CN109647859A - Solidifying/stabilizing material for lead and chromium in waste incineration fly ash and solidifying method thereof - Google Patents
Solidifying/stabilizing material for lead and chromium in waste incineration fly ash and solidifying method thereof Download PDFInfo
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- CN109647859A CN109647859A CN201811623428.6A CN201811623428A CN109647859A CN 109647859 A CN109647859 A CN 109647859A CN 201811623428 A CN201811623428 A CN 201811623428A CN 109647859 A CN109647859 A CN 109647859A
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- gangue
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- 239000000463 material Substances 0.000 title claims abstract description 64
- 239000010881 fly ash Substances 0.000 title claims abstract description 32
- 239000011651 chromium Substances 0.000 title claims abstract description 25
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 22
- 230000000087 stabilizing effect Effects 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title abstract description 19
- 238000004056 waste incineration Methods 0.000 title abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 238000001723 curing Methods 0.000 claims description 41
- 239000007787 solid Substances 0.000 claims description 39
- 238000000227 grinding Methods 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 23
- 239000012190 activator Substances 0.000 claims description 21
- 239000002689 soil Substances 0.000 claims description 21
- 150000005846 sugar alcohols Polymers 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 235000019353 potassium silicate Nutrition 0.000 claims description 16
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 238000000498 ball milling Methods 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- 238000012423 maintenance Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000003701 mechanical milling Methods 0.000 claims description 2
- 239000002910 solid waste Substances 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 9
- 239000003245 coal Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 238000005065 mining Methods 0.000 abstract 1
- 239000011133 lead Substances 0.000 description 22
- 238000002386 leaching Methods 0.000 description 20
- 229910001385 heavy metal Inorganic materials 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- 230000006835 compression Effects 0.000 description 14
- 238000007906 compression Methods 0.000 description 14
- 229910052782 aluminium Inorganic materials 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- 239000003513 alkali Substances 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 11
- 230000006641 stabilisation Effects 0.000 description 10
- 239000010430 carbonatite Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 239000010813 municipal solid waste Substances 0.000 description 7
- 238000007711 solidification Methods 0.000 description 7
- 230000008023 solidification Effects 0.000 description 7
- 238000011105 stabilization Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000004913 activation Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 239000002920 hazardous waste Substances 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000002956 ash Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000002925 chemical effect Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 230000000192 social effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000000638 stimulation Effects 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910002566 KAl(SO4)2·12H2O Inorganic materials 0.000 description 1
- 229910003243 Na2SiO3·9H2O Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 231100000820 toxicity test Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/20—Agglomeration, binding or encapsulation of solid waste
- B09B3/25—Agglomeration, binding or encapsulation of solid waste using mineral binders or matrix
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B2101/00—Type of solid waste
- B09B2101/30—Incineration ashes
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a solidifying/stabilizing material of lead and chromium in waste incineration fly ash and a solidifying method thereof, wherein the solidifying/stabilizing material is prepared from red mud and coal gangue, and the mass percentage of the red mud and the coal gangue is 60-90%: 10 to 40 percent. The material adopts industrial solid wastes such as red mud and coal gangue associated in the processes of metallurgy, coal mining and the like as main raw materials, not only can obtain ideal performance, but also can utilize the solid wastes as resources, reduce the manufacturing cost of the material, reduce the land occupation and pollution risk of the solid wastes, and has good industrial prospect and great social significance.
Description
Technical field
The present invention relates to a kind of flyash curing/stabilization materials, in particular to it is poly- soil to be blended using red mud-gangue
It closes after object passes through mechanical stress effect and chemical effect excitation activation and curing/stabilizing material, then the sharp curing/stabilizing is made
The method of heavy metal element lead, chromium, belongs to solid waste resource recovery using neck in the efficiently fixed incineration of refuse flyash of material
Domain.
Background technique
What is generated in incineration of refuse flyash, that is, incineration process of domestic garbage being trapped by flue gas system or being settled in flue
Flying dust, major pollutant are heavy metal, including lead, chromium, cadmium, zinc, arsenic, nickel etc., the content of each heavy metal species because of region not
With difference.Numerous countries are classified as hazardous waste, and China is also included in " Hazardous Waste List " very early.China is early
" the Hazardous Wastes Management technological policy for treatment " for being that 2001 formulate must be independent with regard to clear stipulaties domestic garbage incineration flyash
Processing generating has to pass through necessary solidification and stabilization processing, it is necessary to carry out security landfill disposition.
The processing of incineration of refuse flyash includes physical method, chemical method and physical chemistry integrated treatment etc., such as electric osmose
Analysis, chemical leaching, curing stabilization method, wherein curing/stabilizing technology is considered as that processing heavy metal pollution is solid all the time
The optimal path of body waste, and most commonly used processing means both at home and abroad.Curing/stabilizing method is especially with cement solidification
Stabilize the most universal, technology is extremely mature and stablizes, however as the formation that the control carbon emission in global range is known together,
Cement will gradually update as high carbon emission product.In recent years, soil polyalcohol is as a kind of low-carbon cementitious material,
Heavy metals immobilization stabilizes field and gradually attracts attention, and is especially used using the soil polyalcohol that solid waste is developed as raw material
With the curing/stabilizing of heavy metal pollution solid waste, while realizing pair of solid wastes recycling, Heavy Metal Pollution Control
Weight target.Under this trend, the soil polyalcohol using red mud as main material is increasingly becoming research hotspot.However since red mud is living
Property is totally lower, therefore the selection of its auxiliary material and the technique of preexciting are most important.Gangue is useless as a kind of clay class mineral
Gurry, mainly by forming for kaolinite and quartz, raw material components ratio can effectively be adjusted by being blended with red mud, and activated
Under the conditions of a certain amount of activity of metakaolin ingredient is provided, therefore it has adequate condition as the auxiliary material of red mud and carries out soil
Polymer preparation.
Summary of the invention
In view of the problems of the existing technology, red mud and gangue solid are utilized the purpose of the present invention is to provide a kind of
Waste be raw material and low-carbon energy-saving, function admirable incineration of refuse flyash in lead, chromium curing/stabilizing material.The material
The industrial solid castoff red mud of association, gangue can not only obtain during using metallurgy, mine etc. for primary raw material
Ideal performance, and material manufacturing cost can be reduced with resource utilization solid waste, reduce solid waste soil
Occupancy and pollution risk have good industrial prospect and great social effect.
In order to achieve the above technical purposes, the present invention provides solidification/stabilizations of lead, chromium in a kind of incineration of refuse flyash
Change material, be made of red mud and gangue, the mass percent of the red mud and gangue be 60%~90%:10%~
40%.
The mass percent of preferred scheme, the red mud and gangue is 80%:20%.
For the present invention under preferred proportion, red mud-gangue mixture compression strength is the most prominent, and activity preferably, works as coal
When spoil excess, the development of material alkali-activated carbonatite intensity can be inhibited instead, influence the compression strength and curing performance of material.
The present invention also provides the curing method of lead, chromium in the curing/stabilizing material processing incineration of refuse flyash,
Red mud and gangue mixing and ball milling are obtained into preexciting solid powder, progress precuring obtains red mud-bastard coal after alkali-activator is added
Soil polyalcohol slurry is blended in stone, adds incineration of refuse flyash to be processed, obtains induration after maintenance molding.
Preferred scheme, red mud desiccation under field conditions (factors) first, then drying to constant weight at 105 DEG C, by it
It is crushed to partial size≤10mm；The gangue is milled to partial size≤200 μm.
Red mud is pureed slurry, develops cementitious material using it, it is necessary to first by its desiccation under field conditions (factors), drying
It is crushed afterwards stand-by；Gangue is blocky spoil solid, using preceding broken using destroyer；Since red mud is in mechanical grinding mistake
Reunion depositional phenomenon easily occurs in journey, in order to improve influence of this phenomenon to grinding process, it is necessary to add necessary grinding aid
Agent, and inherently a kind of inorganic grinding aid of gangue, therefore gangue undertakes the auxiliary work of grinding aid in intergrinding process
With.
Preferred scheme, the mechanical milling process use vertical-type planetary ball milling, and rotational speed of ball-mill is 1500~3000r/min, excellent
It is selected as 2000r/min；Ball-milling Time is at least 10min, preferably 20min；Ratio of grinding media to material is 15~25:1；Preferably 20:1.This
Invention uses ball milling mixing, under the conditions of certain revolving speed and ratio of grinding media to material, with the increase of Ball-milling Time, compression strength by
It is cumulative plus, when preferably 20min, grain diameter reaches optimal distribution state, and compression strength reaches maximum, and the time continues growing,
Its compression strength has a declining tendency instead.
Preferred scheme, the alkali-activator select the blend solution of waterglass and NaOH solution, and blend solution swashs with pre-
The liquid-solid ratio for sending out solid powder is 0.3~0.5.
Preferred scheme, the modulus of water glass are 3.0~4.0, preferably 3.4M；NaOH solution concentration be 3~
The molar ratio of 10mol/L, preferably 5mol/L, the waterglass and NaOH solution is not less than 1.65, preferably 1.66.
NaOH mainly provides alkaline condition in exciting agent system while providing Na in the present invention+, work as Na+Ion increases
When, ion balance increases in soil polyalcohol three-dimensional net structure, a part of Na+Exist with impurity in ionized state, in maintenance processes
In gradually there is " anti-frost " phenomenon in release in hole, to reduce the strength of materials；However material initial set and final setting time by
Decrescence small, this concentration for being mainly due to alkali-activator is continuously increased, and causes alkali-activated carbonatite slurry viscosity to increase, while exciting agent
PH is consequently increased, and alumino-silicate is depolymerized to alkali soluble balance and gathers again in advance.
Preferred scheme, the precuring condition be 80~90 DEG C of thermostatic curings at least for 24 hours.
The mass ratio of preferred scheme, the incineration of refuse flyash solid powder and preexciting solid powder is 50%:
50%~20%:80%.
Preferred scheme, the condition of the maintenance are 20 DEG C ± 2 DEG C of temperature, relative humidity 95%.
This material is made by red mud and gangue.Gangue contains about 50% kaolin mineral phase, can be regarded as low
Grade kaolin has certain probability then activating using this method to it.However in the activity excitation process of gangue
In, in order to increase the content of activity Al, Si after gangue preexciting, a certain amount of alkalinity need to be generally added in excitation process
Oxide, and a certain amount of Na of remaining just in red mud2O, the two blending just can effectively solve the problems, such as this, while red mud
As a kind of hydrometallurgy waste residue, main component is based on sticky soil property, easily aggregation adherency during mechanical grinding,
Need to add a certain amount of grinding aid, and containing a small amount of primary coal in gangue, can be used as inorganic grinding aid uses,
The two is blended grinding excitation while solving this problem in that.Since mixture itself is active lower, thus need to using mechanical stress effect and
Chemical effect excites red mud and gangue mixture.Red mud-gangue after exciting is blended in soil polyalcohol,
Heavy metal lead stabilization procedures are primarily involved in polymerization reaction, enter unformed soil polyalcohol condensate silicon by ion exchange
Aluminium network structure, and the stabilisation of heavy metal chromium mainly passes through into the realization of soil polyalcohol three-dimensional net structure duct.
Free state heavy metal lead, chromium stabilization multidirectional greatly under the curing/stabilizing effect of soil polyalcohol, in garbage flying ash
State conversion, to reduce the Leaching of heavy metal element lead, chromium.Result, it is believed that red mud and gangue cooperate with therebetween
Effect is obvious, and the performance of material solidification/stabilisation heavy metal element lead, chromium can be improved.
Opposite current material, this material bring advantageous effects:
1) present invention regard red mud and gangue both industrial solid wastes as curing/stabilizing material after overactivation
The raw material of material, can not only obtain the performance of heavy metal lead, chromium in excellent efficient consolidation incineration of refuse flyash, but also can be with
Abundant resource utilization red mud and gangue, reduce the production cost of curing/stabilizing material, have good industrial prospect
With great social effect.
2) this material is not only using industrial solid wastes as the raw material of curing/stabilizing material, and to heavy metal lead,
The solidification ratio of chromium is higher, can increase substantially treating capacity.
3) this material is good to the stable curing effect of heavy metal lead, chromium, and garbage flying ash is after this material solidification/stabilisation
Heavy metal lead, chromium leaching concentration are below right in national standard GB5085.3-2007 " hazardous waste judging standard leaching characteristic identification "
The limits value answered.
4) use of this material can use for reference existing moulding process, not have particular/special requirement to equipment, easy to operate, low
Cost is conducive to industrialization promotion.
Specific embodiment
Illustrate embodiments of the present invention below by embodiment, following embodiment be intended to illustrate invention without
It is limitation of the invention further.
Two kinds of incineration of refuse flyash samples selected by this experiment are taken respectively from Chongqing and Guangdong municipal solid waste incinerator,
Wherein M1 is derived from Chongqing, and M2 is derived from Guangzhou, chemical composition such as table 1, the content of beary metal such as lead, chromium such as table 2, the huge sum of money such as lead, chromium
Belong to leaching concentration such as table 3.
The chemical composition of 1 incineration of refuse flyash of table
| Na2O | MgO | Al2O3 | SiO2 | P2O5 | SO3 | K2O | CaO | Fe2O3 | Cl | Other | |
| M1 (%) | 7.26 | 1.30 | 1.97 | 8.22 | 0.77 | 7.25 | 7.10 | 33.45 | 1.42 | 24.45 | 4.07 |
| M2 (%) | 9.07 | 1.53 | 2.18 | 3.35 | 0.45 | 9.04 | 5.58 | 38.64 | 0.69 | 28.32 | 2.68 |
The content of beary metal such as lead, the chromium of 2 incineration of refuse flyash of table
| Pb | Cr | Zn | Cd | |
| M1(mg/kg) | 88.40 | 3980.70 | 13960.84 | 229.81 |
| M2(mg/kg) | 1050.58 | 385.25 | 8585.43 | 203.21 |
The Leaching of Heavy Metals concentration such as lead, the chromium of 3 incineration of refuse flyash of table
| Pb | Cr | Zn | Cd | |
| M1(mg/L) | 0.08 | 35.07 | 135.49 | 1.01 |
| M2(mg/L) | 1.35 | 2.35 | 97.23 | 0.76 |
Embodiment 1
Mechanization activation parameter is selected: being set drum's speed of rotation as 2000r/min, is set ratio of grinding media to material as 20:1, mix
Ball-milling Time is 20min；
Mixing and ball milling is carried out using the sample of different red muds and gangue mass ratio, obtains preexciting solid powder；
Use 3.4M waterglass and 5mol/LNaOH blend solution for alkali-activated carbonatite liquid, molar ratio 5:3 first will be pre-
Solid powder and alkali-activator mixing are excited, liquid-solid ratio 0.4 is poured into 20mm × 20mm mold, so after quickly stirring 5min
Conserve 1d at 80 DEG C afterwards, demoulding be placed in 20 DEG C ± 2 DEG C of temperature, relative humidity 95%RH or more standard curing box in conserve
To 7d, red mud and influence of the gangue mass ratio to material compressive property are differentiated with its compression strength, analyze result such as 4 institute of table
Show.
4 red mud of table and influence of the gangue mass ratio to material compressive property
| Red mud and gangue mass ratio | 7d compression strength/MPa |
| 90%:10% | 12.01 |
| 80%:20% | 16.29 |
| 60%:40% | 10.52 |
| 50%:50% | 4.94 |
As shown in Table 4, when red mud and gangue mass ratio are 80%:20%, compression strength is the most prominent, shows condition
Lower red mud-gangue mixture activity preferably, also illustrates the hair that can inhibit material alkali-activated carbonatite intensity under gangue excess conditions
Exhibition.
Embodiment 2
Activationary time is selected: according to embodiment 2 as a result, the use of red mud and gangue mass ratio being 80%:20%'s
Sample is studied, and is set drum's speed of rotation as 2000r/min, is set ratio of grinding media to material as 20:1；
It sets different grinding times to be studied, obtains preexciting solid powder；
Use 3.4M waterglass and 5mol/LNaOH blend solution for alkali-activated carbonatite liquid, mixing ratio 5:3 first will be pre-
Solid powder and alkali-activator mixing are excited, liquid-solid ratio 0.4 is poured into 20mm × 20mm mold, so after quickly stirring 5min
Conserve 1d at 80 DEG C afterwards, demoulding be placed in 20 DEG C ± 2 DEG C of temperature, relative humidity 95%RH or more standard curing box in conserve
To 7d, influence of the grinding time to material compressive property is differentiated with its compression strength, the results are shown in Table 5 for analysis.
Influence of 5 grinding time of table to material compressive property
| Grinding time (min) | 7d compression strength/MPa |
| 10 | 12.12 |
| 20 | 17.85 |
| 40 | 17.52 |
| 60 | 17.06 |
As shown in Table 5, when grinding time is 20min, intensity has reached maximum, as grinding time continues growing, material
The intensity of material is on a declining curve instead, this is because material granule partial size has reached optimal distribution state in grinding 20min.
Embodiment 3
Mechanization activation parameter is selected: being set drum's speed of rotation as 2000r/min, is set ratio of grinding media to material as 20:1, mix
Ball-milling Time is 20min；
NaOH solution concentration is selected in alkali-activator: since user friendly alkali-activator must satisfy SiO2: M2O rubs
You consider that waterglass cost is higher than sodium hydroxide than being greater than 1.65, and the dosage of waterglass is reduced as far as possible, SiO2: M2O ratio
It is then the smaller the better within the allowable range, therefore commercially available more universal waterglass (3.4M) is selected, and determine that alkali-activator is equipped with
When be fixed as SiO2:Na2O=1.66,
The NaOH solution for preparing various concentration is studied；
Preexciting solid powder and alkali-activator are mixed first, liquid-solid ratio 0.4, is poured into after quickly stirring 5min
In 20mm × 20mm mold, 1d is then conserved at 80 DEG C, demoulding is placed in 20 DEG C ± 2 DEG C of temperature, relative humidity 95%RH or more
Standard curing box in maintenance to 28d, shadow of the NaOH solution to material compressive property of various concentration is differentiated with its compression strength
It rings, the results are shown in Table 6 for analysis.
Influence of the NaOH solution of 6 various concentration of table to material compressive property
| NaOH solution concentration (mol/L) | 28d compression strength/MPa |
| 3 | 11.65 |
| 5 | 24.75 |
| 10 | 22.35 |
As shown in Table 6, when NaOH solution is 5mol/L, intensity has reached maximum, illustrates material obtained with this condition
Expect that performance is the most excellent.
Embodiment 4
Mechanization activation parameter is selected: being set drum's speed of rotation as 2000r/min, is set ratio of grinding media to material as 20:1, mix
Ball-milling Time is 20min；
Alkali-activated carbonatite condition is selected: using 3.4M waterglass and 5mol/LNaOH blend solution for alkali-activated carbonatite liquid, mixing ratio
For 5:3, preexciting solid powder and alkali-activator mixing, liquid-solid ratio 0.4；
The mass ratio of incineration of refuse flyash solid powder and preexciting solid powder is selected: in sample alkali-activated carbonatite process
In, the incineration of refuse flyash of different proportion is added, carries out solidification and stabilization research.
It must be noted that predetermined soil polyalcohol liquid-solid ratio is 0.4, after mixing incineration of refuse flyash, this
One liquid-solid ratio can not make slurry reach enough fluidities, consider neither to change soil polyalcohol preparation process and meet simultaneously
Enough fluidities.Therefore, it on the basis of explorative experiment, determines and individually prepares soil polyalcohol slurry in preparation process
Body and garbage flying ash add water slurry body (liquid-solid ratio 0.5), and high-speed stirred 5min then is blended in the two, are uniformly mixed it, so
After pour into mold conserve molding.The volume of incineration of refuse flyash sample M1, M2 according to soil polyalcohol solid powder material
Mass ratio determination be respectively as follows: 80%:20%, 60%:40%, 50%:50%, 40%:60%, 20%:80%.Sample
Leach toxicity test uses TCLP Leaching detection method.Curing time is 28d.Incineration of refuse flyash M1, M2 volume pair
The impact analysis result of induration Leaching is respectively as shown in table 7, table 8.
Influence of the volume of 7 incineration of refuse flyash M1 of table to induration Leaching
Influence of the volume of 8 incineration of refuse flyash M2 of table to induration Leaching
| Incineration of refuse flyash volume | Pb curing degree (%) | Cr curing degree (%) |
| 80%:20% | 60.19 | 96.82 |
| 60%:40% | 79.01 | 100.00 |
| 50%:50% | 91.18 | 100.00 |
| 40%:60% | 100.00 | 100.00 |
| 20%:80% | 100.00 | 100.00 |
By table 7, table 8 it is found that when soil polyalcohol solid powder volume is 50% or more, material burns two kinds of rubbish
The curing efficiency for burning heavy metal in flying dust can reach 90% or more.
Comparative example 1
Due in soil polyalcohol polymerization process first stage, that is, preexciting solid powder alumino-silicate in alkali-activated carbonatite
Be decomposed into Al, Si activated monomer under agent effect, thus Al, Si leaching characteristic of preexciting solid powder for material whether
It is extremely critical soil polyalcohol can effectively to be prepared.
It is red mud: gangue=80%:20% that 100% red mud sample S1,100% gangue sample S2, mass ratio, which is arranged,
Sample S3 compare experiment.
The alkali-activator used is 3.4M waterglass and 5mol/LNaOH mixed solution, mixing ratio 5:3, liquid-solid ratio
It is 0.4, first mixes preexciting solid powder and alkali-activator, is poured into 20mm × 20mm mold after quickly stirring 5min,
Then conserve 1d at 80 DEG C, demoulding be placed in 20 DEG C ± 2 DEG C of temperature, relative humidity 95%RH or more standard curing box in support
It protects to 28d.Experiment show that Al, Si leaching rate of S1 and S2 is as shown in table 9.
Different sample Al, Si leaching rates in 9 comparative example 1 of table
| Sample number into spectrum | Al leaching rate (%) | Si leaching rate (%) |
| S1 | 9.62 | 6.50 |
| S2 | 2.71 | 14.85 |
| S3 | 19.62 | 25.26 |
As shown in Table 9,100% red mud sample S1,100% gangue Al, Si leaching rate be significantly lower than mass ratio
Red mud: gangue=80%:20% sample illustrates that red mud and gangue can effectively facilitate Al, Si of material by being blended
Alkali soluble goes out, to greatly promote material property.
Comparative example 2
It is aluminium ore slag: gangue=80%:20% sample S1, red mud: flyash=80%:20% that mass ratio, which is arranged,
Sample S2, aluminium ore slag: flyash=80%:20% sample S3, mass ratio be red mud: gangue=80%:20% sample
Product S4 compares experiment.
The alkali-activator used is 3.4M waterglass and 5mol/LNaOH mixed solution, mixing ratio 5:3, liquid-solid ratio
It is 0.4, first mixes preexciting solid powder and alkali-activator, is poured into 20mm × 20mm mold after quickly stirring 5min,
Then conserve 1d at 80 DEG C, demoulding be placed in 20 DEG C ± 2 DEG C of temperature, relative humidity 95%RH or more standard curing box in support
It protects to 28d.Experiment show that Al, Si leaching rate of S1, S2, S3, S4 are as shown in table 10.
Different sample Al, Si leaching rates in 10 comparative example 2 of table
| Sample number into spectrum | Al leaching rate (%) | Si leaching rate (%) |
| S1 | 10.35 | 5.09 |
| S2 | 8.82 | 9.83 |
| S3 | 5.54 | 15.70 |
| S4 | 19.62 | 25.26 |
As shown in Table 10, in the sample of 4 kinds of different components, mass ratio is red mud: gangue=80%:20% sample
Product promote Al, Si alkali result of extraction of material the most obvious.
Comparative example 3
Different alkali-activator S1 (NaCO is set3)、S2(Na2SiO3·9H2O)、S3(KAl(SO4)2·12H2O) and
The solution S 4 that 3.4M waterglass and 5mol/LNaOH mixing ratio are 5:3 compares experiment.
4 kinds of alkali-activators are mixed with liquid-solid ratio 0.4 with preexciting solid powder, pour into 20mm after quickly stirring 5min
In × 20mm mold, 1d is then conserved at 80 DEG C, demoulding is placed in the mark of 20 DEG C ± 2 DEG C of temperature, relative humidity 95%RH or more
It conserves in quasi- curing box to 7d.Experiment show that the 7d compression strength of S1, S2, S3, S4 are as shown in table 11.
The 7d compression strength of the different samples of 11 comparative example of table 3
As can be seen from Table 11, different alkali-activators have larger difference, part alkali-activator to the stimulation effect of material
It will lead to strength of materials decline, no excitating performance.3.4M waterglass and 5mol/LNaOH mixing ratio is selected to make for the solution of 5:3
There is preferable stimulation effect for alkali-activator.
Claims (10)
1. the curing/stabilizing material of lead, chromium in a kind of incineration of refuse flyash, it is characterised in that: it is made of red mud and gangue,
The mass percent of the red mud and gangue is 60%~90%:10%~40%.
2. curing/stabilizing material according to claim 1, it is characterised in that: the quality hundred of the red mud and gangue
Divide than being 80%:20%.
3. the curing method of lead, chromium in curing/stabilizing material processing incineration of refuse flyash of any of claims 1 or 2, special
Sign is: red mud and gangue mixing and ball milling being obtained preexciting solid powder, progress precuring obtains red after addition alkali-activator
Soil polyalcohol slurry is blended in mud-gangue, adds incineration of refuse flyash to be processed, obtains induration after maintenance molding.
4. curing method according to claim 3, it is characterised in that: red mud desiccation under field conditions (factors) first, so
Drying to constant weight at 105 DEG C afterwards, is crushed to partial size≤10mm；The gangue is milled to partial size≤200 μm.
5. curing method according to claim 3, it is characterised in that: the mechanical milling process uses vertical-type planetary ball milling, ball
Mill revolving speed is 1500~3000r/min；Ball-milling Time is at least 10min；Ratio of grinding media to material is 15~25:1.
6. curing method according to claim 3, it is characterised in that: the alkali-activator selects waterglass and NaOH solution
Blend solution, the liquid-solid ratio of blend solution and preexciting solid powder is 0.3~0.5.
7. curing method according to claim 6, it is characterised in that: the modulus of water glass is that 3.0~4.0, NaOH is molten
Liquid concentration is 3~10mol/L, and the molar ratio of the waterglass and NaOH solution is not less than 1.65.
8. curing method according to claim 3, it is characterised in that: the precuring condition is 80~90 DEG C of thermostatic curings
At least for 24 hours.
9. curing method according to claim 3, it is characterised in that: the incineration of refuse flyash solid powder and preexciting
The mass ratio of solid powder is 50%:50%~20%:80%.
10. curing method according to claim 3, it is characterised in that: the condition of the maintenance is 20 DEG C ± 2 DEG C of temperature,
Relative humidity 95%.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110028973A (en) * | 2019-04-29 | 2019-07-19 | 武汉大学 | A kind of heavy metal curing agent and its application based on polypropylene fibre and boiler ash |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289332A (en) * | 2008-06-06 | 2008-10-22 | 昆明理工大学 | Low-temperature ceramic foam material and production method thereof |
| WO2008144838A1 (en) * | 2007-05-31 | 2008-12-04 | Commonwealth Scientific And Industrial Research Organisation | Method for treating residue from a bayer process |
| CN101624267A (en) * | 2009-08-11 | 2010-01-13 | 山西鑫秀工矿废渣利用有限公司 | Low-temperature ceramic curing agent of red mud from Bayer process |
| CN103193429A (en) * | 2013-04-26 | 2013-07-10 | 建研建材有限公司 | Iron core tailing curing agent, iron core all-tailing cementing composition containing iron core tailing curing agent and application of iron core all-tailing cementing composition to gob of mine |
| CN105130363A (en) * | 2015-08-09 | 2015-12-09 | 肖德意 | Permanent heavy metal waste curing method |
| CN106348712A (en) * | 2016-08-30 | 2017-01-25 | 北京玉锦资源与环境技术研究院（有限合伙） | Cementing filling material for co-processing lead-containing dangerous wastes of mine and preparation method of cementing filling material |
| AU2015269119B2 (en) * | 2014-06-03 | 2017-11-02 | Egreen Co., Ltd. | Method for preparing coated, whole cottonseed from which germination function is removed |
| 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 |
-
2018
- 2018-12-28 CN CN201811623428.6A patent/CN109647859A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008144838A1 (en) * | 2007-05-31 | 2008-12-04 | Commonwealth Scientific And Industrial Research Organisation | Method for treating residue from a bayer process |
| CN101289332A (en) * | 2008-06-06 | 2008-10-22 | 昆明理工大学 | Low-temperature ceramic foam material and production method thereof |
| CN101624267A (en) * | 2009-08-11 | 2010-01-13 | 山西鑫秀工矿废渣利用有限公司 | Low-temperature ceramic curing agent of red mud from Bayer process |
| CN103193429A (en) * | 2013-04-26 | 2013-07-10 | 建研建材有限公司 | Iron core tailing curing agent, iron core all-tailing cementing composition containing iron core tailing curing agent and application of iron core all-tailing cementing composition to gob of mine |
| AU2015269119B2 (en) * | 2014-06-03 | 2017-11-02 | Egreen Co., Ltd. | Method for preparing coated, whole cottonseed from which germination function is removed |
| CN105130363A (en) * | 2015-08-09 | 2015-12-09 | 肖德意 | Permanent heavy metal waste curing method |
| CN106348712A (en) * | 2016-08-30 | 2017-01-25 | 北京玉锦资源与环境技术研究院（有限合伙） | Cementing filling material for co-processing lead-containing dangerous wastes of mine and preparation method of cementing filling material |
| 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 |
Non-Patent Citations (3)
| Title |
|---|
| 张娜，孙恒虎，张吉秀，万建华: "复合热活化对赤泥-煤矸石胶凝性能的影响", 《稀有金属材料与工程》 * |
| 曲选辉: "《粉末冶金原理与工艺》", 31 May 2013 * |
| 赵云龙、徐洛屹: "《石膏应用技术问答》", 30 September 2016 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110028973A (en) * | 2019-04-29 | 2019-07-19 | 武汉大学 | A kind of heavy metal curing agent and its application based on polypropylene fibre and boiler ash |
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| CN110922108B (en) * | 2019-12-09 | 2021-08-10 | 大连理工大学 | Method for solidifying municipal solid waste incineration fly ash based on rice hull ash-red mud composite cementing material |
| CN110981302B (en) * | 2019-12-13 | 2021-06-11 | 华中科技大学 | Method for solidifying lead alkaline residue by microwave-assisted fly ash-based geopolymer |
| CN110981302A (en) * | 2019-12-13 | 2020-04-10 | 华中科技大学 | Method for solidifying lead alkaline residue by microwave-assisted fly ash-based geopolymer |
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| CN112552921B (en) * | 2020-12-18 | 2021-10-12 | 安徽理工大学环境友好材料与职业健康研究院(芜湖) | Heavy metal contaminated soil remediation material, preparation method and soil remediation method |
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| CN113441526A (en) * | 2021-07-07 | 2021-09-28 | 中国电建集团河北省电力勘测设计研究院有限公司 | Method for stabilizing heavy metals in waste incineration fly ash by compounding coal gangue and calcium oxide |
| CN113441526B (en) * | 2021-07-07 | 2023-03-03 | 中国电建集团河北省电力勘测设计研究院有限公司 | Method for stabilizing heavy metals in waste incineration fly ash by compounding coal gangue and calcium oxide |
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