CN106316307B - A kind of domestic garbage incineration flyash composite passivant and its restorative procedure - Google Patents

A kind of domestic garbage incineration flyash composite passivant and its restorative procedure Download PDF

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Publication number
CN106316307B
CN106316307B CN201610696709.9A CN201610696709A CN106316307B CN 106316307 B CN106316307 B CN 106316307B CN 201610696709 A CN201610696709 A CN 201610696709A CN 106316307 B CN106316307 B CN 106316307B
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China
Prior art keywords
domestic garbage
garbage incineration
incineration flyash
slag
restorative procedure
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CN201610696709.9A
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Chinese (zh)
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CN106316307A (en
Inventor
邵雁
李社锋
王文坦
陶玲
赵波
郭华军
陈堃
刘子豪
覃慧
徐秀英
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武汉都市环保工程技术股份有限公司
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Publication of CN106316307A publication Critical patent/CN106316307A/en
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/08—Slag cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00017—Aspects relating to the protection of the environment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00767—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes

Abstract

The present invention provides a kind of domestic garbage incineration flyash composite passivants, including following component by mass percentage: slag 65~85%, clinker 8~20%, alkali-activator 2~8%, hydroxyapatite 3~10%.The composite passivant raw material uses industrial solid wastes, cheap and easy to get, reduces cost, the useless pollution treatment of benefit；And domestic garbage incineration flyash restorative procedure provided by the invention, it is easy to operate, pass through substance caused by mineral aquation, solidification and stabilization is carried out to heavy metal anion radical in domestic garbage incineration flyash and both sexes heavy metal cation, effect is obvious, solidification early stage can reduce Leaching of Heavy Metals concentration, medium-term and long-term persistently to be reacted, and Leaching of Heavy Metals concentration keeps decreasing trend.

Description

A kind of domestic garbage incineration flyash composite passivant and its restorative procedure

Technical field

The invention belongs to hazardous wastes to administer environmental technology field, and in particular to a kind of domestic garbage incineration flyash is compound blunt Agent and its restorative procedure.

Background technique

With the expansion of China's city size, the raising of economic level and living standards of the people, rubbish caused by city Rubbish amount is also increasingly increasing, and incineration method can not only accomplish that recuperation of heat utilizes in processing domestic waste, also has obvious Volume reduction, it is innoxious the advantages that, obtaining extensive promotion and application in recent years.But it is generated during the burning process Incineration of refuse flyash is all identified as hazardous waste because concentrating a large amount of heavy metal, in many countries, is finally located to it Harmless treatment must be carried out before setting.

Mainly there are heat treating process (sintering, vitrifying and molten to city garbage burning flying ash method for innocent treatment at present Melt), chemical agent stabilization method, landfill method (acid extracts, and alkali carries take and biological reagent extracts etc.) and solidification are stablized Change 4 kinds of processing methods.Solidification and stabilization technology is especially applicable in due to its good effect, short processing time, applied widely In containing the advantages such as the high hazardous waste of heavy metal concentration and soil, and it is concerned.U.S.EPA was once referred to as toxic having The optimization process technology of evil waste.Noxious pollutant can not only be become low-solubility, hypotoxicity and Hypomobility by the technology Substance, and be formed by solidified body after handling and can also be used (roadbed, ground, construction material) by building trade.

And in solidification and stabilization processing method, cement solidification has cost compared with glass solidification, organic curing etc. Low, using convenient advantage, hazard waste landfill at home and abroad disposes aspect extensive use and technology maturation.But the method In the presence of to Zn2+、Pb2+Equal parts divalent both sexes heavy metal cation and high price heavy metal anion radical such as CrO4 2-Equal solidifications are stablized The problem of fettering low efficiency.Amphoteric metal Zn2+、Pb2+It will form zincate or plumbite under high pH conditions and by precipitating It is converted to soluble salt, and the anion radical of high price heavy metal such as CrO4 2-It is moved Deng in overbasic environment with very high Shifting property.

Therefore, searching and research can effectively fetter heavy metal anion radical and both sexes heavy metal in domestic garbage incineration flyash Noval chemical compound (mineral facies) system of cation, is the basis of new inorganic solidified stabilisation matrix design, and endanger in the world The hot spot of dangerous waste pollution control investigation of materials.

Summary of the invention

The purpose of the present invention is overcome the prior art to heavy metal anion radical in domestic garbage incineration flyash and both sexes weight The problem of constraint low efficiency, is stablized in metal cation solidification.

For this purpose, the present invention provides a kind of domestic garbage incineration flyash composite passivant, including by mass percentage Following component: slag 65~85%, clinker 8~20%, alkali-activator 2~8%, hydroxyapatite 3~10%.

Further, above-mentioned slag is water quenching granulating blast-furnace cinder.

Further, the total content of the silica in both above-mentioned slag and clinker and alchlor accounts for slag and clinker For the two gross mass not less than 70%, the mass ratio of silica and alchlor is 2~5.

Further, above-mentioned alkali-activator is white lime, in potassium hydroxide, sodium hydroxide, sodium metasilicate, potassium metasilicate One kind or in which two kinds and two or more compounds.

In addition, including the following steps: the present invention also provides a kind of domestic garbage incineration flyash restorative procedure

1) by 65~85% slag, 8~20% clinker is uniformly mixed, then mixture progress ball is clayed into power, spare.

2) according to domestic garbage incineration flyash optimum moisture content institute to be dealt with water requirement, the hydrochloric acid that pH is 2.2 is prepared 3~10% hydroxyapatite is dissolved in the hydrochloric acid solution by solution, is then uniformly added into flying dust, and strong stirring is uniformly stood afterwards, Obtain mixture.

3) alkali-activator of the mixture powder of step 1) and 2~8% is mixed to join in the mixture of step 2), It is uniformly mixed, and carries out mechanical ramming molding.

4) by test block maintenance molding in step 3) 7~28 days.

Further, above-mentioned steps 1) in the specific surface area of mixture powder after ball milling be greater than or be equal to 600m2/kg。

Further, above-mentioned steps 2) in be added flying dust quality and composite passivant mass ratio be 3~6.

Further, above-mentioned steps 2) in hydroxyapatite specific surface area be greater than or be equal to 800m2/kg。

Further, above-mentioned steps 2) in the strong stirring time be 3min, time of repose 30min.

Further, above-mentioned steps 3) in compacting factor (i.e. actual measurement dry density and maximum dry density ratio) be more than or equal to 0.9。

Utilize domestic garbage incineration flyash composite passivant solidification and stabilization domestic garbage incineration flyash provided by the invention Mechanism it is as follows:

(1) special construction of hydroxyapatite determines it with certain special performances, occupied by additional anionic " structure channel " position and cation present in two kinds of different crystal chemical environments, make hydroxyapatite to different valence state Heavy metal has powerful absorption and exchange interaction, and to the other elements in flying dust in addition to As, especially Pb pollution element has Preferable stabilizing power.

(2) slag is the glass state material with latent hydraulicity, in the case where there being chemical activator, can be relied on Itself chemical composition generates gum material to which hydration reaction occur, can also in flying ash chloride and sulfate it is raw At calcium chloroaluminate and entringite, hydrated calcium silicate, calcium chloroaluminate, entringite, stratlingite and hydrogen-oxygen are ultimately formed Change the mineral systems such as calcium, this mineral system can be precipitated by physically encapsulation, chemisorption to form cenotype and ion exchange is formed The modes such as solid solution realize effective constraint to As；In addition the physicochemical property of its also changeable flying dust, enhances to heavy metal pollution Buffer capacity.

(3) hydroxyapatite is combined with both slags, action compensating, is that the solidification of heavy metal in incineration of refuse flyash is steady Fixedization provides guarantee.

Compared with prior art, beneficial effects of the present invention:

(1) raw material sources of this domestic garbage incineration flyash composite passivant provided by the invention are in typical industry Solid waste, raw material are cheap and easy to get, have achieved the purpose that sharp useless pollution treatment, advantageously reduced cost, have it is significant economical and Environmental benefit.

(2) gel that this domestic garbage incineration flyash restorative procedure provided by the invention mainly passes through mineral aquation is opposite Heavy metal carries out solidification and stabilization, solidifies to heavy metal anion radical in domestic garbage incineration flyash and both sexes heavy metal cation Stabilization effect is obvious, and solidification early stage can reduce Leaching of Heavy Metals concentration, medium-term and long-term persistently to be reacted, Leaching of Heavy Metals Concentration keeps decreasing trend.

Specific embodiment

The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field Art personnel all other embodiment obtained without making creative work belongs to the model that the present invention protects It encloses.

Embodiment 1

Process object be Guangzhou MSW Incineration Plant flying dust, TCLP leach statistics indicate that, the house refuse Lead (12.32mg/L) in flying ash, barium (31.43mg/L), chromium (11.27mg/L) seriously exceed threshold value.

Domestic garbage incineration flyash composite passivant of the invention is prepared, in terms of mass percentage content, slag 77% is ripe Material 14%, sodium metasilicate 4%, hydroxyapatite 5%, wherein slag be active water quenching granulating blast-furnace cinder, clinker be up to To clinker national standard product, the total content of silica and alchlor accounts for both slag and clinker in slag and clinker The 78% of gross mass；Above-mentioned domestic garbage incineration flyash and composite passivant mass ratio 3:1.

According to restorative procedure of the present invention, above-mentioned slag and clinker are uniformly mixed first, then mixture is subjected to ball It clays into power, the specific surface area of control mixture powder is greater than or is equal to 600m2/kg；Then, according to above-mentioned life to be dealt with Incineration of refuse flyash optimum moisture content institute water requirement living prepares the hydrochloric acid solution that pH is 2.2, above-mentioned hydroxyapatite is dissolved in this Hydrochloric acid solution, is then uniformly added into above-mentioned domestic garbage incineration flyash, and strong stirring 3min stands 30min, obtains mixture 1； Finally, above-mentioned mixture powder and sodium metasilicate are mixed to join in mixture 1, it is uniformly mixed, and carries out machinery pressure Real molding, compacting factor conserve 7d up to 0.9 or more.

The leaching prepared according to " solid waste Leaching leaching method hac buffer method " (HJ/T 300) program Liquid carries out toxotest to the domestic garbage incineration flyash after solidification and stabilization, the result shows that, in domestic garbage incineration flyash Each heavy metal concentration can achieve the pollution concentration in " household refuse landfill sites contamination control standard " (GB16889-2008) Limit value.

Embodiment 2

Process object be Wuhan garbage incinerating power plant flying dust, TCLP leach statistics indicate that, the consumer waste incineration The TCLP leaching concentration of chromium in flying dust, arsenic and lead is respectively 13.43mg/L, 6.12mg/L and 8.32mg/L, exceeds threshold value.

Domestic garbage incineration flyash composite passivant of the invention is prepared, in terms of mass percentage content, slag 65% is ripe Material 20%, white lime 8%, hydroxyapatite 7%, wherein slag is active water quenching granulating blast-furnace cinder, and clinker is to reach Clinker national standard product, it is total to account for both slag and clinker for the total content of silica and alchlor in slag and clinker The 83% of quality；Above-mentioned domestic garbage incineration flyash and the composite passivant mass ratio are 5:1.

According to restorative procedure of the present invention, above-mentioned slag and clinker are uniformly mixed first, then mixture is subjected to ball It clays into power, the specific surface area of control mixture powder is greater than or is equal to 600m2/kg；Then, according to above-mentioned life to be dealt with Incineration of refuse flyash optimum moisture content institute water requirement living prepares the hydrochloric acid solution that pH is 2.2, above-mentioned hydroxyapatite is dissolved in this Hydrochloric acid solution, is then uniformly added into above-mentioned domestic garbage incineration flyash, and strong stirring 3min stands 30min, obtains mixture 1； Finally, above-mentioned mixture powder and sodium metasilicate are mixed to join in mixture 1, it is uniformly mixed, and carries out machinery pressure Real molding, compacting factor conserve 7d up to 0.9 or more.

Incineration of refuse flyash TCLP test result after the present embodiment solidification and stabilization shows all Leaching of Heavy Metals concentration Also National Hazard waste judging standard and household refuse landfill sites admissions criteria be can achieve.

Embodiment 3

Process object be Shenzhen MSW Incineration Plant flying dust, TCLP leach statistics indicate that, the house refuse The TCLP leaching concentration of lead and cadmium in flying ash is respectively 46.43mg/L and 12.13mg/L, exceeds threshold value.

Domestic garbage incineration flyash composite passivant of the invention is prepared, in terms of mass percentage content, slag 85% is ripe Material 10%, calcium hydroxide 2%, hydroxyapatite 3%.Wherein, slag be active water quenching granulating blast-furnace cinder, clinker be up to To clinker national standard product, the total content of silica and alchlor accounts for both slag and clinker in slag and clinker The 80% of gross mass；Above-mentioned domestic garbage incineration flyash and composite passivant mass ratio 4:1.

According to the restorative procedure of embodiment 1, the composite passivant of the present embodiment and domestic garbage incineration flyash are mixed Stirring is closed, compaction moulding conserves 28d.

Toxotest is carried out to the domestic garbage incineration flyash after solidification and stabilization, the result shows that after solidification and stabilization Each heavy metal concentration can achieve " household refuse landfill sites contamination control standard " (GB16889- in domestic garbage incineration flyash 2008) the pollution concentration limit value in.

Embodiment 4:

Process object be Wuhan MSW Incineration Plant flying dust, TCLP leach statistics indicate that, the house refuse Lead (6.43mg/L) in flying ash, arsenic (5.32mg/L), chromium (6.27mg/L) seriously exceed threshold value.

Domestic garbage incineration flyash composite passivant of the invention is prepared, in terms of mass percentage content, slag 76% is ripe Material 8%, potassium hydroxide 6%, hydroxyapatite 10%, wherein slag be active water quenching granulating blast-furnace cinder, clinker be up to To clinker national standard product, the total content of silica and alchlor accounts for both slag and clinker in slag and clinker The 73% of gross mass；Above-mentioned domestic garbage incineration flyash and composite passivant mass ratio 5:1.

According to the restorative procedure of embodiment 1, the composite passivant of the present embodiment and domestic garbage incineration flyash are mixed Stirring is closed, compaction moulding conserves 28d.

The leaching prepared according to " solid waste Leaching leaching method hac buffer method " (HJ/T 300) program Liquid carries out toxotest to the domestic garbage incineration flyash after solidification and stabilization, the result shows that, in domestic garbage incineration flyash Each heavy metal concentration can achieve the pollution concentration in " household refuse landfill sites contamination control standard " (GB16889-2008) Limit value.

In conclusion this composite passivant raw material provided by the invention uses industrial solid wastes, and it is cheap and easy to get, it reduces Cost, the useless pollution treatment of benefit；And its restorative procedure is easy to operate, carries out solidification stabilization with respect to heavy metal by the gel of mineral aquation Change, it is obvious to heavy metal anion radical in domestic garbage incineration flyash and both sexes heavy metal cation solidification and stabilization effect, Gu Leaching of Heavy Metals concentration can be reduced by changing early stage, medium-term and long-term persistently to be reacted, and Leaching of Heavy Metals concentration keeps decreasing trend.

The foregoing examples are only illustrative of the present invention, does not constitute the limitation to protection scope of the present invention, all It is within being all belonged to the scope of protection of the present invention with the same or similar design of the present invention.

Claims (9)

1. a kind of domestic garbage incineration flyash composite passivant, it is characterised in that: including following component by mass percentage: Slag 65~85%, clinker 8~20%, alkali-activator 2~8%, hydroxyapatite 3~10%, in both the slag and clinker Silica and the total content of alchlor account for both slag and clinker gross mass not less than 70%, silica and three oxidations The mass ratio of aluminium is 2~5.
2. domestic garbage incineration flyash composite passivant as described in claim 1, it is characterised in that: the slag is water quenching grain Change blast-furnace cinder.
3. domestic garbage incineration flyash composite passivant as described in claim 1, it is characterised in that: the alkali-activator is One of white lime, potassium hydroxide, sodium hydroxide, sodium metasilicate, potassium metasilicate or in which two kinds and two or more compound Object.
4. based on the domestic garbage incineration flyash restorative procedure of any one of claims 1 to 3 composite passivant, feature exists In: include the following steps:
1) by 65~85% slag, 8~20% clinker is uniformly mixed, then mixture progress ball is clayed into power, spare；
2) according to domestic garbage incineration flyash optimum moisture content institute to be dealt with water requirement, the hydrochloric acid solution that pH is 2.2 is prepared, 3~10% hydroxyapatite is dissolved in the hydrochloric acid solution, is then uniformly added into flying dust, strong stirring uniformly stands afterwards, mixed Close object；
3) alkali-activator of the mixture powder of step 1) and 2~8% is mixed to join in the mixture of step 2), is stirred It is uniformly mixed, and carries out mechanical ramming molding；
4) by test block maintenance molding in step 3) 7~28 days.
5. domestic garbage incineration flyash restorative procedure as claimed in claim 4, it is characterised in that: in the step 1) after ball milling Mixture powder specific surface area be greater than or be equal to 600m2/kg。
6. domestic garbage incineration flyash restorative procedure as claimed in claim 4, it is characterised in that: be added in the step 2) The mass ratio of flying dust quality and composite passivant is 3~6.
7. domestic garbage incineration flyash restorative procedure as claimed in claim 4, it is characterised in that: hydroxyl phosphorus in the step 2) The specific surface area of lime stone is greater than or is equal to 800m2/kg。
8. domestic garbage incineration flyash restorative procedure as claimed in claim 4, it is characterised in that: strength is stirred in the step 2) Mixing the time is 3min, time of repose 30min.
9. domestic garbage incineration flyash restorative procedure as claimed in claim 4, it is characterised in that: compacting system in the step 3) Number is more than or equal to 0.9.
CN201610696709.9A 2016-08-22 2016-08-22 A kind of domestic garbage incineration flyash composite passivant and its restorative procedure CN106316307B (en)

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CN103420631B (en) * 2013-08-12 2015-03-25 郑州大学 Waste incineration fly ash heavy metal dual-curing treatment method
JP5751503B1 (en) * 2014-03-26 2015-07-22 住友大阪セメント株式会社 Cement clinker and cement composition
CN105152609B (en) * 2015-07-13 2017-08-29 四川方大新型建材科技开发有限责任公司 Building brick prepared with the flying dust after consumer waste incineration or slag and preparation method thereof

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Address after: 430205 No. 59 Liufang Avenue, Donghu High-tech Development Zone, Wuhan City, Hubei Province

Patentee after: Zhongye Southern Urban Environmental Protection Engineering Technology Co., Ltd.

Address before: 430071 Dongsha Building, 122 North Road, Wuchang District, Wuhan City, Hubei Province, 15th Floor

Patentee before: Wuhan Urban Environment Protection Engineering Techn Co., Ltd.