CN1830885A - Ceramicite using ash from incineration of refuse as raw material and its prodn. method - Google Patents
Ceramicite using ash from incineration of refuse as raw material and its prodn. method Download PDFInfo
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- CN1830885A CN1830885A CNA2006100133367A CN200610013336A CN1830885A CN 1830885 A CN1830885 A CN 1830885A CN A2006100133367 A CNA2006100133367 A CN A2006100133367A CN 200610013336 A CN200610013336 A CN 200610013336A CN 1830885 A CN1830885 A CN 1830885A
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- haydite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
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Abstract
A haydite is prepared from the fly ash (20-80 Wt%) generated by burning garbage and clay (rest) through mixing, granulating, and high-temp calcining at 1000-1400 deg.C.
Description
Technical field
The present invention relates to a kind of haydite and preparation method thereof, relate in particular to a kind of haydite and method thereof of utilizing incineration of refuse flyash for raw material.
Background technology
The increasing rapidly of domestic waste becomes a major issue of restriction urban sustainable development, shows according to statistics: calendar year 2001 the year domestic refuse amount of Chinese city reached 1.35 hundred million tons, and the harmless treatment degree has only 20%.The rubbish of storing up has over the years reached 7,000,000,000 tons, has occupied about 800,000 mu of soils, and environment has been caused potential influence and harm.Garbage incineration technology can destroy organic toxicant effectively, reduce the volume (generally can reduce to original volume 5%～30%) of rubbish greatly, the waste heat that burn to produce can also be recycled, and this has become garbage as resource on the our times, innoxious and subtract one of main mode of appearanceization treatment technology.But meeting produces the incineration residue of some amount after the waste incineration.Incineration residue is under the fire grate of incinerator and collected ejecta such as smoke duster, waste heat boiler, mainly is made up of jointly bottom ash (Bottom Ash or Slag) and flying dust (Fly Ash).Bottom ash system burns the resistates that the back is discharged by the siege tail end, accounts for cindery 80%～90% (quality meter) greatly; And flying dust be meant flue gas purification system (Air Pollution Control System, APC) collect and resistates, in lime-ash, account for 10%～20% (quality meter) greatly.The harmful substance contents of bottom ash is less, usually as general disposition of solid waste.But " national Hazardous wastes register " classifies the solid waste burning flying dust as Hazardous wastes numbering HW18251.Flying dust toxicity major reason for higher is, waste incineration makes part heavy metal vaporization at high temperature, then in flue gas purification system condensation attached on the fly ash granule; In addition, the Dioxins of waste incineration generation also can be attached on the fly ash granule.Therefore, incineration of refuse flyash often contains the lead (Pb) and the cadmium heavy metals such as (Cd) of higher leaching concentration, also contains the Dioxins of high density, generally needs to handle through curing/stabilizing earlier before it is carried out ultimate disposal.
At present, the common method that flying dust is disposed mainly contains: cement solidification, bituminization, melting and solidification technology, chemical agent solidification and stabilization etc., through the product after the solidification and stabilization processing, leach toxicity criterion or recycling standard as satisfying, can enter common landfill yard and carry out the landfill disposal or carry out recycling.The brief introduction of various flying dust method of disposal is as follows: (1) cement solidification technology is exactly to form flying dust and cement concrete mixing solid-state, behind hydration reaction, form hard solidified cement body, reduce the purpose that hazard component leaches in the flying dust thereby reach, its ultimate principle is by the surface-area that solidify to contain reduces flying dust and reduces its permeability, reaches stabilization, innoxious purpose.This technology is comparatively simple and reliable, but shortcoming is that the cement consumption is big, causes refuse increase-volume significantly, the processing costs height; (2) the melting and solidification method also is called the vitrifying technology, this technology is that pending flying dust and glass filler are added in high-temperature electric arc stove or the plasma heating furnace, handle by high-temperature fusion, make it generate glassy silicate form, the processable component is wrapped in its dissolving is not come out.This technology needs specific equipment, and investment is high, and disposal costs is also higher; (3) chemical stabilization is to utilize chemical agent to make hazardous and noxious substances change the process of low-solubility, low migration and hypotoxicity material into by chemical reaction.This technology still is in development period, and disposal costs is relatively low.Though it is comparatively desirable that subject matter is the treatment effect of heavy metal, then do not have positive effect for Dioxins.
Because above these flying dust method of disposal costs of disposal are generally higher, present most flying ash is still and carries out simple landfill.Domestic practical situation are: on the one hand, the landfill yard land used is in short supply at present, and construction investment is big, and flying dust carries out the expense too high (1500 yuan/ton～2500 yuan/ton) of landfill earlier again through cement solidification; On the other hand, flying ash adopts direct landfill disposal options, and its heavy metal stripping will can not be ignored the hazardness of HUMAN HEALTH and living environment.Therefore how to take suitable technical finesse flying ash, and reach stabilization, resource utilization and innoxious target, become when last important scientific research project.The patent of invention of Tongji University oblige living ZL200410016744.9 number " utilizing the city garbage burning lime-ash to fire the method for eco-cement grog " is disposed flying ash for building material industry new thinking is provided.The present invention utilizes flying ash to prepare New Building Materials first---haydite.Haydite is a kind of light skeletal for building, can replace traditional rubble, cobble etc. to make light aggregate concrete goods such as holllow building block, light weight board etc. with it.The research that utilizes solid waste to produce haydite more and more comes into one's own, and constantly obtains new breakthrough.New variety such as existing lytag, sludge ceramsite, garbage ceramsites are come out.The lytag that wherein utilizes coal-fired station's by product flyash to form through high-temperature firing for main raw material(s) is to occur the earliest, obtains the widest environment-friendly type ceramic product of practical application.This invention has also been used for reference the successful experience of lytag to a great extent.Because the main component of city garbage burning flying ash is harmless salt, the flyash in its component and common fuel-burning power plant is comparatively approaching, produce haydite so can be used as main raw material(s), can be in innocent treatment procedure, participate in solid state reaction, liquid phase reaction and ceramisite sintered process between the haydite materials directly, finally form haydite.Meanwhile, flying dust is carried out high temperature incineration, the heavy metal melting and solidification in the flying dust in haydite, is carried out high temperature pyrolysis with Dioxins, thereby realize innoxious, recycling treatment by the haydite kiln system.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, by the haydite kiln system solid waste flying dust is carried out high temperature incineration, with the heavy metal melting and solidification in the flying dust in haydite, Dioxins is carried out high temperature pyrolysis, thereby realize, recycling treatment innoxious, and it is effectively utilized as resource the solid waste flying dust, avoid secondary pollution, reduce the wasting of resources, but both safe disposal incineration of refuse flyash utilizes city garbage burning flying ash to prepare haydite economically, feasible again.
For achieving the above object, the present invention is achieved by the following technical programs.
Utilize the haydite of incineration of refuse flyash for raw material, its raw material is formed and weight percent content is: flying dust 20%～80%, and all the other are clay;
Utilize the preparation method of porcelain granule of incineration of refuse flyash, press raw material composition and weight percent content batching for raw material: flying dust 20% ~ 80%, all the other are clay; Make haydite through granulation, high-temperature calcination;
The sintering temperature of described high-temperature calcination is 1000 ℃～1400 ℃;
Preferable haydite materials is formed and weight percent content is: flying dust is 40%～60%, and all the other are clay;
Preferable sintering temperature is 1150 ℃～1250 ℃.
The invention has the beneficial effects as follows, turn waste into wealth, with danger wastes---incineration of refuse flyash is as the haydite materials regeneration, by the haydite kiln system solid waste flying dust is carried out high temperature incineration, with the heavy metal melting and solidification in the flying dust in haydite, Dioxins is carried out high temperature pyrolysis, thereby realize, recycling treatment innoxious to the solid waste flying dust, and it is effectively utilized as resource in addition, avoid secondary pollution, reduce the wasting of resources, but both safe disposal incineration of refuse flyash utilizes city garbage burning flying ash to prepare haydite economically, feasible again.Both reduced the cost of disposal of flying dust, reduced the demand of haydite industry again natural matter (as clay etc.).
Embodiment
The used incineration of refuse flyash of the present invention is taken from Tianjin Dual dock garbage incinerating power plant flue gas purification system, and the main chemical compositions of flying dust sees Table 1.
Main chemical compositions/the % of table 1 incineration of refuse flyash
| Name of material | Loss on ignition | SiO 2 | Al 2O 3 | Fe 2O 3 | CaO | MgO | K 2O | Na 2O | SO 3 | Cl - |
| Flying dust | 7.3~ 9.5 | 41.5~ 52.5 | 12.8~ 19.5 | 3.6~ 6.8 | 12.6~ 14.5 | 3.0~ 4.2 | 2.2~ 3.8 | 2.0~ 2.6 | 3.1~ 3.5 | 1.6~ 2.3 |
The chemical ingredients of haydite materials is the principal element that causes haydite swelling.Can be divided into 3 classes by its effect:
(1) becomes Tao Chengfen, SiO is arranged
2, Al
2O
3, Fe
2O
3, in raw material, account for 3/4;
(2) composition of fluxing mainly has been the flux oxide compound of fluxing action, and K is arranged
2O, Na
2O, MgO, CaO, FeO etc.;
(3) composition of getting angry produces gas, as H when material high temperature
2O, O
2, CO
2, CO, H
2Deng.
The chemical ingredients of haydite materials commonly used requires as shown in table 2.
Table 2 is used haydite materials chemical ingredients requirement/% always
| Composition | SiO 2 | Al 2O 3 | Fe 2O 3 | K 2O+Na 2O |
| Massfraction/% | 48~68 | 12~18 | 5~10 | 2.5~7.0 |
Main chemical compositions in the flying ash is SiO as can be seen from Table 1
2, CaO, Al
2O
3, Fe
2O
3, and each component content can satisfy the requirement of haydite materials chemical ingredients.By the reasonable raw material proportioning, make its chemical Composition Control in the described scope of table 2, can guarantee to burn out qualified ceramic product.
The flying dust of burning away the refuse mainly exists to the haydite quality influence: aspect cylindrical compress strength, tap density, water-intake rate, radioactivity, organic content etc. are several.The embodiment that flying dust and clay allocate by a certain percentage of burning away the refuse and the mensuration of every performance index, undertaken by GB2842--81 " Test methods for lightweight aggregates " relevant regulations, adopt " leca and pottery sand national standard " (GB2839-81), according to the results are shown in Table 3.
The flyash haydite that the different flying dust addition contents of table 3 are fired is 1200 ℃ in sintering temperature, and the emitted dose of gac is 80mg/m in the flue gas
3Correlated performance among embodiment when (flue gas) detects
| Test item | Unit | Standard-required | The flying dust addition content | ||||
| 0％ | 20％ | 40％ | 60％ | 80％ | |||
| Cylindrical compress strength tap density apparent density water-intake rate coefficient of softening | MPa kg/m 3 kg/m 3 ％ / | ≥4.0 710～800 ---- ≤22 ≥0.8 | 4.8 780 ---- 14 1.0 | 4.6 775 ---- 15 0.9 | 4.5 760 ---- 15 0.9 | 4.3 750 ---- 15 0.9 | 4.0 730 ---- 19 0.8 |
| Grain type coefficient boils mass loss loss on ignition sulfur trioxide content of organics clay content ball clay content | / ％ ％ ％ / ％ ％ | ≤2.0 ≤5 ≤5 ≤1.0 ≤3 ---- | 1.5 2 1.0 0.0 are not deeper than reference colour 2---- | 1.6 2 1.2 0.1 are not deeper than reference colour 2---- | 1.6 2 1.3 0.2 are not deeper than reference colour 2---- | 1.6 3 1.4 0.3 are not deeper than reference colour 2---- | 1.9 3 1.8 0.8 are not deeper than reference colour 2---- |
From the result of table 3 as can be seen, admixture incineration of refuse flyash volume is in 0%～80% scope in haydite materials, every quality parameter of the flyash haydite product of being produced all complies with the national standard requirements, but increase along with the flying dust volume, every performance index of haydite have downtrending, and especially after the flying dust volume was above 60%, this downtrending was more obvious, when the flying dust volume reached 80%, multinomial quality parameter was near the national standard limit value.Therefore, admixture incineration of refuse flyash volume should be controlled in 40%～60% scope in haydite materials.
Incineration of refuse flyash is rich in objectionable constituent such as heavy metal substance and sees Table 4.
Heavy metal content and heavy metal thereof leach toxicity in table 4 flying dust
| The heavy metal title | Heavy metal content (mg/kg) | Heavy metal leaches concentration (mg/l) | Solid waste leaches toxicity judging standard (mg/l) |
| Zn Pb Cu Cd Cr | 1500～2900 900～1500 220～450 26～42 110～180 | 59.0～62.5 15.0～19.5 3.2～8.3 0.6～1.4 1.9～2.8 | ≤50 ≤3.0 ≤50 ≤0.3 ≤1.5 |
By table 4 data as can be known, the concentration of Zn, Pb, Cd, Cr all is higher than solid waste leaching toxicity judging standard (GB5085.3-1996) in the flying dust leach liquor.
The dioxins concentration detected result of incineration of refuse flyash shows.The total toxic equivalent of Dioxins (I-TEQ) fluctuation range contained in the flying dust is at 965ng/kg～3560ng/kg.China does not have Dioxins limitation standard in the corresponding solid waste at present as yet.But foreign standard can be used for reference, the limit value of Dioxins toxic equivalent is 1000ng/kg in the quality standard of Germany, Soil Loss, New Zealand is 1500ng/kg, and the dioxins concentration of incineration of refuse flyash is close to or higher than the limit value of Dioxins toxic equivalent in the soil as can be known.
Just because of enrichment simultaneously in the flying ash multiple harmful substances, so intractability is bigger, must takes required measure to give comprehensive safety and dispose, common single disposal options is difficult to prove effective.Utilize the haydite method to dispose incineration of refuse flyash and then possess curing heavy metal and the effect of decomposing Dioxins simultaneously, its know-why is as follows:
(1) ceramisite sintered process is to the fly-ash heavy metal solidification:
Since in the batching of flyash haydite based on flying dust, so the sintering procedure of haydite melting and solidification process of flying dust just.This melting and solidification technology mainly is with the haydite blank after the mixing granulation moulding, fusion for some time under 1000 ℃～1400 ℃ high temperature, be generally 30min～50min (fusion time decides on the difference of flying dust character), heavy metal replaces the portion C a in the silicate minerals in this process
2+, Al
3+And be encapsulated in the netted lattice of silicate, after treating that the physics of flying dust and chemical state change and satisfy ceramisite sintered requirement, cooling makes its curing, forms category of glass or ceramic-like cured body, by the compact crystal structure of this cured body, can guarantee the stable of heavy metal.Melting treatment has preferably loss of weight and subtracts the appearance effect.The leaching yield of heavy metal is very low after the fusion simultaneously, can satisfy present leaching toxicity criterion.Find that by toxicity leaching characteristic experimental result heavy metal leaching yields such as Zn, Cr, Pb, Cd, Cu are all very low, as shown in table 5.
The flyash haydite of the different flying dust addition contents of table 5 is 1200 ℃ in sintering temperature, and the emitted dose of gac is 80mg/m in the flue gas
3Cu, Zn, Pb, Cd, Hg leach concentration mg/L among embodiment when (flue gas)
| The flying dust addition content | 0％ | 20％ | 40％ | 60％ | 80％ | Leach toxicity judging standard value GB5085.3-1996 |
| Cu | 0.05L | 0.05L | 0.05L | 0.05L | 0.05L | ≤50 |
| Zn | 0.16 | 0.17 | 0.20 | 0.18 | 0.21 | ≤50 |
| Pb | 0.2L | 0.2L | 0.2L | 0.2L | 0.2L | ≤3 |
| Cd | 0.05L | 0.05L | 0.05L | 0.05L | 0.05L | ≤0.3 |
| Total Cr | 0.081 | 0.095 | 0.106 | 0.089 | 0.112 | ≤1.5 |
Annotate: " X " represents the method detection limit of this project among the result " XL ", and " L " expression is lower than detection limit.
(2) the ceramsite sintering process is to the pyrogenetic decomposition of Dioxins in the flying dust
The dioxin organism is the extremely strong material of toxicity, mainly is chloride macromolecular compound in the domestic refuse (as dioxin precursors such as polyvinyl chloride, chlorinated benzene, pentachlorophenols), in suitable temperature and at CuCl
2, FeCl
3Katalysis down and HCl, O
2Reaction generates dioxin-like chemical.Relevant result of study shows that it is 300 ℃～500 ℃ that the best of Dioxins generates temperature.Along with temperature in the burning process raises gradually, to about 750 ℃, the dioxin-like chemical that molecular weight is bigger begins to decompose, and dioxin-like chemical will decompose fully during to 1000 ℃ of left and right sides, and Dioxins thoroughly is decomposed into CO in the haydite high-temperature sintering process
2And H
2Innoxious substances such as O.At present, the received view that can decompose fully about dioxin-like chemical is in temperature field, 850 ℃ of left and right sides more than the residence time 2s, or stops several microseconds about 1200 ℃.
Haydite kiln temperature height, gas temperature and temperature of charge are respectively up to 1400 ℃ with 1200 ℃, gas is long by the time in the kiln, gas reached more than 4 seconds in the residence time of high temperature section more than 1200 ℃, thermal inertia in the kiln is big simultaneously, operating mode is stable, the high-temperature gas turbulent flow is strong, help the mixing of gas-solid biphase, heat transfer, mass transfer, decomposition, chemical combination and diffusion, thereby can effectively any organic compound in the crude fuel be decomposed fully, also effectively prevent regenerating of dioxin-like chemical simultaneously.For preventing that the fume emission that produces in the haydite preparation process from causing secondary pollution to environment, the kiln exit gas of haydite kiln is before discharging enters atmosphere, at first in flue, spray objectionable impuritiess such as heavy metal possible residual in the charcoal absorption flue gas, Dioxins, by bagroom dust in flue gas and activated carbon granule are together captured then, formed bagroom captures ash and directly sprays into the high-temperature zone by the kiln hood of haydite kiln to accept calcining again be innoxious substance, and the emitted dose of gac is 10mg/m in the wherein said flue gas
3(flue gas)～300mg/m
3(flue gas).The ratio of preferable flying dust in the haydite raw material of mixed preparing is 40%～60%, and the sintering temperature of haydite is 1150 ℃～1250 ℃, and the emitted dose of gac is 60mg/m in the flue gas
3(flue gas)～120mg/m
3(flue gas).After testing, the total toxic equivalent of Dioxins (I-TEQ) fluctuation range contained in the flyash haydite is at 1.0ng/kg～1.5ng/kg, and the limit value far below Dioxins toxic equivalent in the soil of developed country's formulation can guarantee the safe handling of this product.
Monitoring result to the exhaust gas emission of haydite kiln sees Table 6.
Table 6 flying dust proportion in the haydite raw material is 60%, and sintering temperature is 1200 ℃, and the emitted dose of gac is 80mg/m in the flue gas
3Flyash haydite kiln exhaust gas emission monitoring result when (flue gas)
| Sequence number | The pollutent title | Unit | " dangerous waste incineration pollution control criterion " GB18484-2001 | Monitoring result |
| 1 2 3 4 5 6 7 8 9 10 11 12 13 | Blackness of exhaustion flue dust CO SO 2 HF HCl NO xMercury and compound cadmium thereof and compound arsenic thereof, nickel and compound lead thereof and compound chromium thereof, tin, antimony, copper, manganese and compound dioxin (TEQ) thereof | Lingemann grade mg/m 3 mg/m 3 mg/m 3 mg/m 3 mg/m 3 mg/m 3 mg/m 3 mg/m 3 mg/m 3 mg/m 3 mg/m 3 ng/Nm 3 | 1 80 80 300 7.0 70 500 0.1 0.1 1.0 1.0 4.0 0.5 | 0.5 40 60 120 4.8 29 80 0.06 0.002 0.08 0.107 0.028 0.09 |
Monitoring result to the exhaust gas emission of haydite kiln shows, the content of discharging dioxin-like chemical in the gas in the ceramsite sintering process is very low, the total toxic equivalent of Dioxins can satisfy " dangerous waste incineration pollution control criterion " (GB18484-2001) in, about Dioxins emission limit 0.5ng/Nm
3Requirement.Dust, SO
2, NO
2And the also complete allow compliance with emission standards of the discharge index of heavy metal, can not produce and pollute surrounding environment.Therefore use is safe and reliable to flying ash as haydite materials.
The invention provides a kind of new type of safe utilizes incineration of refuse flyash to prepare the pattern of flyash haydite.Utilize incineration of refuse flyash to prepare haydite, can effectively the heavy metal substance in the flying ash be solidificated in the haydite mineral, and can guarantee that the heavy metal in the flying dust is difficult for leaching from the aquation system, thereby guarantee its safe handling.In actual production, can determine the addition content of incineration of refuse flyash, as long as the main chemical compositions SiO of control haydite blank according to the type of haydite kiln and the character and the composition of local starting material and incineration of refuse flyash
2, CaO, Al
2O
3, Fe
2O
3Content in the described scope of table 2, can burn out the ceramic product that meets national standard.
The present invention utilizes incineration of refuse flyash to burn out to meet the high-quality flyash haydite of national standard, carries out recycling thereby the flying ash that is difficult at present dispose has been become material of construction.Reduced the cost of disposal of flying dust on the one hand significantly, found practicable outlet, helped avoiding causing flying dust illegally to be abandoned or the simply generation of landfill phenomenon because of cost of disposal is too high for the safe disposal of flying dust.Reduced the demand of haydite industry on the other hand again to natural matter (as clay etc.).And haydite solidification to various heavy metal elements in the flying dust in sintering process is very effective, and the overwhelming majority of various heavy metal elements all has been solidificated in the mineral crystalline phase of haydite; Dioxins in the flying dust thoroughly is decomposed into CO in the haydite high-temperature sintering process
2And H
2Innoxious substances such as O; Add strict purifying treatment, can effectively avoid the generation of secondary pollution phenomenon the kiln exit gas of haydite kiln.The present invention disposes the breakthrough that utilizes to the flying ash the like waste, and is all significant at New Building Materials and field of environment engineering.The present invention will produce significant social, economic benefit, and Sustainable development industrial to haydite and the waste incineration industry will produce positive pushing effect.
Claims (5)
1. a haydite that utilizes incineration of refuse flyash for raw material is characterized in that, its raw material is formed and weight percent content is: flying dust 20%～80%, all the other are clay.
Claim 1 utilize the preparation method of porcelain granule of incineration of refuse flyash for raw material, it is characterized in that, press that raw material is formed and the weight percent content batching: flying dust 20%～80%, all the other are clay; Make haydite through granulation, high-temperature calcination,
3. haydite preparation method according to claim 2 is characterized in that, the sintering temperature of described high-temperature calcination is 1000 ℃～1400 ℃.
4. the haydite that utilizes incineration of refuse flyash for raw material according to claim 1 is characterized in that, its raw material is formed and weight percent content is: flying dust is 40%～60%, and all the other are clay.
5. according to claim 2 or 3 described haydite preparation methods, it is characterized in that the sintering temperature of described high-temperature calcination is 1150 ℃～1250 ℃.
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Family Cites Families (1)
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|---|---|---|---|---|
| CN1456533A (en) * | 2002-05-10 | 2003-11-19 | 长春市环境保护技术开发公司 | Method for producing ceramic granules by refuse |
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