is poured out, and is cleaned with deionized water, is dried 2 hours for 105 DEG C in baking oven.
(4) modified zeolite in mass ratio 1 for taking step (3) to obtain:5 ratio is placed in the zirconium oxychloride of concentration 0.1mol/L
(ZrOCl2) carry out in solution it is twice-modified.It is placed in the magnetic agitation instrument that revolving speed is 1600 revs/min to stir 3 hours, makes to be modified
Zeolite is in suspended state.
(5) mixed solution that step (4) obtains is adjusted to pH 9 (with concentration 2mol/L NaOH solution), then carried out
After separation of solid and liquid, using deionized water cleaning solid to supernatant pH 6.5, then solid is placed in 105 DEG C of baking oven and is dried
It does to get the absorption stabilizing and curing agent 1 based on Zeolite modifying is arrived#。
2. adsorbing stabilizing and curing agent 1#Improvement reparation to heavy metal Cd or Zn polluted river channel water body and bed mud
(1) to the improvement of polluted river channel water body
Choose the absorption stabilizing and curing agent 1 that diameter is 1.0mm#, in the nylon net bag of 50 mesh, mesh bag is having a size of 10cm
×10cm×10cm；The gabion slope protection of PVC material, gabion material are wrapped up in the two sides approximately level setting mild steel wire of polluted river channel
For mild steel wire outsourcing PVC material, size of mesh opening is 3cm × 3cm；Two layers of filler point in gabion, bottom, that is, gabion bottom dress
Enter block stone, plays the role of slope protection, upper layer, that is, block stone top is put into the nylon net bag equipped with zeolite adsorbents, for adsorbing water
The thickness proportion of heavy metal Cd and Zn pollutant in body, upper layer and lower layer is 1:1；Steel wire at the top of gabion, which is provided with, can be taken off
The chain link door of nylon net bag.It is openable after especially Cd and Zn ion reaches saturation to zeolite adsorbed water body heavy metal ion
Chain link door is replaced into the nylon net bag equipped with fresh modified zeolite, is continued water pollution removal and is controlled until reaching water body
Manage target.
Fig. 1 gives the absorption of absorption stabilizing and curing agent adsorbed water body cadmium, zinc ion in the present invention based on Zeolite modifying
Isollaothermic chart, wherein (a) is cadmium sorption isollaothermic chart, it is (b) zinc ion adsorption isotherm map.
(2) river bottom mud environmental dredging and curing process
For river heavy metal polluted bed mud (predominantly Cd and Zn pollution), ecological, environmental protective dredging is carried out, is preventing from polluting
Bed mud suspend and diffusion in the case where, using cutter suction dredger by by polluted bed mud twists suction and be pumped into river bank bed mud it is interim
Solidify place.Temporarily solidify place bottom and surrounding using compound HDPE film progress Anti-seeping technology, HDPE film with a thickness of
0.75mm, two sides compound nonwoven cloth.From the bed mud of the training of channel after beta site desiccation to moisture content is 20%, Cd in bed mud
Pollution concentration is that 0.3-0.6mg/kg or Zn pollution concentration is 250-750mg/kg, need to be added based on Cd and Zn polluted bed mud concentration
Add the proportional relation of curing agent ratio, adding proportion is the absorption stabilizing and curing agent 1 of polluted bed mud weight 10%-12% mass#,
Make to adsorb stabilizing and curing agent 1 using blender#It is sufficiently mixed with bed mud, the kind of subsequent river channel ecology slope protection is used for after solidifying 7 days
Plant soil.
After solidification, the occurrence patterns of heavy metal Cd and Zn change in bed mud, change from labile state to stable state,
In, the residual form ratio of Cd increases 43-44%, in bed mud the Cd of 32-34% with Acid extractable and can reduction-state there is conversion
For relatively stable residual form；The residual form ratio of Zn increases 16-18%, in bed mud the Zn of 18-20% with Acid extractable and
Can reduction-state exist be converted into relatively stable oxidable state and residual form, effectively reduce heavy metal Cd and Zn to the danger of environment
Evil.
Fig. 2 gives the fractions distribution variation diagram of Cd and Zn in bed mud under absorption stabilizing and curing agent different administration ratio,
In (a) be Cd in bed mud under different administration ratio fractions distribution variation diagram, (b) be Zn in bed mud under different administration ratio shape
State changes in distribution figure.
(3) pollution by dredging bed mud is repaired by ecological slope protection
The cured bed mud of modified zeolite in place will temporarily be solidified as river channel ecology slope protection planting soil, in the planting soil
Heavy metal Cd and the migration of Zn die down, can effectively prevent or reduce because slope protection soil in heavy metal with precipitation due to import river again
Risk, and this Cd and Zn pollution planting soil be suitable for take water plant further ecology enrichment repair.Do not influencing urban river water
Under the premise of sharp trade culture, Channel slope is rebuild, the cured bed mud of modified zeolite can be as the cladding thickness of planting soil
20cm.Suitable season can be met, the plant of super enrichment Cd and Zn are planted on slope protection.Such as penny cress, sowing are sowed in late March
Method uses drilling, and line-spacing sows 15cm, opens shallow ridges depth 1.5cm, uniformly seed is sowed in ditch；Mountain buckwheat is transplanted before and after Clear and Bright
Wheat selects mature branch, by distance between rows and hills 15cm × 5cm insertion slope protection planting soil.The root system of enriching plant can be by cured base
Heavy metal Cd and Zn in mud gradually shift in enrichment to the tissues such as plant stem-leaf.Before plant is withered, by heavy metal accumulation plant
After gathering in, drying, burning disposal is carried out, and carries out flying dust trapping and remaining bottom ash disposing task, to be processed and disposition amount are compared
Greatly reduce in Dredged bed mud.According to the leach toxicity test of heavy metal in flying dust and remaining bottom ash and《Hazardous waste mirror
Other standard leaching characteristic identification》(GB 5085.3-2007), reaches the standard of hazardous waste, carries out at processing by hazardous waste
It sets；To the flying dust for not reaching hazardous waste standard and remaining bottom ash, press《General industry waste storage, disposal site contamination control mark
It is quasi-》(GB18599-2001) it is handled and is disposed.
Embodiment 2
1. preparing the absorption stabilizing and curing agent 2 based on Zeolite modifying#
(1) clinoptilolite crosses 10 meshes after broken, screening and grinding, after being rinsed well with deionized water, obtains grain
Diameter is the zeolite of 2.0mm.
(2) particulate zeolites for taking step (1) to obtain 500 DEG C of roastings in Muffle furnace, remove and exist in its hole and hole
Impurity and hydrone, roasting 2-3 hours after, be cooled to room temperature.
(3) modified zeolite in mass ratio 1 for taking step (2) to obtain:The NaOH that 25 ratio is placed in concentration 2.0mol/L is molten
In liquid, 100 DEG C heating water bath 3 hours, 240 revs/min isothermal vibration 10 hours, be sufficiently mixed zeolite with NaOH solution.It will
Supernatant is poured out, and is cleaned with deionized water, is dried 3 hours for 105 DEG C in baking oven.
(4) modified zeolite in mass ratio 1 for taking step (3) to obtain:10 ratio is placed in the oxychlorination of concentration 0.15mol/L
Zirconium (ZrOCl2) carry out in solution it is twice-modified.It is placed in the magnetic agitation instrument that revolving speed is 1700 revs/min to stir 3.5 hours, make
Modified zeolite is in suspended state.
(5) mixed solution that step (4) obtains is adjusted to pH 10 (with concentration 2mol/L NaOH solution), then carried out
After separation of solid and liquid, using deionized water cleaning solid to supernatant pH 7.0, then solid is placed in 105 DEG C of baking oven and is dried
It does to get the absorption stabilizing and curing agent 2 based on Zeolite modifying is arrived#。
Fig. 3 gives the electron microscope before the present embodiment Zeolite modifying.Fig. 4 (is based on after giving the present embodiment Zeolite modifying
The absorption stabilizing and curing agent 2 of Zeolite modifying#) electron microscope.Fig. 5 gives the FTIR figure before and after the present embodiment Zeolite modifying,
In upper solid line be natural zeolite；Middle solid line：Zeolite after high temperature modified；Lower solid line：The zeolite after high temperature, NaOH and modified zirconia
(the absorption stabilizing and curing agent 2 based on Zeolite modifying#)
2. adsorbing stabilizing and curing agent 2#Improvement reparation to heavy metal Cd or Zn polluted river channel water body and bed mud
(1) to the improvement of polluted river channel water body
Choose the absorption stabilizing and curing agent 2 that diameter is 2.0mm#, in the nylon net bag of 80 mesh, mesh bag is having a size of 25cm
×25cm×25cm；The gabion slope protection of PVC material, gabion material are wrapped up in the two sides approximately level setting mild steel wire of polluted river channel
For mild steel wire outsourcing PVC material, size of mesh opening is 6cm × 6cm；Two layers of filler point in gabion, bottom, that is, gabion bottom dress
Enter block stone, plays the role of slope protection, upper layer, that is, block stone top is put into the nylon net bag equipped with zeolite adsorbents, for adsorbing water
The thickness proportion of heavy metal Cd and Zn pollutant in body, upper layer and lower layer is 1:2；Steel wire at the top of gabion, which is provided with, can be taken off
The chain link door of nylon net bag.It is openable after especially Cd and Zn ion reaches saturation to zeolite adsorbed water body heavy metal ion
Chain link door is replaced into the nylon net bag equipped with fresh modified zeolite, is continued water pollution removal and is controlled until reaching water body
Manage target.
(2) river bottom mud environmental dredging and curing process
For Cd or Zn polluted river channel heavy metal polluted bed mud, ecological, environmental protective dredging is carried out, is preventing polluted bed mud from suspending
And in the case where diffusion, temporarily solidify field for polluted bed mud to be twisted to the bed mud for inhaling and being pumped into river bank using cutter suction dredger
Ground.The bottom for temporarily solidifying place and surrounding are using compound HDPE film progress Anti-seeping technology, and HDPE film is with a thickness of 0.75mm, two sides
Compound nonwoven cloth.From the bed mud of the training of channel after beta site desiccation to moisture content is 25%, Cd pollution concentration is in bed mud
0.6-1.0mg/kg or Zn pollution concentration is 750-1000mg/kg, need to add curing agent ratio based on Cd and Zn polluted bed mud concentration
The proportional relation of example, adding proportion are the absorption stabilizing and curing agent 2 of polluted bed mud weight 12%-14% mass#, utilize blender
Make to adsorb stabilizing and curing agent 2#It is sufficiently mixed with bed mud, the planting soil of subsequent river channel ecology slope protection is used for after solidifying 7 days.
After solidification, the occurrence patterns of heavy metal Cd and Zn change in bed mud, change from labile state to stable state,
In, the residual form ratio of Cd increases 44-48%, in bed mud the Cd of 34-36% with Acid extractable and can reduction-state there is conversion
For relatively stable residual form；The residual form ratio of Zn increases 18-20%, in bed mud the Zn of 20-22% with Acid extractable and
Can reduction-state exist be converted into relatively stable oxidable state and residual form, effectively reduce heavy metal Cd and Zn to the danger of environment
Evil.
(3) pollution by dredging bed mud is repaired by ecological slope protection
The cured bed mud of modified zeolite in place will temporarily be solidified as river channel ecology slope protection planting soil, in the planting soil
Heavy metal Cd and the migration of Zn die down, can effectively prevent or reduce because slope protection soil in heavy metal with precipitation due to import river again
Risk, and this Cd and Zn pollution planting soil be suitable for take water plant further ecology enrichment repair.Do not influencing urban river water
Under the premise of sharp trade culture, Channel slope is rebuild, the cured bed mud of modified zeolite can be as the cladding thickness of planting soil
20cm.Suitable season can be met, the plant of super enrichment Cd and Zn are planted on slope protection.Such as penny cress, sowing are sowed in late March
Method uses drilling, and line-spacing sows 180cm, opens shallow ridges depth 2.0cm, uniformly seed is sowed in ditch；Mountain is being transplanted around Clear and Bright
Buckwheat selects mature branch, by distance between rows and hills 15cm × 5cm insertion slope protection planting soil.
It is consistent described in remaining process and embodiment 1.
Embodiment 3
1. preparing the absorption stabilizing and curing agent 3 based on Zeolite modifying#
(1) clinoptilolite crosses 5 meshes after broken, screening and grinding, after being rinsed well with deionized water, obtains grain
Diameter is the zeolite of 4.0mm.
(2) particulate zeolites for taking step (1) to obtain 550 DEG C of roastings in Muffle furnace, remove and exist in its hole and hole
Impurity and hydrone, roasting 4 hours after, be cooled to room temperature.
(3) modified zeolite in mass ratio 1 for taking step (2) to obtain:The NaOH that 30 ratio is placed in concentration 3.0mol/L is molten
In liquid, 105 DEG C heating water bath 3.5 hours, 260 revs/min isothermal vibration 11 hours, be sufficiently mixed zeolite with NaOH solution.
Supernatant is poured out, is cleaned with deionized water, is dried 4 hours for 105 DEG C in baking oven.
(4) modified zeolite in mass ratio 1 for taking step (3) to obtain:15 ratio is placed in the oxychlorination of concentration 0.2mol/L
Zirconium (ZrOCl2) carry out in solution it is twice-modified.It is placed in the magnetic agitation instrument that revolving speed is 1800 revs/min to stir 5 hours, makes to change
Property zeolite is in suspended state.
(5) mixed solution that step (4) obtains is adjusted to pH 11 (with concentration 2mol/L NaOH solution), then carried out
After separation of solid and liquid, using deionized water cleaning solid to supernatant pH 7.5, then solid is placed in 105 DEG C of baking oven and is dried
It does to get the absorption stabilizing and curing agent 3 based on Zeolite modifying is arrived#。
2. adsorbing stabilizing and curing agent 3#Improvement reparation to heavy metal Cd or Zn polluted river channel water body and bed mud
(1) to the improvement of polluted river channel water body
Choose the absorption stabilizing and curing agent 1 that diameter is 4.0mm#, in the nylon net bag of 140 mesh, mesh bag having a size of
50cm×50cm×50cm；The gabion slope protection of PVC material, gabion are wrapped up in the two sides approximately level setting mild steel wire of polluted river channel
Material is mild steel wire outsourcing PVC material, and size of mesh opening is 10cm × 10cm；Two layers of filler point, bottom, that is, gabion in gabion
Bottom is packed into block stone, plays the role of slope protection, upper layer, that is, block stone top is put into the nylon net bag equipped with zeolite adsorbents, is used for
The thickness proportion of heavy metal Cd and Zn pollutant in adsorbed water body, upper layer and lower layer is 1:3；Steel wire at the top of gabion is provided with
It can be taken off the chain link door of nylon net bag.After especially Cd and Zn ion reaches saturation to zeolite adsorbed water body heavy metal ion,
Openable chain link door is replaced into the nylon net bag equipped with fresh modified zeolite, continues water pollution removal until reaching
Water body treating target.
(2) river bottom mud environmental dredging and curing process
Ecological, environmental protective dredging is carried out for river Cd and Zn polluted bed mud, the case where preventing polluted bed mud from suspending and diffusion
Under, temporarily solidify place for polluted bed mud to be twisted to the bed mud for inhaling and being pumped into river bank using cutter suction dredger.Interim solidification field
The bottom on ground and surrounding are using compound HDPE film progress Anti-seeping technology, and HDPE film is with a thickness of 0.75mm, two sides compound nonwoven cloth.From
The bed mud of the training of channel is after beta site desiccation to moisture content is 30%, and Cd pollution concentration is 1.2mg/kg in bed mud, and Zn is dirty
Dye concentration is 1200mg/kg.The leach toxicity test of heavy metal is carried out to it, the concentration of Zn is 12mg/l in leachate, is lower than
The concentration limits value 100mg/l of its leachate Zn；The concentration 0.2mg/l of Cd in leachate, the concentration limit lower than its leachate Zn
Value 1mg/l processed.The proportional relation of curing agent ratio need to be then added based on Cd or Zn polluted bed mud concentration, adding proportion is pollution bottom
The absorption stabilizing and curing agent 3 of 16% mass of mud weight#, make to adsorb stabilizing and curing agent 3 using blender#It is sufficiently mixed with bed mud, Gu
The planting soil of subsequent river channel ecology slope protection is used for after changing 7 days.
After solidification, the occurrence patterns of heavy metal Cd and Zn change in bed mud, change from labile state to stable state,
In, the residual form ratio of Cd increases 43-47%, in bed mud the Cd of 32-35% with Acid extractable and can reduction-state there is conversion
For relatively stable residual form；The residual form ratio of Zn increases 17-20%, in bed mud the Zn of 20-21% with Acid extractable and
Can reduction-state exist be converted into relatively stable oxidable state and residual form, effectively reduce heavy metal Cd and Zn to the danger of environment
Evil.
(3) pollution by dredging bed mud is repaired by ecological slope protection
The cured bed mud of modified zeolite in place will temporarily be solidified as river channel ecology slope protection planting soil, in the planting soil
Heavy metal Cd and the migration of Zn die down, can effectively prevent or reduce because slope protection soil in heavy metal with precipitation due to import river again
Risk, and this Cd and Zn pollution planting soil be suitable for take water plant further ecology enrichment repair.Do not influencing urban river water
Under the premise of sharp trade culture, Channel slope is rebuild, the cured bed mud of modified zeolite can be as the cladding thickness of planting soil
20cm.Suitable season can be met, the plant of super enrichment Cd and Zn are planted on slope protection.Such as penny cress, sowing are sowed in late March
Method uses drilling, and line-spacing sows 20cm, opens shallow ridges depth 2.5cm, uniformly seed is sowed in ditch；Mountain buckwheat is transplanted before and after Clear and Bright
Wheat selects mature branch, by distance between rows and hills 15cm × 5cm insertion slope protection planting soil.
It is consistent described in remaining process and embodiment 1.
Claims (8)
1. a kind of restorative procedure in cadmium zinc pollution river, characterized in that include the following steps：
(1) the absorption stabilizing and curing agent based on Zeolite modifying is prepared:
1. clinoptilolite crosses 18-5 mesh after broken, screening and grinding, after being rinsed well with deionized water, partial size is obtained
For the zeolite of 1.0-4.0mm；
2. the particulate zeolites for taking step 1. to obtain 450-550 DEG C of roasting in Muffle furnace, removes present in its hole and hole
Impurity and hydrone are cooled to room temperature after roasting 2-4 hours；
3. the modified zeolite for taking step 2. to obtain in mass ratio 1:The NaOH that the ratio of 20-30 is placed in concentration 1.0-3.0mol/L is molten
In liquid, 90-105 DEG C heating water bath 2.5-3.5 hours, 220-260 revs/min isothermal vibration 9-11 hours, make zeolite and NaOH
Solution is sufficiently mixed, and supernatant is poured out, and is cleaned with deionized water, 105 DEG C drying 2-4 hours in baking oven；
4. the modified zeolite for taking step 3. to obtain in mass ratio 1:The ratio of 5-15 is placed in the oxychlorination of concentration 0.1-0.2mol/L
Carried out in zirconium solution it is twice-modified, be placed in revolving speed be 1600-1800 revs/min magnetic agitation instrument stir 3-5 hours, make to be modified
Zeolite is in suspended state；
5. 4. mixed solution that step is obtained is adjusted to pH 9-11, after being then separated by solid-liquid separation, cleaned using deionized water
Then it is steady to get the absorption to modified zeolite to be placed in 105 DEG C of drying in oven to supernatant pH 6.5-7.5 by solid for solid
Determine curing agent；
(2) improvement reparation is carried out to Cd and Zn polluted river channel using the absorption stabilizing and curing agent based on Zeolite modifying：
1. the absorption to polluted river water is administered：
Absorption stabilizing and curing agent is fitted into mesh bag, gabion slope protection, setting in gabion are set in the two sides approximately level of polluted river channel
Upper layer and lower layer filler, lower layer are block stone, and upper layer is the mesh bag equipped with absorption stabilizing and curing agent, for heavy metal Cd in adsorbed water body
With Zn pollutant；
2. carrying out dredging and curing process to polluted river channel bed mud：
For river heavy metal Cd and Zn polluted bed mud, in the case where preventing polluted bed mud from suspending and diffusion, dug using twisting to inhale
Mud ship temporarily solidifies place for polluted bed mud to be twisted to the bed mud for inhaling and being pumped into river bank, temporarily solidifies bottom and the surrounding in place
Anti-seeping technology is carried out, after temporarily Dredged bed mud is carried out screening process by solidification place, removes the sandstone sundries of 2-5mm or more,
It in beta site desiccation to moisture content is 20-30% by the lower bed mud of sieve；
If Cd concentration is less than 10mg/kg in the bed mud under sieve, and Zn pollution concentration is less than 1000mg/kg, and 10- is pressed into bed mud
14% weight ratio adds the absorption stabilizing and curing agent based on Zeolite modifying, and stirs and be sufficiently mixed, and solidification is used after 7-10 days
In the planting soil of subsequent river channel ecology slope protection；If Cd concentration is in 10mg/kg or more or Zn pollution concentration in the bed mud under sieve
In 1000mg/kg or more, then the leach toxicity test of heavy metal is carried out to it, if exceeding leaching characteristic identification standard value,
Processing disposition is carried out by hazardous waste；If be based on into bed mud by the weight ratio addition of 15-20% without departing from the standard
The absorption stabilizing and curing agent of Zeolite modifying, and stir and be sufficiently mixed, the kind of subsequent river channel ecology slope protection is used for after solidifying 7-10 days
Plant soil；
3. repairing pollution by dredging bed mud by ecological slope protection：
Under the premise of not influencing river water conservancy trade culture, Channel slope is rebuild, will temporarily solidify the curing process bottom in place
Mud is meeting suitable season as river channel ecology slope protection planting soil, and the plant of plantation enrichment Cd and Zn, plant are withered on slope protection
It is preceding by plant harvesting, carry out burning disposal after drying.
2. the restorative procedure in cadmium zinc pollution according to claim 1 river, characterized in that the absorption to polluted river water
In improvement, the partial size of the absorption stabilizing and curing agent is 1.0-4.0mm, and mesh bag perforation size is 50-140 mesh.
3. the restorative procedure in cadmium zinc pollution according to claim 1 river, characterized in that the absorption to polluted river water
In improvement, the mesh bag is having a size of 10-50cm × 10-50cm × 10-50cm.
4. the restorative procedure in cadmium zinc pollution according to claim 1 river, characterized in that the absorption to polluted river water
In improvement, the gabion is mild steel wire outsourcing PVC material, and size of mesh opening is 3-10cm × 3-10cm.
5. the restorative procedure in cadmium zinc pollution according to claim 1 river, characterized in that the absorption to polluted river water
In improvement, the thickness proportion of upper layer filler and lower layer's filler is 1 in the gabion:1-3.
6. the restorative procedure in cadmium zinc pollution according to claim 1 river, characterized in that the absorption to polluted river water
In improvement, net door is set at the top of the gabion, after zeolite adsorbed water body Cd and Zn ion reaches saturation, opens net door, replacement
Mesh bag.
7. the restorative procedure in cadmium zinc pollution according to claim 1 river, characterized in that dredged by ecological slope protection reparation
In polluted bed mud, the curing process bed mud is 20-40m as the cladding thickness of planting soil.
8. the restorative procedure in cadmium zinc pollution according to claim 1 river, characterized in that dredged by ecological slope protection reparation
In polluted bed mud, the plant of the plantation enrichment Cd and Zn is to sow penny cress in late March, and type of seeding uses drilling, row
Away from sowing 15-20cm, shallow ridges depth 1.5-2.5cm is opened, uniformly seed is sowed in ditch；Polygonum aubertii is being transplanted around Clear and Bright, is being selected
Mature branch, by distance between rows and hills 15cm × 5cm insertion slope protection planting soil.
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