CN106377867A - Curing agent and curing method for heavy metals in fly ash from mswi (municipal solid waste incineration) - Google Patents
Curing agent and curing method for heavy metals in fly ash from mswi (municipal solid waste incineration) Download PDFInfo
- Publication number
- CN106377867A CN106377867A CN201610699989.9A CN201610699989A CN106377867A CN 106377867 A CN106377867 A CN 106377867A CN 201610699989 A CN201610699989 A CN 201610699989A CN 106377867 A CN106377867 A CN 106377867A
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- Prior art keywords
- incineration
- refuse flyash
- aluminum
- curing
- high silicon
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Classifications
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/33—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by chemical fixing the harmful substance, e.g. by chelation or complexation
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/40—Inorganic substances
- A62D2101/43—Inorganic substances containing heavy metals, in the bonded or free state
Abstract
The invention provides a curing agent and a curing method for heavy metals in fly ash from mswi (municipal solid waste incineration). The curing agent comprises an aluminum-rich high-silicon material and an alkaline exciting agent, wherein the mass of the aluminum-rich high-silicon material is 15% to 25% of the mass of the fly ash from mswi; the mass of the alkaline exciting agent is 3% to 5% of the mass of the fly ash from mswi. The curing agent adopts industrial waste residues, and raw materials are cheap and easy to obtain; according to the curing method, lots of calcium oxide, chloride and sulfide existing in the fly ash from mswi have a hydration reaction with the aluminum-rich high-silicon material to generate a C-S-H (calcium silicate hydrate), Friedel (calcium chloroaluminate) phase and Aft (ettringite) phase system; during the formation process of the mineral system, a solid solution is formed through ion exchange, a new phase is formed through coprecipitation, and a relatively strong stable constraint effect can be played on heavy metals through physical adsorption and coating, so that wastes can be treated by using wastes, and harmless treatment of the fly ash from mswi and resource utilization of the industrial waste residues are realized.
Description
Technical field
The invention belongs to trade waste resource and danger wastes administer environmental technology field and in particular to a kind of rubbish
Rubbish incinerating flyash, heavy metal firming agent and its curing.
Background technology
With the expansion of China's city size, the raising of economic level and living standards of the people, rubbish produced by city
Rubbish amount is also increasingly increasing, and due to unique advantage in terms of minimizing with recycling for the burning method, makes it in recent years to rubbish
The handling rate of rubbish is in rising trend always.But produced incineration of refuse flyash is a large amount of because concentrating in Refuse Incineration Process
Heavy metal, be all identified as hazardous waste in much countries, harmless treatment before it is carried out with final disposal, must be carried out.
, due to its process is simple, raw material is cheap and easy to get, applied widely for solidification and stabilization method, is particularly suited for containing weight
The features such as metal concentration high pollutant, and receive much concern, Environmental protection general bureau is referred to as poisonous and harmful waste
Optimization process technology.
At present, portland cement is still that incineration of refuse flyash harmless treatment uses most curing substrates, and it occurs water
Change reaction and form rigid solid, so that heavy metal contaminants is tended towards stability by physically encapsulation and chemical bond effect, but wherein main
The a large amount of use wanting composition grog then can cause direct energy resource consumption and indirectly environmental pollution, in addition with laws and regulations pair
The requirement more and more higher of heavy metals immobilization body leaching concentration, then when solidifying pollutant, usage amount also greatly increases cement, makes
It loses inexpensive advantage.Therefore, in heavy metal contaminants solidification and stabilization processing procedure, reduce grog as far as possible
Use, as much as possible using some industrial residues, find and study can effectively fetter heavy metal anion radical and both sexes a huge sum of money
Belong to the noval chemical compound of cation（Mineral facies）System, reaches the treatment of wastes with processes of wastes against one another, is the heat of environment pollution control investigation of materials in the world
Point.
Content of the invention
The deficiency existing for the existing technology processing heavy metal in incineration of refuse flyash, it is an object of the invention to provide
A kind of firming agent that heavy metal in incineration of refuse flyash can be made to obtain solidification, this firming agent uses industrial residue, and raw material is inexpensively easy
, and meet environmental requirement.
Another object of the present invention is to provide a kind of curing of heavy metal in incineration of refuse flyash, this solidification side
Method produces hydration reaction using a large amount of calcium oxide existing of incineration of refuse flyash itself, chloride and sulfide and solidifies stable,
Reduce the consumption of firming agent, thus realizing the relatively intense beam of wherein heavy metal ion is tied up.
The technical scheme is that and provide a kind of incineration of refuse flyash heavy metals immobilization agent, the high silicon materials of rich aluminum and alkali
Property exciting agent, described richness the high silicon materials of aluminum be incineration of refuse flyash quality 15～25%, alkali-activator be incineration of refuse flyash
The 3～5% of quality.
Further, how miscellaneous include slag, flyash, CFB fly ash, spoil mine tailing, high silicon for the above-mentioned richness high silicon materials of aluminum
River silt sand, one of thermal activation Kaolin, inclined kaolin, alumina cement, aluminate cement, silica flour, slag, red mud or
Two of which and two or more mixture.
Further, the silica alumina ratio in the above-mentioned richness high silicon materials of aluminum is 1:1～1:1.5, sial total content is 55～75%,
It is grouped into sound response ratio with incineration of refuse flyash group so as to hydration reaction is complete.
Further, above-mentioned alkali-activator includes grog, Calx, potassium hydroxide (KOH), sodium hydroxide (NaOH),
Sodium metasilicate (Na2SiO3), potassium metasilicate (K2SiO3), one of strong base-weak acid salt or two of which and two or more answering
Compound.
In addition, a kind of present invention also offers solidification side processing heavy metal in incineration of refuse flyash using above-mentioned firming agent
Method, comprises the steps：
1) high for rich aluminum silicon materials mechanical grinding is become powder, standby.
2) in pending incineration of refuse flyash add step 1) the high silicon material powder of rich aluminum, obtain mixed-powder.
3) to step 2) mixed-powder in add water and alkali-activator, mix homogeneously is stirred at room temperature, obtains batch mixing.
4) by step 3) the batch mixing molding that obtains, standard curing 7～28 days is so as to form firming body.
Further, above-mentioned steps 1) in the rich aluminum high silicon material powder specific surface area that obtains be more than or equal to 600m2/kg.
Further, above-mentioned steps 2) in the rich high silicon material powder of aluminum and incineration of refuse flyash dry weight ratio for 1:4
～1:6.
Further, above-mentioned steps 2) in water and mixed-powder mass ratio be 0.20～0.45, alkali-activator quality accounts for
The 3～5% of mixed-powder gross mass.
Further, above-mentioned steps 3) Plays maintenance condition be temperature be 25 ± 3 DEG C, relative humidity be 99%.
The mechanism of action of the present invention is as follows：
Incineration of refuse flyash is the Ca-Si-Al-S-Cl system belonging to rich Ca, S, Cl and lean Si, Al, in this system, if given
Give the high silicon materials of rich aluminum of certain match ratio, by alkaline excitation, hydration reaction occur, just have can be formed heavy metal have stronger
The hydrated calcium silicate of constraint effect（C-S-H）, calcium chloroaluminate（Friedel）Phase and entringite（AFt）Phase.
And hydrated calcium silicate therein（C-S-H）, the initial stage is mainly made up of 2 μm of long fibers, mid-term predominantly similar to
Netted or honey comb structure exists, and later stage size becomes thick, and uniformly unifies, and has very big specific surface area, can inhale
Receive the heavy metal stablizing the dissolved in incineration of refuse flyash.
Calcium chloroaluminate（Friedel）, in layer structure, the Cl of its inter-layer position-And H2O passes through Van der Waals force and electrical work
With linking up lamella, such as CrO can be substituted by monovalence or high-valence anion4 2-, AsO4 3-, SeO4 2-, SeO3 2-And OH-
Deng.
Entringite（AFt）, in needle-like or column structure, when making its component change in the form of ion exchange, calcium
Alumen has the ability that structure does not change, and its ion exchange can occur in Ca2+, A13+And SO4 2-Position on, typically
For Ca2+Can be replaced by many bivalent cations, such as Pb2+, Cd2+And Zn2+Deng SO4 2-Can be by some dianions
Group or low price anion substitute, such as CrO4 2-, AsO4 3-, SeO4 2-, SeO3 2-And OH-Deng.
Compared with prior art, beneficial effects of the present invention：The present invention utilizes a large amount of oxygen existing in incineration of refuse flyash
Change calcium, chloride and sulfide, with rich aluminum high silicon materials, hydration reaction occurs, generate hydrated calcium silicate（C-S-H）, calcium chloroaluminate
（Friedel）Phase and entringite（AFt）Phase system, forms solid solution by ion exchange in this mineral system forming process
Body, co-precipitation forms cenotype, and physical absorption and parcel heavy metal have stronger stable constraint effect, reach and are controlled with useless
Useless it is achieved that the recycling of the harmless treatment of incineration of refuse flyash and industrial residue.
Specific embodiment
Below the embodiment it is clear that described is clearly and completely described to the technical scheme in the embodiment of the present invention
It is only a part of embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, the common skill in this area
All other embodiment that art personnel are obtained under the premise of not making creative work, broadly falls into the model of present invention protection
Enclose.
Embodiment 1
Deal with objects the incineration of refuse flyash mixture for Guangzhou garbage incinerating power plant during normal operation different periods, be in
Light gray, calcium content 44.31%, chlorinty 21.74%, sulfur content 9.45%, its TCLP leaching concentration shows, a huge sum of money in this flying dust
Belong to lead（22.47mg/L）, cadmium（3.32mg/L）, zinc（108.73mg/L）Seriously exceed threshold value.
The incineration of refuse flyash heavy metals immobilization agent being provided using the present invention and curing are to above-mentioned incineration of refuse flyash
Processed, wherein, the high silicon materials of rich aluminum take the mixed of Wuhan factory aquation blast-furnace cinder, flyash, silica flour and aluminate cement
Compound, after mechanical grinding, testing sial total content in the high silicon materials of this rich aluminum through component is 67%, and silica alumina ratio is 1:1.5, rich aluminum
High silicon material powder specific surface area is more than or equal to 600m2/ kg, alkali-activator takes Na2SiO3.
Concrete solidification process is as follows：Claim 160g incineration of refuse flyash, the 40g richness high silicon materials of aluminum, carry out mixing to obtain mixed powder
End, then add water and alkali-activator, compaction moulding after stirring, water and mixed-powder mass ratio in mixed-powder
0.20, alkali-activator takes 4.8g, standard curing（Temperature is 25 ± 3 DEG C, and relative humidity is 99%）7 days.
Through TCLP test, show that the incineration of refuse flyash Leaching of Heavy Metals concentration after cured stablizing all can reach country's danger
Dangerous waste judging standard and household refuse landfill sites admissions criteria require.
Embodiment 2
Deal with objects as Wuhan garbage incinerating power plant flying dust, calcium content 39.31%, chlorinty 19.74%, sulfur content
12.45%, its chromium, the TCLP leaching concentration of arsenic and lead exceeds threshold value（8.23mg/L, 5.32mg/L and 11.33mg/L）.
The incineration of refuse flyash heavy metals immobilization agent being provided using the present invention and curing are to above-mentioned incineration of refuse flyash
Processed, wherein, the high silicon materials of rich aluminum take from the aquation blast-furnace cinder of Wuhan factory, CFB fly ash, inclined kaolin and
The mixture of red mud, testing its silica alumina ratio through component after mechanical grinding is 1：1.32, sial total content is 75%, the high silicon material of rich aluminum
Material Specific Surface Area Measurement is more than or equal to 600m2/ kg, alkali-activator takes grog and Na2SiO3Mixture, grog and Na2SiO3's
Mass ratio is 1:1.
With embodiment 1, the incineration of refuse flyash TCLP test result after result shows solidification and stabilization shows other steps,
All Leaching of Heavy Metals concentration all can reach National Hazard waste judging standard and household refuse landfill sites admissions criteria.
Embodiment 3
Deal with objects as Shenzhen MSW Incineration Plant flying dust, this flying dust calcium content 37.41%, chlorinty 17.23%, contain
Sulfur content 18.12%, its chromium, the TCLP leaching concentration of lead and cadmium exceeds threshold value（13.83mg/L, 2.32mg/L and 4.33mg/L）.
The incineration of refuse flyash heavy metals immobilization agent being provided using the present invention and curing are to above-mentioned incineration of refuse flyash
Processed, wherein, the high silicon materials of rich aluminum take the high silicon materials of rich aluminum similarly to Example 2, alkali-activator take KOH and
K2SiO3Mixture, KOH and K2SiO3Mass ratio be 2:1.
Concrete solidification process is as follows：Take 180g incineration of refuse flyash, the 30g richness high silicon materials of aluminum, carry out mixing to obtain mixed powder
End, then add water and alkali-activator, compaction moulding after stirring, water and mixed-powder mass ratio in mixed-powder
0.40, the quality of alkali-activator takes 9g, standard curing 7d.
Through TCLP leaching test, show that its Leaching of Heavy Metals concentration all can reach National Hazard waste judging standard requirement
And household refuse landfill sites admissions criteria, reach the purpose of heavy metal in solidification and stabilization incineration of refuse flyash, simultaneously
Realize the efficient resource utilization to rich aluminum high silicon trade waste material.
Embodiment 4：
Deal with objects the incineration of refuse flyash mixture for Wuhan garbage incinerating power plant during normal operation different periods, contain
Calcium amount 36.24%, chlorinty 16.61%, sulfur content 19.45%, its TCLP leaching concentration shows, heavy metal lead in this flying dust
（20.43mg/L）, cadmium（6.76mg/L）, arsenic（11.82mg/L）Seriously exceed threshold value.
The incineration of refuse flyash heavy metals immobilization agent being provided using the present invention and curing are to above-mentioned incineration of refuse flyash
Processed, wherein, the high silicon materials of rich aluminum take Wuhan factory aquation blast-furnace cinder, how miscellaneous high silicon river silt be husky and slag mixed
Compound, after mechanical grinding, testing sial total content in the high silicon materials of this rich aluminum through component is 55%, and silica alumina ratio is 1:1, rich aluminum is high
Silicon material powder specific surface area is more than or equal to 600m2/ kg, alkali-activator takes Na2CO3.
Concrete solidification process is as follows：Claim 200g incineration of refuse flyash, the 30g richness high silicon materials of aluminum, carry out mixing to obtain mixed powder
End, then add water and alkali-activator, compaction moulding after stirring, water and mixed-powder mass ratio in mixed-powder
0.45, alkali-activator takes 8g, standard curing（Temperature is 25 ± 3 DEG C, and relative humidity is 99%）7 days.
Through TCLP test, show that the incineration of refuse flyash Leaching of Heavy Metals concentration after cured stablizing all can reach country's danger
Dangerous waste judging standard and household refuse landfill sites admissions criteria require.
The only illustration to the present invention exemplified as above, does not constitute the restriction to protection scope of the present invention, all
It is that same or analogous design belongs within protection scope of the present invention with the present invention.
Claims (9)
1. a kind of incineration of refuse flyash heavy metals immobilization agent it is characterised in that：Including the rich high silicon materials of aluminum and alkali-activator, institute
State the high silicon materials of rich aluminum be incineration of refuse flyash quality 15～25%, alkali-activator be incineration of refuse flyash quality 3～
5%.
2. incineration of refuse flyash heavy metals immobilization agent as claimed in claim 1 it is characterised in that：Described richness aluminum high silicon materials bag
Include slag, flyash, CFB fly ash, spoil mine tailing, high silicon how miscellaneous river silt sand, thermal activation Kaolin, inclined kaolin, vitriol
One of soil-cement, aluminate cement, silica flour, slag, red mud or two of which and two or more mixture.
3. incineration of refuse flyash heavy metals immobilization agent as claimed in claim 2 it is characterised in that：In the described richness high silicon materials of aluminum
Silica alumina ratio be 1:1～1:1.5, sial total content is 55～75%.
4. incineration of refuse flyash heavy metals immobilization agent as claimed in claim 1 it is characterised in that：Described alkali-activator includes
Grog, Calx, one of potassium hydroxide, sodium hydroxide, sodium metasilicate, potassium metasilicate, strong base-weak acid salt or two of which
And two or more complex.
5. process the curing of heavy metal in incineration of refuse flyash based on firming agent described in any one of Claims 1 to 4, it is special
Levy and be：Comprise the steps：
1) high for rich aluminum silicon materials mechanical grinding is become powder, standby；
2) in pending incineration of refuse flyash add step 1) the high silicon material powder of rich aluminum, obtain mixed-powder；
3) to step 2) mixed-powder in add water and alkali-activator, mix homogeneously is stirred at room temperature, obtains batch mixing；
4) by step 3) the batch mixing molding that obtains, standard curing 7～28 days is so as to form firming body.
6. firming agent as claimed in claim 5 process heavy metal in incineration of refuse flyash curing it is characterised in that：Described
Step 1) in the rich aluminum high silicon material powder specific surface area that obtains be more than or equal to 600m2/kg.
7. firming agent as claimed in claim 5 process heavy metal in incineration of refuse flyash curing it is characterised in that：Described
Step 2) in the rich high silicon material powder of aluminum and incineration of refuse flyash dry weight ratio for 1:4～1:6.
8. firming agent as claimed in claim 7 process heavy metal in incineration of refuse flyash curing it is characterised in that：Described
Step 2) in water and mixed-powder mass ratio be 0.20～0.45, alkali-activator quality be incineration of refuse flyash quality 3～
5%.
9. firming agent as claimed in claim 5 process heavy metal in incineration of refuse flyash curing it is characterised in that：Described
Step 3) Plays maintenance condition be temperature be 25 ± 3 DEG C, relative humidity be 99%.
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| CN108117291A (en) * | 2017-12-28 | 2018-06-05 | 江西省建筑材料工业科学研究设计院 | A kind of discarded copper tailing slag efficient activator and preparation method thereof |
| CN108261712A (en) * | 2018-04-02 | 2018-07-10 | 长沙绿邦环保科技有限公司 | A kind of incineration of refuse flyash curing agent, preparation method and flying dust method of disposal |
| CN108298839A (en) * | 2018-01-11 | 2018-07-20 | 中国恩菲工程技术有限公司 | Cement cementitious material and its method for preparing cement cementitious material using flying dust |
| CN108409176A (en) * | 2018-05-18 | 2018-08-17 | 萧县沃德化工科技有限公司 | A kind of domestic garbage incineration flyash geopolymer and preparation method thereof |
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