CN110330196A - Dredge stabilizer of heavy metal polluted bed mud and preparation method thereof and application method - Google Patents
Dredge stabilizer of heavy metal polluted bed mud and preparation method thereof and application method Download PDFInfo
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- CN110330196A CN110330196A CN201910492634.6A CN201910492634A CN110330196A CN 110330196 A CN110330196 A CN 110330196A CN 201910492634 A CN201910492634 A CN 201910492634A CN 110330196 A CN110330196 A CN 110330196A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/004—Sludge detoxification
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Organic Chemistry (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention discloses a kind of stabilizers for dredging heavy metal polluted bed mud, including following component: Wyoming type bentonite 40-49%；Sodium thiosulfate 25-30%；Disodium hydrogen phosphate 14-20%；Stablize additive 0.5-5%；Mullite powder 10-20%；Wherein, above-mentioned all the components aqueous dose rate < 1%.The present invention makes full use of industrial residue and industrial auxiliary material, turns waste into wealth, and lime is not added, carbide slag, binder, early strength agent, the materials such as cement, setting fog room is not needed, energy saving, production cost is low, and stablizing effect is good, supplementary material setting is obtained to be generated without special processing and secondary pollution, can be widely applied to technical field of sludge treatment.
Description
Technical field
The present invention relates to technical field of sludge treatment.It is more particularly related to dredge heavy metal polluted bed mud
Stabilizer and preparation method thereof and application method.
Background technique
China's Present Situation of Environmental Quality causes anxiety, and environmental improvement is gradually thus lifted to critical role.It is newest according to Chinese environmental report
Number, China's urban wastewater treatment reaches 1.62 hundred million m at present3/ d, the sludge of association are about 33,590,000 tons (moisture content > 80%),
In 31.03% be used for landfill, 13.79% direct heap is abandoned, 3.45% blended landfill.Thus caused soil is occupied seriously,
For 2017, about 17,000,000 tons of excess sludges are discharged into refuse landfill or storage hole, land occupation about 81.1~162.2 ten thousand
m2, accumulative land occupation is more than 30,000,000 m within nearly 30 years2；In addition, industrial enterprise can generate containing a large amount of weights in engineering construction production process
The tailings of metal also contains plurality of heavy metal.And in contaminated river, lake, heavy metal and organic matter pass through long-term
Physics, chemistry and bioprocess eventually enter into the bed mud of deposition.According to statistics, in the waters of national offshore 80%, heavy metal is (such as
Pb, Hg, Cu, Cd) have at different degrees of over-standard phenomenon, especially Haikou and river population and seaport area, heavy metals exceeding standard
Phenomenon is particularly acute.These contain tail mud, bed mud and the sludge of heavy metal, the mode such as abandoned using simple landfill, heap, leaching
Heavy metal ion will cause huge harm to environment, seriously threaten human health.Therefore, how it is carried out safely, quickly,
Efficient processing is one of current environmental improvement and key issues in protection field and research topic, and at present in the field
Hot subject.Solidification and stabilization is a kind of more mature and cost-effective technology, but curing agent master used in the technology
The problems such as using the hydraulic materials such as cement, gypsum and lime, sludge or other solid wastes is often made to generate hardening, increase-volume,
It is unfavorable for subsequent disposition and utilization.Therefore, novel heavy metal stabilizer is researched and developed to be of great practical significance.
The processing mode of traditional heavy metal sewage sludge is largely that after being handled using organic sequestering agent, sludge is pacified
Full landfill.And organic sequestering agent majority is imported product, and it is expensive, and there are certain limitations for its chelating process itself
Property, and cause to use and promote on a large scale.Therefore, the heavy metal stabilizer of exploitation, needing to accomplish can be by weight in sludge
Stable processing is inside sludge well for metallic pollution ion, and environmental sound, itself does not change the object of sludge itself
Attribute is managed, and is conducive to its subsequent engineering and recycles.From discussed above it is found that carrying out the exploitation work of heavy metal stabilizer
Make, processing and the recycling that can not only promote sludge are horizontal, are also beneficial to China's core technology with independent intellectual property rights
Foundation, be to kill two birds with one stone, this develops the transition and upgrade of enterprise very important.
The existing heavy metal stabilizer applied to heavy metal polluted bed mud: being core with carboxylic acid sodium side by triethanolamine
The four carbodithioic acid sodium of star dissaving polymer and Alkylenediamine of base and carbodithioic acid sodium end group forms, wherein three
Ethanol amine is the chemical formula of the star dissaving polymer with carboxylic acid sodium side group and carbodithioic acid sodium end group of core are as follows: N
[CH2CH2OCOCH2CH2(COONa)N(CSSNa)CH2(CH2)nCH2N(CSSNa)2]3, wherein n is the positive integer between 0~4；
Four carbodithioic acid Sodium chemistry formula of Alkylenediamine are as follows: (NaSSC)2NCH2(CH2)nCH2N(CSSNa)2, wherein n is between 0~4
Positive integer；N benzoyl N phenyl hydroxyamine can be used as domestic garbage incineration flyash processing heavy metal stabilizer, N- benzoyl-
N-Phenylhydroxylamine to the heavy metal in domestic garbage incineration flyash have stabilization, and it is cheap and easy to get, dosage is few, at stabilisation
Reason method is simple, at low cost, without secondary pollution.But it finds in use, above-mentioned heavy metal stabilizer in the prior art
The treatment effeciency for handling heavy metal polluted bed mud is low, is unsatisfactory for National Environmental relevant emission standards.
Summary of the invention
High, high treating effect the stabilization for dredging heavy metal polluted bed mud that the object of the present invention is to provide a kind for the treatment of effeciencies
Agent and its application method.
In order to realize these purposes and other advantages according to the present invention, a kind of dredging heavy metal polluted bed mud is provided
Stabilizer, which is characterized in that including following component:
Wyoming type bentonite 40-49%；
Sodium thiosulfate 25-30%；
Disodium hydrogen phosphate 14-20%；
Stablize additive 0.5-5%；
Mullite powder 10-20%；
Wherein, above-mentioned all the components aqueous dose rate < 1%.
Preferably, the stabilizer of the dredging heavy metal polluted bed mud, the stable additive are calcium formate, FDN
The mixture of high efficiency water reducing agent and triethanolamine.
Preferably, the stabilizer of the described dredging heavy metal polluted bed mud, calcium formate, FDN in the stable additive
The mass ratio of high efficiency water reducing agent and triethanolamine is 1:2:1.
Preferably, the stabilizer of the dredging heavy metal polluted bed mud, the mullite powder is before using through peracid
Change and is activated.
Preferably, the stabilizer of the dredging heavy metal polluted bed mud, the Wyoming type bentonite is before use
By modification, detailed process is as follows:
By in the pure water of neopelex investment mass fraction 4%, the modification of mass fraction 12% is prepared
Solution is put into sealing container, then the Wyoming type bentonite of aforementioned proportion is put into container, wherein every Wyoming 1kg type
Bentonite corresponds to 10L modified solution；It is finished to the dispensing of Wyoming type bentonite, nitrogen to container inner pressure is passed through into container and is reached
0.06MPa, 1200r/min high-speed stirred 45min, stirring finish, and stand, washing, and are dried, and modified processing is obtained
Wyoming type bentonite.
A kind of preparation method of stabilizer that dredging heavy metal polluted bed mud, comprising the following steps:
S1, neopelex is put into the pure water of mass fraction 4%, changing for mass fraction 12% is prepared
Property solution, put into sealing container in, then into container put into aforementioned proportion Wyoming type bentonite, wherein every Wyoming 1kg
Type bentonite corresponds to 10L modified solution；It is finished to the dispensing of Wyoming type bentonite, nitrogen is passed through into container to container inner pressure
Up to 0.06MPa, 1200r/min high-speed stirred 45min, stirring is finished, and is stood, washing, and is dried, and modified processing is obtained
Wyoming type bentonite, it is spare；
S2, by sodium thiosulfate, the disodium hydrogen phosphate of Wyoming type bentonite and aforementioned proportion after S1 modification
And stablize additive, mixing and water adding, 1200r/min high-speed stirred stands for 24 hours, is filtered by vacuum, and drying obtains the first mixing
Object；
S3, the mullite powder of aforementioned proportion is taken to be immersed in the H of 0.1mol/L2SO4It is activated in solution, 1000r/
Min stirs 30-40min, is filtered by vacuum, dry, the mullite powder after must activating；
S4, by S3 activate after mullite powder under nitrogen atmosphere, 400-500 DEG C of high-temperature calcination 4-5h, after obtaining calcining
Mullite powder；
S5, the calcined mullite powder that the first obtained mixture of S2 and S4 are obtained, mixes to obtain the second mixture；After
It is continuous to be placed in 500-550 DEG C of high-temperature calcination 3-4h, it grinds, obtains the stabilizer of target product dredging heavy metal polluted bed mud.
Preferably, the preparation method of the stabilizer of heavy metal polluted bed mud is dredged, in S5,500-550 DEG C of high temperature 4-5h,
It is specifically divided into first stage, second stage and phase III:
First stage: with 5 DEG C/min of heating rate from room temperature to 250 DEG C, 10min is kept the temperature；
Second stage: with 10 DEG C/min of heating rate from room temperature to 400 DEG C, 30min is kept the temperature；
Phase III: with 10 DEG C/min of heating rate from room temperature to 250 DEG C, 4-5h is kept the temperature.
A kind of application method of stabilizer that dredging heavy metal polluted bed mud, comprising the following steps:
Step 1: the stabilizer of the dredging heavy metal polluted bed mud of mass ratio 100:1-4 and sludge to be processed are mixed,
It is placed in blender, stirs evenly；
Step 2: standing 7 days.
The present invention is include at least the following beneficial effects:
1, the present invention makes full use of industrial residue and industrial auxiliary material, turns waste into wealth, and lime is not added, carbide slag, bonding
Agent, early strength agent, the materials such as cement do not need setting fog room, and energy saving, the heavy metal stabilizer of production uses additive ratio
Example: heavy metal stabilizer and heavy metal polluted bed mud mass ratio=2~4:100, production cost is low, and stablizing effect is good, supplementary material
Setting is obtained to be generated without special processing and secondary pollution.
2, the present invention has made intensive studies the component of conversion processing, and it is steady to obtain this heavy metal for selected various components
Determine the formula of agent；This heavy metal stabilizer main ingredient is made of the elements salt such as calcium, magnesium, silicon, aluminium, phosphorus, steady to heavy metal
The cardinal principle of determining effect is: by mixing with sludge agitation, medicament is uniformly contacted with bed mud, and is formed in gelling environment
The nothing of many oxide determines phase constitution substance, and the substance has very strong attraction to heavy metal ion such as copper, lead, cadmium, zinc
Power.When the heavy metals such as institute's cupric, lead, cadmium, zinc chance water dissolution exudation in sludge, determine to be adsorbed by it after phase substance contacts with nothing,
Occur precipitation reaction, complex reaction and form the mines such as complexing formula cupric relatively stable, harmless, that solubility is extremely low, lead, cadmium, zinc
Substance, to achieve the purpose that heavy metal stabilization.This heavy metal stabilizer Environmental security, nontoxic secondary influence, processing heavy metal
Pollute reliable and stable, main raw material(s) is derived from industrial residue, and it is low in cost, accomplish the treatment of wastes with processes of wastes against one another.
3, the processing and disposal efficiency of heavy metal polluted bed mud can be improved in the heavy metal stabilizer of the application, can be effective
Stabilization bed mud in heavy metal components, heavy metal toxicity dissolution lower than national environmental protection provide discharge threshold.It can also subtract simultaneously
The generation of few consumption and secondary pollution in heavy metal stabilizer production environment important raw material is national energy conservation and emission reduction, wound
The development for building green heavy metal pollution control technology contributes, and solves a heavy metal stabilizer processing huge sum of money in the prior art
The technical issues for the treatment of effeciency for belonging to polluted bed mud is low, is unsatisfactory for National Environmental relevant emission standards.
4, the synthetic method of this heavy metal stabilizer is low in cost, is conducive to be mass produced.This heavy metal stabilizer
Application method is simple, operates easy, suitable large-scale promotion application.
5, by being activated and 400-500 DEG C of temperature calcination 3h-4h, can be changed into after mullite powder a kind of unformed
Metastable state structure, mullite powder form needle-shaped, sheet crystal, and the graininess knot largely formed by sheet and needle-shaped accumulation
Structure, these nutty structures are intermeshed to accumulate by needle-shaped, laminated structure and be formed, this kind of state is needle-shaped, convenient for generating in sludge
Heavy metal precipitation, be adhered on mullite powder, strengthened to heavy metal precipitation attraction by ion surface adsorption capacity；
Mullite powder after activation burning is mixed with Wyoming type bentonite, Wyoming type bentonite can be made successively to lose
The combination water in surface water, water of hydration and structural framework is removed, reduces moisture film to the absorption resistance of polluter；Part is located at swelling
Impurity in native channel and gap is pulled away together with the moisture lost, and channel and gap are opened, to keep Wyoming type swollen
Moisten native absorption property to change, and bentonite will not be made to undergo phase transition, bentonite skeleton structure will not be destroyed.
After Wyoming type bentonite, sodium thiosulfate, disodium hydrogen phosphate, stable additive and sludge agitation, and it is being gelled
The nothing that many oxide is formed in environment determines phase constitution, which has very strong attraction to heavy metals such as copper, lead, cadmium, zinc.
When the heavy metals such as institute's cupric, lead, cadmium, zinc chance water dissolution exudation in flying dust, it will be adsorbed by it after contact, precipitation reaction, network occurs
It closes reaction and forms the minerals such as complexing formula cupric relatively stable, harmless, that solubility is extremely low, lead, cadmium, zinc, to reach weight
Metal-stabilized purpose.
6, modified solution is prepared in neopelex, and high-pressure stirring impregnates Wyoming type bentonite,
In sodium ion enter Wyoming type bentonite crystal layer space, be modified sheet surfaces, crystal layer spacing increase so that bosom Russia
The bright bentonitic interfloor distance of type increases, to increase the compatibility of Wyoming type bentonite and heavy metal ion, enhances
Type bentonitic adsorption capacity in Wyoming can be very good absorption Heavy Metals in Sludge ion；And entire modifying process is in height
It is carried out under pressure condition, sodium ion can be accelerated to enter Wyoming type bentonite crystal layer space.
Further advantage, target and feature of the invention will be partially reflected by the following instructions, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Specific embodiment
The present invention will be further described in detail below with reference to the embodiments, to enable those skilled in the art referring to specification
Text can be implemented accordingly.
It should be noted that experimental method described in following embodiments is unless otherwise specified conventional method, institute
Reagent and material are stated, unless otherwise specified, is commercially obtained；
Organic sludge is selected from Wuhan City Xun Si river organic contamination bed mud and is handled in the present embodiment and comparative example, patrols Si He
The content of heavy metal ion in organic contamination bed mud: Cu 486.12mg/l, Pb 151.98mg/l, Zn 945.09mg/l, Cd
35.11mg/l,Cr 186.13mg/l；
It includes: 49 parts of Wyoming type bentonite, thiosulfuric acid that the stabilizer of heavy metal polluted bed mud is dredged in the present embodiment
25 parts of sodium, stablizes 1 part of additive, 10 parts of mullite powder at 15 parts of disodium hydrogen phosphate；Wherein, the aqueous dose rate of above-mentioned all the components
< 1%；
In the present embodiment dredge heavy metal polluted bed mud stabilizer the preparation method is as follows:
S1, neopelex is put into the pure water of mass fraction 4%, changing for mass fraction 12% is prepared
Property solution, put into sealing container in, then into container put into aforementioned proportion Wyoming type bentonite, wherein every Wyoming 1kg
Type bentonite corresponds to 10L modified solution；It is finished to the dispensing of Wyoming type bentonite, nitrogen is passed through into container to container inner pressure
Up to 0.06MPa, 1200r/min high-speed stirred 45min, stirring is finished, and is stood, washing, and is dried, and modified processing is obtained
Wyoming type bentonite, it is spare；
S2, by sodium thiosulfate, the disodium hydrogen phosphate of Wyoming type bentonite and aforementioned proportion after S1 modification
And stablize additive, mixing and water adding, 1200r/min high-speed stirred stands for 24 hours, is filtered by vacuum, and drying obtains the first mixing
Object；
S3, the mullite powder of aforementioned proportion is taken to be immersed in the H of 0.1mol/L2SO4It is activated in solution, 1000r/
Min stirs 30-40min, is filtered by vacuum, dry, the mullite powder after must activating；
S4, by S3 activate after mullite powder under nitrogen atmosphere, 400-500 DEG C of high-temperature calcination 4-5h, after obtaining calcining
Mullite powder；Wherein, 500-550 DEG C of high temperature 4-5h, is specifically divided into first stage, second stage and phase III: first
Stage: with 5 DEG C/min of heating rate from room temperature to 250 DEG C, 10min is kept the temperature；Second stage: with 10 DEG C/min of heating rate
From room temperature to 400 DEG C, 30min is kept the temperature；Phase III: with 10 DEG C/min of heating rate from room temperature to 250 DEG C, heat preservation
4-5h。
S5, the calcined mullite powder that the first obtained mixture of S2 and S4 are obtained, mixes to obtain the second mixture；After
It is continuous to be placed in 500-550 DEG C of high-temperature calcination 3-4h, it grinds, obtains the stabilizer of target product dredging heavy metal polluted bed mud.
The application method of the stabilizer of heavy metal polluted bed mud is dredged in the present embodiment, comprising the following steps:
Step 1: the stabilizer of the dredging heavy metal polluted bed mud of mass ratio 100:4 and sludge to be processed are mixed, set
In blender, stir evenly；
Step 2: standing 7 days, measurement display toxicity leaches result.
The preparation method of measurement display toxicity leaching result is identical in 1-embodiment of embodiment 5, and handles organic sludge
Method is identical.
Comparative example: the existing another heavy metal stabilizer weight ratio of constituents applied to heavy metal pollution sludge is calculated as 40%
Ore dressing chelating agent (disodium ethylene diamine tetraacetate) and 60% high polymer coagulant (cationic polyacrylamide), mixing and
At the processing method are as follows: the chemical heavy metal stabilizer is made into the aqueous solution that mass concentration is 3%, by aqueous solution plus
Enter into flying dust, weight ratio 1.5: 1, uniform stirring, stable glue-like solid matrix is made, then dries, save, surveys
Amount display toxicity leaches result and is unsatisfactory for National Environmental relevant criterion discharge threshold, the results are shown in Table 2.
The component of 1-embodiment of embodiment 5 is as shown in the table:
The ratio summary table of the component of 1 embodiment 1- embodiment 5 of table
The river Wuhan City Xun Si heavy metal polluted bed mud is handled according to said ratio, sludge leachate carries out sample by treated
Product examine is surveyed, and discovery is fairly obvious to sludge heavy-metal stablizing effect, the results are shown in Table 2.
2 embodiment 1-5 of table and comparative example handle the result summary sheet after sludge
By upper table result it is found that after the present embodiment 1-5 processing sludge, the toxicity of sludge leaches result and has reached national row
Put standard, it was demonstrated that stabilizer prepared by the present invention has good leaching process effect to sludge heavy-metal.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily
Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited
In specific details and embodiment shown and described herein.
Claims (8)
1. a kind of stabilizer for dredging heavy metal polluted bed mud, which is characterized in that including following component:
Wyoming type bentonite 40-49%；
Sodium thiosulfate 25-30%；
Disodium hydrogen phosphate 14-20%；
Stablize additive 0.5-5%；
Mullite powder 10-20%；
Wherein, above-mentioned all the components aqueous dose rate < 1%.
2. a kind of as described in claim 1 stabilizer of dredging heavy metal polluted bed mud, which is characterized in that it is described stablize it is additional
Agent is the mixture of calcium formate, FDN high efficiency water reducing agent and triethanolamine.
3. a kind of as claimed in claim 2 stabilizer of dredging heavy metal polluted bed mud, which is characterized in that it is described stablize it is additional
The mass ratio of calcium formate, FDN high efficiency water reducing agent and triethanolamine is 1:2:1 in agent.
4. a kind of stabilizer of dredging heavy metal polluted bed mud as described in claim 1, which is characterized in that the mullite powder
Using preceding acidified activation processing.
5. a kind of stabilizer of dredging heavy metal polluted bed mud as described in claim 1, which is characterized in that the Wyoming type
Bentonite is passing through modification using preceding, and detailed process is as follows:
By in the pure water of neopelex investment mass fraction 4%, the modified solution of mass fraction 12% is prepared,
It puts into sealing container, then puts into the Wyoming type bentonite of aforementioned proportion into container, wherein the every Wyoming 1kg type bentonite
Corresponding 10L modified solution；It is finished to the dispensing of Wyoming type bentonite, nitrogen to container inner pressure is passed through into container and is reached
0.06MPa, 1200r/min high-speed stirred 45min, stirring finish, and stand, washing, and are dried, and modified processing is obtained
Wyoming type bentonite.
6. a kind of preparation method of the stabilizer of dredging heavy metal polluted bed mud a method as claimed in any one of claims 1 to 5, feature
It is, comprising the following steps:
S1, neopelex is put into the pure water of mass fraction 4%, the modification that mass fraction 12% is prepared is molten
Liquid is put into sealing container, then the Wyoming type bentonite of aforementioned proportion is put into container, wherein every Wyoming 1kg type is swollen
The corresponding 3L modified solution of profit soil；It is finished to the dispensing of Wyoming type bentonite, nitrogen to container inner pressure is passed through into container and is reached
0.06MPa, 1200r/min high-speed stirred 45min, stirring finish, and stand, washing, and are dried, and modified processing is obtained
Wyoming type bentonite, it is spare；
S2, by the sodium thiosulfate of Wyoming type bentonite and aforementioned proportion after S1 modification, disodium hydrogen phosphate and
Stablize additive, mixing and water adding, 1200r/min high-speed stirred stands for 24 hours, is filtered by vacuum, and drying obtains the first mixture；
S3, the mullite powder of aforementioned proportion is taken to be immersed in the H of 0.1mol/L2SO4It is activated in solution, 1000r/min is stirred
30-40min is mixed, is filtered by vacuum, dry, the mullite powder after must activating；
S4, by S3 activate after mullite powder under nitrogen atmosphere, 400-500 DEG C of high-temperature calcination 4-5h, obtain it is calcined not
Carry out mountain flour；
S5, the calcined mullite powder that the first obtained mixture of S2 and S4 are obtained, mixes to obtain the second mixture；Continue to set
In 500-550 DEG C of high-temperature calcination 3-4h, grinding obtains the stabilizer of target product dredging heavy metal polluted bed mud.
7. a kind of preparation method of the stabilizer of dredging heavy metal polluted bed mud as claimed in claim 6, which is characterized in that S5
In, 500-550 DEG C of high temperature 4-5h is specifically divided into first stage, second stage and phase III:
First stage: with 5 DEG C/min of heating rate from room temperature to 250 DEG C, 10min is kept the temperature；
Second stage: with 10 DEG C/min of heating rate from room temperature to 400 DEG C, 30min is kept the temperature；
Phase III: with 10 DEG C/min of heating rate from room temperature to 250 DEG C, 4-5h is kept the temperature.
8. a kind of application method of the stabilizer of dredging heavy metal polluted bed mud a method as claimed in any one of claims 1 to 5, feature
It is, comprising the following steps:
Step 1: the stabilizer of the dredging heavy metal polluted bed mud of mass ratio 100:1-4 and sludge to be processed are mixed, it is placed in
In blender, stir evenly；
Step 2: standing 7 days.
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| CN112876120A (en) * | 2021-02-05 | 2021-06-01 | 上海复洁环保科技股份有限公司 | Sludge incineration ash-based composite admixture and preparation method and application thereof |
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