CN1226655A - Method and materials for treatment of purifying harmful gases and cinders at bottom of cremator - Google Patents
Method and materials for treatment of purifying harmful gases and cinders at bottom of cremator Download PDFInfo
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- CN1226655A CN1226655A CN99100417A CN99100417A CN1226655A CN 1226655 A CN1226655 A CN 1226655A CN 99100417 A CN99100417 A CN 99100417A CN 99100417 A CN99100417 A CN 99100417A CN 1226655 A CN1226655 A CN 1226655A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D47/06—Spray cleaning
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- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/14—Disinfection, sterilisation or deodorisation of air using sprayed or atomised substances including air-liquid contact processes
- A61L9/145—Disinfection, sterilisation or deodorisation of air using sprayed or atomised substances including air-liquid contact processes air-liquid contact processes, e.g. scrubbing
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/005—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by heat treatment
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/64—Heavy metals or compounds thereof, e.g. mercury
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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Abstract
A method for treating and purifying wastes is disclosed in the invention. The characteristic is in that: bringing an aqueous film forming inorganic compound material consisting of siloxane and a silanol salt(s) into contact with a combustion gas of harmful waste and flying ashes, thereby generating a film-making expansion foam and a combustion residue containing a black smoke and malodor, harmful gas and heavy metal, and meanwhile sealing these wastes comprised of the black smoke and malodor, harmful gas and heavy metal as harmful materials inside to combust the same. Accordingly, the generated harmful materials, i.e., the black smoke and malodor, harmful gas and heavy metal, etc. are concurrently sealed and purified.
Description
The present invention relates to contain the material for treatment of purifying and the purifying treatment method thereof of black smoke and stench and heavy metal, the pernicious gas of flying dust and the residual ash of piling up in the incinerator bottom etc.
Needless to say produce black smoke and stench when coming from the waste combustion of living environment, even public hazards that the stripping of the harmful heavy metal that contains in the flying dust to the burning that jettisons ash and discharging causes and also should in addition strict restriction in the discharging of the strict restriction in Europe De bioxin.
Yet administrative guidance requires to be converted to by the medium and small incinerator of the discontinuous running of present processing discarded object the large-scale melting furnace burning method of continuous running.But if afore mentioned rules is arranged, in the operation local autonomy body of port and be engaged in the middle of offal treatment person will be forced to drop into the great number reforming equipment or stop doing business but the suggestion of the reality that does not also address this problem.
As long as in discarded object, contain metal and composition Cl, certainly lead to the precursor of pernicious gas bioxin behind the organic compound combustion.In the final operation of pump-down process, use the bag hose of non-refractory in addition, even in delivering to the bag hose way, carry out cooling processing and washer processing, also can produce bioxin, handle with inorganic matter and mineral sorption, but residue thing and sorbent need to handle again.Handle fully for making, the complicated treatment technology and the equipment of great number also must be arranged.
In the residual ash of incineration residue, the remaining heavy metal that public hazards are arranged jettisoned banketing of appointment after handling with chelating agent in the past and handles with burying, but it is generally acknowledged the long-time stability deficiency, had safety issue in addition.Particularly ， bioxin and heavy metal remain in wherein after concentrating in flying dust, handle very difficult with chelating agent.
In addition, because generation black smoke and stench bring influence to surrounding resident, this is applied the incinerator expense costliness of countermeasure, therefore wish to search out simple and cheap method with small incinerator.
Environmental Agency is if will reach the Dui bioxin and the setting of other gases and heavy metal; then the improvement expenses costliness of existing incinerator can only decommission, in addition; the various fusion reducing furnaces that are used for handling fully need spend huge fund, worry to increase the resident's who protects environment burden.
The effluent air temp of incinerator is up to 200-800 ℃, do not have to filter the organic matter filter of black smoke and stench, after cooling processing or washer processing, other suggestions are arranged perhaps, after ceramic catalyst or sorption body processing cooling, be transported in the bag hose again.Thereby because device costs an arm and a leg, resistant to elevated temperatures inorganic filter device and the sorbent material that does not need to adopt post processing found in expectation.The present invention will address this problem.
In the past, known processing contains the residual ash of heavy metal and the method for flying dust, have the organic matter chelating agent that produces of the isocyanides acid facture of mixing for example, this method is widely used, but be difficult to estimate the stability of chelating method, so need find a kind of method that can make heavy metal carry out stable ions binding with chemical mode with the mode of chemistry.
In Europe, come into effect the countermeasure of handling bioxin very early, but also account for main flow in recent years with the method that emission gases is cooled off, the precursor of bioxin is under the situation that HCl exists in the light of recent researches, bioxin be can produce at low temperatures,, the activated carbon that can also use more than 450 ℃ and the sorption method of calcium hydroxide effectively utilized for addressing this problem.But also exist the post processing problem of this sorbent.However, bag hose or necessity because must handle the flying dust of missing that contains remaining heavy metal therein.That is to say, in handling the emission gases process, certainly need be to containing the flying dust of bioxin precursor and iron chloride and heavy metal, or the Dui bioxin catalyst of decomposition and public hazards thing arranged the suction-operated filter arranged, also need post processing for re-using filter.
The present invention has considered each each side that relates to, even so in the middle port of discontinuous running, use the present invention, also be easy to reach and be considered as the most inaccessible bioxin setting, adopt the present invention can reduce the transformation expense of installation cost and existing stove, alleviate resident's burden, also can be widely used on other industries.
Will " autofrettage of waterborne film-forming inorganic compound " (speciallyying permit No. 2028203 the fair 7-14801 of spy number) after the suggestions such as present inventor, " take precautions against natural calamities, fire prevention, refractory composite " (speciallyying permit No. 2015694) etc. be referred to as preceding invention silanol salting liquid.Invention silanol salting liquid before this adopts metallic silicon and borax and sodium fluoride, zincic acid or its salt, and alkali metal (Na, K Li), are made by solid and concentrated alkali solution reaction and to form, and it is different with waterglass, is made of siloxanes and silane alkoxide.
Fig. 1-the 4th, the heat-resisting inorganic matter of representing to use in the present invention of waterborne film-forming inorganic compound (LC) 250 ℃, 550 ℃, in the time of 960 ℃, in FTIR analyzes, reduce the figure that demonstrates film forming at 20 ℃ with temperature rising hydrone peak value.Transverse axis represents that WAVE NUMBERS (wave number), the longitudinal axis represent ABSORVANCE (absorbance) in Fig. 1 to Fig. 4.Analysis report in this beautiful research center, east, the FTIR of figure (1-4) shows at 780cm in analyzing
-1The time siloxanes exist, and 900,1000,2400-3800cm
-1The time silanol exist.The silanol salting liquid of aforementioned invention is even be a kind of all have hear resistance and Undec heat proof material when the temperature of discharging gas is in 200-1000 ℃ of such high temperature range.
Aforesaid invention silanol salting liquid has dilatancy (intumescence).According to above-mentioned eastern beautiful analysis report, there is opal (afrodite) to generate in the time of 650 ℃.(X raydiffraction X line resolver, it is the special device of only analyzing the Si compound to 500 ℃ the XRD that Fig. 5 represents.) peak value, judge relatively with the peak value difference of waterglass to obtain that its crystallization speed is fast.In Fig. 5, the longitudinal axis is the absorption spectra cm2/g of X line, and transverse axis is that wavelength is made target with Cu.The peak crystallization of preceding invention silanol salting liquid is very clear, and being illustrated in low temperature becomes solid phase precursor film forming, and this can explain if possess the water evaporation and intumescent reason then occur.In fact, be that 50% liquid is coated on the iron plate with preceding invention silanol salting liquid solid constituent, all produce foamed phenomenon from lower heating or from the upper nozzle heating.This phenomenon lasts till 650 ℃, with the heating-up temperature rising foaming and intumescing phenomenon spectrumization then that disappears, is coated with membranization later on.Heating microscope with Japanese high-tech ヅ ャ パ Application Ha ィ テ ッ Network (strain) can be observed this phenomenon.Represent this phenomenon with the schematic diagram of Fig. 6.Epimere figure among Fig. 6 be the expression waterborne film-forming inorganic compound (LC) thus because of exhaust foamed, one-tenth membranization become colloid filter, the schematic diagram of the state of purified treatment gases such as discharge water steam, carbon dioxide.Stage casing figure represents that when residue thing temperature reduced, foaming was the schematic diagram of calmization state.Hypomere figure is illustrated in when turning back to normal temperature, comprises the schematic diagram of the state of exhaust residue thing in filming.This waterborne film-forming inorganic compound (LC) colloid plays the effect of heat-resisting filter.Contain high-temperature gas and the flying dust that contains heavy metal in the burning exhaust of discarded object, preceding invention silanol salting liquid in order to comprise above-mentioned exhaust, must expand into the degree that is full of the exhaust pipe arrangement.Because preceding invention silanol salting liquid becomes the film forming dilatant because of high-temperature exhaust air, thereby has reached purpose of the present invention and effect.
The heating silanol, its H and OH dehydration becoming silica alcohol have been final conclusion, therefore think if heavy metal is arranged, will be combined into-Si-O-R (R is a metal) this moment.Preceding invention silanol salting liquid contains thing with heavy metal and mixes, the incinerated matter of analysis of mixtures, and the result shows that heavy metal does not have stripping, demonstrates this fact.If as coating is coated hidden, so test material to be pulverized, heavy metal will inevitably stripping.But adopt the method for test material being pulverized and experimentizing, the result does not observe heavy metal stripping from solidify crushed material under 800 ℃ or above high temperature, therefore think that this is the effect of ions binding, that is to say that showing has the seizure effect to heavy metal.
Preceding invention silanol salting liquid is the colloid of 0.5-1 micron.Observe the FTIR of above-mentioned Fig. 1-4, also do not disappear even temperature reaches 900 ℃ of hydroxys.Fig. 7 represents preceding invention silanol solution, when the gas heating-up temperature at 450 ℃, nozzle temperature makes the microphotograph of its powdered, the foaming nodularization state of 50-80 micron-scale with spray dryer in the time of 180 ℃.Observe the schematic diagram of inferring of Fig. 6, if under the condition that excessive water exists, heat by high-temperature gas, the colloid that film forming expands because of the gelling material on surface by deposited, this thinks that gel possesses water evaporates, and under the effect of filter the solid constituent of discarded object is wrapped in inside and the residue thing is piled up.Harmful exhaust De bioxin is reflected at 450 ℃ or above existing final conclusion can not take place, if therefore capture the precursor and the hydrochloric acid composition of bioxin, even then be cooled to generate easily 400 ℃ of the temperature of bioxin or following, also can control the generation of bioxin.
The silanol salting liquid of aforementioned invention is an alkali metal salt soln.With outlet temperature be 200 ℃ spray dryer with residual moisture blow away make its powdered after, it is mixed with PVC with weight ratio 40%, do 750 degree combustion analyses with road graceful (De-マ ソ) elementary analysis meter, from analysis result, volatility hydrochloric acid reduces to very little, non-volatile HCl is increased to 6000 times, catches analytic approach with filter and obtains that ash reduces to about 25%, volatility hydrochloric acid and ash significantly reduces, and stench also reduces.Fig. 8 is solid particulate thing shown in Figure 7 mixes the gas of back calcining with PVC a analysis report table, and analysis center provides by Japanese geon (ゼ オ Application).According to result of study, infer that the reason that the black smoke stench reduces is that preceding invention silanol salting liquid has the effect of catching gas.Even especially the Li salt of hydrochloric acid is caught Cl, also be difficult at low temperatures decompose.Invention silanol salting liquid can effectively tackle PVC De bioxin before can thinking.
Pb content is maximum in the heavy metal of discarded object, therefore with it as model, if when containing Pb composition 500-2000ppm in the residual ash, then containing 15, in the ash of 000ppm flying dust, according to the weight content of Pb wherein, before mixing invention silanol salting liquid to 10%-140%, be heated to 900 ℃ or more than.No matter under which kind of condition, in the dissolution test result of Pb, the stable type assay value that obtains all is the 0.01ppm/ liter, can think to have generated the siloxane bond of above-mentioned explanation.
The CCA that uses in timber preservative contains copper, chromium and arsenic, adds 10% aforementioned invention silanol salting liquid in its 5% solution, is green after 900 ℃ of heat cures, carries out dissolution test, chromium, and copper, the content of arsenic are all at 0.01ppm or following.This thinks that these heavy metals also are ions binding.
If the silanol salting liquid of invention before the spraying in 200 ℃ or above high-temperature exhaust air, because instantaneous gel film forming and expanded foamization is included in black smoke and stench wherein like this.This presentation of results gel colloid has the effect of filter, and spraying is an effective method in exhaust.It is necessary that the spraying means adopt instantaneous enlargement method, therefore if use the ejector spray that produces high pressure, produce enough negative pressure of suction, generation makes exhaust be included in effect in the film forming dilatant of aforementioned silanol salting liquid, generation comprises the residue thing of the gelation of flying dust, carry the back to pile up because of difference in specific gravity residue thing pressure, only steam is evaporated.No matter be pressure atomization in the exhaust of air blast air-supply, or in the air-supply exhaust, drip and all produce same effect.Before invention silanol salting liquid force feed, to spray, drip be necessary means.The contact method of preceding invention silanol salting liquid and above-mentioned exhaust, no matter be in the exhaust that is sucked air-supply, to spray, or drip silanol solution, still with opposite, high-temperature exhaust air is blown in the aforementioned silanol salting liquid contacts with it, all film forming expands and produces same action effect.Because it is pile up, so also effective even mix inorganic material powders such as kaolin and carbon dust because of difference in specific gravity produces.
The discarded object that contains organic matter or heavy metal, soil, moisture etc. mixes mutually with preceding invention silanol salting liquid easily.As above-mentioned, if combustion of organic matter, the aforementioned silanol salting liquid that has mixed will the film forming expansionization after, thereby burning gases are comprised and make it carbonization and gasification, catch ash or Cl gas, play the effect that only makes the filter that steam passes through, mix with residual ash simultaneously.If the aforementioned silanol salting liquid of spraying then can be brought into play the purified treatment effect of the present invention that residual ash and gas purify simultaneously in above-mentioned exhaust.
With the above-mentioned exhaust residue deposit or the residual ash that contain preceding invention silanol salting liquid, 800 ℃ or more than, for example in rotary furnace, burn, even then wherein contain harmful heavy metal, after the potteryization, can make the stable type valuables of not stripping be reduced to designated ratio.
For solving above-mentioned problem, technical solution of the present invention is as follows:
1. a kind of material for treatment of purifying is provided, it is characterized in that, the burning gases of waterborne film-forming inorganic compound that is made of siloxanes and silane alkoxide and the bazardous waste that contains black smoke and stench and heavy metal, flying dust are contacted, form the film forming dilatant, become the combustion residue thing that comprises black smoke and stench and pernicious gas and heavy metal therein, thus simultaneously will be as above-mentioned black smoke and stench and the pernicious gas and the heavy metal sealing of nuisance and public hazards thing.
2. in addition, another material for treatment of purifying is provided, it is characterized in that, the waterborne film-forming inorganic compound that is made of siloxanes and silane alkoxide is mixed with the residual ash of piling up in the incinerator bottom of burning waste, form the mixture of residual ash and waterborne film-forming inorganic compound, thereby obtain being overlayed on the combustion residue thing on surface, simultaneously with nuisance and the sealing of public hazards thing by the film of above-mentioned waterborne film-forming compound.
3. in addition, above-mentioned the 1st and 2 described handled thing is characterized in that, the 1st or 2 described above-mentioned film by the waterborne film-forming inorganic compound overlayed on the combustion residue thing on surface or both mixtures at 800 ℃ or above temperature lower calcination.
4. in addition, the invention provides a kind of purifying treatment method of discarded object, it is characterized in that, the waterborne film-forming inorganic compound that is made of siloxanes and silane alkoxide is contacted with the burning gases and the flying dust of discarded object, form the film forming dilatant, become the combustion residue thing that comprises black smoke and stench and pernicious gas and heavy metal therein, the discarded object that black smoke and stench and pernicious gas and heavy metal constituted that seals simultaneously as nuisance and public hazards thing is burnt, handle simultaneously the nuisance that contains thing etc. of the black smoke that generates and stench and pernicious gas and heavy metal and public hazards thing are carried out enclosed purification.
5. in addition, the purifying treatment method of above-mentioned the 4th described discarded object is characterized in that, above-mentioned contact is to be realized by the waterborne film-forming inorganic compound that siloxanes and silanol constitute by spraying in the burning gases of discarded object.
6. in addition, the purifying treatment method of above-mentioned the 5th described discarded object, it is characterized in that, when above-mentioned waterborne film-forming inorganic compound is contacted with the burning gases of discarded object, on flue or attraction side line, the pressure atomization device is installed, spraying water-based film forming inorganic compound aspirates above-mentioned black smoke and stench and pernicious gas and heavy metal by the negative pressure that produce this moment.
7. in addition, the purifying treatment method of above-mentioned the 4th described discarded object, it is characterized in that, when above-mentioned waterborne film-forming inorganic compound is contacted with the burning gases of discarded object, in above-mentioned waterborne film-forming inorganic compound, be blown into 200 ℃ or above waste combustion gas, become and comprise the residue thing that above-mentioned black smoke and stench and pernicious gas and heavy metal contain thing therein.
8. in addition, the purifying treatment method of another kind of discarded object is provided, it is characterized in that, the waterborne film-forming inorganic compound that is made of siloxanes and silane alkoxide is contacted with the residual ash of burning discarded object, form the film forming dilatant, handle nuisance and public hazards thing with enclosed purification.
9. in addition, the purifying treatment method of the described discarded object of above-mentioned 4-8 item, it is characterized in that, the handled thing of above-mentioned nuisance and public hazards thing will be sealed simultaneously, perhaps above-mentioned waterborne film-forming inorganic compound is mixed with the residual ash and the flying dust of discarded object after burning, make its potteryization 800 ℃ or above heating, prevent the stripping of nuisance and public hazards thing.
At above-mentioned 3 kinds of material for treatment of purifying, in 5 kinds of refuse processing methods, as the above-mentioned waterborne film-forming inorganic compound that constitutes by siloxanes and silanol, what preferably use is to make metallic aluminium or metallic silicon, borax with hydration, boric acid, sodium fluoride or fluoric acid and zincic acid compound, and caustic potash, when caustic soda or the reaction of causticity lithium alkali metal, in water or in the solution of above-mentioned inorganic acid compound, above-mentioned metal solid and above-mentioned alkali-metal concentrated solution reaction take place, this reaction heat is controlled in 50 ℃-100 ℃, and, the proportion of product become 1.1 or more than, the waterborne film-forming inorganic compound of generation.In addition, make the superfluous effect of metal ingredient fine if in the waterborne film-forming inorganic compound of above-mentioned generation, add metallic compound.In addition, add or do not add the alcohols of inorganic acid and the proportion 1.3 that generates or above sediment are better if be mixed in hydrotropism's film forming inorganic compound.Adding natural or synthetic mineral dust or mineral fibres, mineral lamellar thing in hydrotropism's film forming inorganic compound, to carry out the words of tackify effective.In addition, can add hydroxide metallic compound or hydraulic-composition in hydrotropism's film forming inorganic compound.
Various result of the tests can prove do not having under the situation of bag hose, can be to the black smoke of castoff burning gas and stench He the hydrochloric acid of bioxin precursor and the flying dust and the heavy metal that become hotbed catch.In addition, different with liquids in general, demonstrate the film forming swelling, carry out the result of gel cured coating filmization, water evaporates wraps in inner residue thing and piles up with gel, if be heated to 900 ℃ or the above stable valuables that become heavy metal can stripping again.No matter be that aforementioned silanol salting liquid is blown in the high-temperature exhaust air, still in contrast, exhaust be blown in the aforementioned silanol salting liquid, all produce identical action effect.
The De bioxin is the most harmful gas in the exhaust, but owing to be final conclusion at 450 ℃ or the above chlorine that can not synthesize its precursor, therefore if be removed, just can stop the generation of bioxin, can at high temperature not have the filter may be for use but have so far in this stage.Aforementioned invention silanol salting liquid such as hear resistance that 1-4 is shown with, colloid expanded foamization as shown in Figure 6, as the schematic diagram of Fig. 6, play the effect of filter, and as described above, because be alkali metal salt, can catch HCl, make it become nonvolatile component, can also control the ash generation and disperse.Fig. 9 Figure 10 is the general dust (MSW) that uses in combustion test and the Industrial Analysis and the results of elemental analyses table of Shi Laote dust (SD).The preceding invention silanol salting liquid that is blown in the exhaust uses a large amount of water dilutions, but aforementioned silanol salting liquid is at high temperature so not big than thermal change, and with the water coexistence of surplus, and then the effect of performance heat absorption cooling makes the gas cooled of discharging.Because middle-size and small-size stove is discontinuous running, easily form 200-450 ℃ environment temperature, be easy to generate bioxin, therefore, think dangerous.But if aforementioned silanol salting liquid of the present invention is blown into, even then under the condition of discontinuous running, even without high-temperature calcination, also can realize nuisancelessization.
If in aforementioned silanol salting liquid of the present invention, be blown into 200-800 ℃ high-temperature exhaust air, water evaporates on one side then, the aforementioned silanol salting liquid film forming in one side, demonstrate swelling, black smoke and stench that organic compound combustion is produced are included in wherein, become heat-resisting inorganic filter device, thereby realize innoxious.
The simple declaration of accompanying drawing
[Fig. 1-4] is the heat-resisting inorganic matter of the waterborne film-forming inorganic compound (LC) of expression the present invention use, and during the FTIR in the time of 20 ℃, 250 ℃, 550 ℃, 960 ℃ analyzed, Yin Jiawen hydrone peak value reduced and the figure of film forming.
[Fig. 5] is Care MSU of rock hand university committee, adopts Si-MAS-NMR that LC is analyzed, and comparison of aforementioned invention silanol salting liquid and waterglass is at 500 ℃ product, finds out that LC only has the film forming affirmation figure of peak value.
[Fig. 6] will have the silanol salting liquid of the preceding invention of excessive water to be blown in the high-temperature exhaust air, carry out bloatedization of film forming Peng, become heat-resisting filter, and temperature descends and is coated with the schematic diagram of membranization.
[Fig. 7] is to be 450 degree at gas temperature, and the sprayer outlet temperature is the microphotograph figure of the actual film-forming foam particle that produces in 180 ℃ the spray dryer.
[Fig. 8] is curing shot-like particle shown in Figure 7 and the PVC gas analysis data through mixed calcining, the table that it is provided by Japanese geon (ゼ オ Application) analysis center.
The general rubbish (MSW) that use in combustion test [Fig. 9 10] and the Industrial Analysis and the results of elemental analyses table of Shi Laite ash (SD).
[Figure 11] is the schematic diagram of the incinerator that uses of the present invention.
The result who deals with problems is described by following embodiment.
Even the silanol saline solution LC of preceding invention heating is not decomposed yet, it dewaters gradually to 1000 ℃, and the process that will change siloxanes into uses 20 ℃, 250 ℃, 550 ℃, 950 ℃ FTIR figure (analysis result in eastern beautiful research center) among Fig. 1-4 to represent.The peak value that demonstrates along with temperature ascending water molecule reduces and film forming.
The constituent analysis value of the LC that embodiment 1 is used is shown in table 1.Though LC contains the element that uses raw material, the element constituent ratio of analyzing is not limited by this.
Table 1
Invention silanol salting liquid before the ground-coat enamel
Composition ratios (weight)
55 SlO
2 60.27
20 Na
2O 21.92
15 B
2O
3 16.44
5 CaF
21.37 F is converted into CaF2
* the analysis result of ア グ ネ technique center
The such composition component ratio and the assay value of base enamel are approximate, thus equally can heat hardening and pottery be coated with membranization.
The solid constituent of the silanol salting liquid LC-150 of preceding invention is 50%, proportion is 1.5, PH=12.2, it is possessed moisture be shown in table 2 in the diminishing amount of different temperature ranges, in addition, with the specific heat between 20-1200 ℃, diffusion coefficient and adiabatic coefficent are shown in table 3 (ア ダ ネ technique center assay value).Dehydration lasts till high temperature, even during from normal temperature to 1000 ℃, specific heat still be that adiabatic coefficent changes is not very greatly, and these all show, though LC-150 at high temperature temperature also be difficult to rising, LC-150 still can work as the heat absorbent of emission gases.If there is superfluous water to exist, then because synergy has the heat absorption cooling effect.
[table 2]
Heating diminishing component analysis result
Heating-up temperature ℃ diminishing amount/possess water
20～200 94.07
200～500 4.643
500～1000 1.282
[table 3]
The insulating characteristics analysis result
Temperature specific heat thermal diffusion coefficient thermal conductivity
℃ Cal/g·℃ cm
2/S cal/cm·S·℃
20 0.200 0.00696 0.00203
300 0.363 0.00340 0.00175
400 0.310 0.00356 0.00161
600 0.312 0.00352 0.00160
800 0.326 0.00392 0.00167
1000 0.358 0.00239 0.00126
Utilize the device of the former chemical industry machine in great river, under the condition of 180 ℃ of 450 ℃ of outlet temperatures of LPG gas temperature to preceding invention silanol saline solution LC-150 jet drying.Because LC is colloid and dilatancy is arranged,, the microphotograph of this foamed is shown in Fig. 7 so form the foam of 50-80 micron.In the stabilizing agent and other addings PVC with its 20-50 weight portion and Ding Fa, with its mixing sheet material that is configured as.Fig. 8 represents ゼ オ Application analysis center to its analysis result 750 ℃ of burnings, adopts graceful (De-マ ソ) the elementary analysis meter in road and the chromatography of ions and filter traps method to analyze.Analysis result shows that even at 750 ℃ of burning PVC, volatility hydrochloric acid amount also reduces, and the fixedness hydrochloric acid content becomes 6000 times, and ash reduces to 25%.That is to say, also to have and catch the volatility Cl that impels bioxin formation and the effect that hinders bioxin formation even burning or Cl contain thing.Also can hinder simultaneously the generation of ash and stench.
With the characteristic of Si-MAS-NMR (unique analytical equipment of MSU's exploitation) the above-mentioned LC-150 of analysis, show the result in Fig. 5 (result of the test that Care MSU of committee of rock hand university obtains).The result shows that LC is made of dimer and trimer, and Fig. 5 has shown preceding invention silanol salting liquid significant crystallization peak value when 500 ℃ of average exhaust, and waterglass is owing to be amorphous state and do not show the crystallization peak value.This illustrates that above-mentioned silanol salting liquid has filming function when delivery temperature is 400-800 ℃.That is to say that above-mentioned LC colloid is if residual moisture disappears, colloid gathers the film forming with heat-resisting heat absorptivity and forms function.
Embodiment 6
Above-mentioned LC-150 is coated on the corrosion resistant plate, with the high temperature viewing microscope of Japanese high-tech (strain), from normal temperature heat to 900 ℃ on one side, on one side with the video camera observation of making a video recording.By 100 ℃ to 300 ℃ foamed, eyepiece is cleared away lens then and is observed once more beyond the Great Wall, observe to arrive 650 near the time swelling continue, be cured as the opal shape, be water stain shape 800 ℃ or above plasticizing gel then.The schematic diagram of Fig. 6 has been represented above-mentioned behavior.I.e. spraying during LC in the smokejack of burning and gas-exhausting can be thought the instantaneous foamed of LC and expands.Functioning efficiency height when the LC foamed is full of the diameter of smokejack.Also can produce identical accumulation effect in the above-mentioned silanol salting liquid even the exhaust of high temperature imported to.
Embodiment 7
Fig. 6 is the schematic diagram of expression effect of the present invention.In Fig. 6, aforementioned silanol salting liquid of the present invention is because of the exhaust foamed, its colloid film forming and become filter, and the steam that purified, carbon dioxide etc. are released, and then the foam calmness changes into and is gel mould.Above-mentioned result of the test has obtained fully and the same state of schematic diagram.
Embodiment 8
The assay value that will contain the flying dust of the PbO that 2220mg/ rises is shown in table 4, with respect to the above-mentioned flying dust of 100 weight portions, mixes 20-100 weight portion LC, with it after 900 ℃ of burnings, Prefectura de Kanagawa industry comprehensive study dissolution test the results are shown in table 5.Which kind of situation no matter, all the setting 0.01 of stable type valuables or below, illustrate that LC has the effect of purification of heavy metal.
It is as follows to burn the ash analysis value, and the stripping quantity of Pb is the 222mg/ liter.
Table 4
The ash analysis value
SiO
2 9.7 K 4.73 ZnO 0.62
Al
2O
3 5.75 Na 2.54 PbO 0.18
CaO 42.15 Cl 13.31 CuO 0.05
MgO 2.02 SO
4 4.34 Fe
2O
3 1.09
Table 5
The analysis result of stripping quantity 0.01 0.01 0.01 research institute
Following or below
Embodiment 9
Below be that urban waste flying ash and the sewage sludge that Kobe Steel, Ltd provides burns the heavy metal assay value that contains in the ash.Mix the back in 950 degree calcinings to the LC-140 that wherein adds the 10-20 weight portion (solid constituent 40%), the dissolution test of Kobe Steel, Ltd be the results are shown in table 6.Heavy metal Pb, As, the stripping quantity of Ce is below the stable type setting.
The heavy metal assay value
Heavy metal urban waste sewage sludge
Pb?mg/K 503 200
AS?mg/K 1.2 40
Ce?mg/K 0.4 ＜0.1
[table 6]
Sewage sludge flying ash mixing LC weight portion Pbmg Asmg Cemg
10 part 0.007 0.007＜0.001
15 part 0.002 0.005＜0.001
20 part 0.005 0.005＜0.001
10 part 0.01 of urban waste flying ash＜＜
15 part 0.009＜＜
20 part 0.004＜＜
Soil environment a reference value 0.01mg 0.01mg 0.01mg
Figure 11 is an experimental rig, side line (b) is installed on the flue of common incinerator (a), jar (c) by the aqueous solution of the aforementioned LC-140 of the present invention that is mixed with 20 parts by volume/1m3 (50 times), is blown into above-mentioned LC dilute solution in the side line (b) through spraying (e) with high-pressure pump (d).LC solution is with high-pressure pump the suction function down exhaust of suction and flying dust in foamed is included on one side on one side, dropping into stillpot (f) then becomes mud and piles up, treated not only do not had black smoke but also ordorless steam and carbon dioxide etc. are discharged from outlet (g), will be by the mud of stillpot bottom taking-up, put in the rotation kiln (h), 900 ℃ of calcinings, effluent (ⅰ) becomes the stable type valuables.
Embodiment 11
Fig. 9 is the Industrial Analysis and the results of elemental analyses of general rubbish (MSW) and Shi Laite ash (SD).Cl content reaches 2.2% in above-mentioned SD.Figure 10 has put down in writing the analysis result of heavy metal and micro-rare metal in this burning ash.Fe as the bioxin precursor
2O
3Be 42.72%, Cu is 25, and 700mg, Zn are 38,000mg/Kg.With the burning of the incineration experiment device in previous embodiment RDF.Not adding has black smoke and stench to exist under the situation of LC, but if when beginning to be blown into LC liquid under the pressure of 200Kg/cm2, then the black smoke in the exhaust steam (ⅰ) still is that stench all disappears.This work is finished according to the analysis of JIS pernicious gas analytic approach by (strain) steel pipe instrumentation.Delivery temperature is the easiest generation bioxin in the time of 260-350 ℃, but reduces to 2.4-2.9ppm as the HCl that generates essential factor from 250-1100ppm is sharp, be 200ngTEQ/Nm3 at steam outlet De bioxin, but mean value is 1.9ngTEQ/Nm3.Do not use bag hose not use lime and sorbent in the present embodiment yet, purify hydrochloric acid with bioxin thereby aforementioned silanol saline solution of the present invention plays heat-resisting filter.The result of its mud calcining back dissolution test in rotation kiln (h) shows that harmful heavy metal is at 0.01ppm or following.Even put a towel at steam outlet, do not find carbon attached to top yet, do not smell foul smell yet.Because the heat-absorbing action of LC, the temperature of stillpot (h) can not generate bioxin at 100 ℃ or following 50-70 ℃ under this environment temperature.
Embodiment 12
The heavy metal Pb that SD volume among Fig. 9,10 contains reaches 1313ppm, and Cd reaches 29ppm, and Zn reaches 38,000ppm, and Cr reaches 831ppm, and As reaches 29ppm.It is pressed SD and LC=10: after 10 (solid constituent ratios) mix, calcined 2 hours down for 950 ℃ in electric furnace, do the JIS dissolution test then, result of the test has reached in above-mentioned soil environment a reference value or following target.
Embodiment 13
Pulverize the SD among Fig. 9, add the invention described above silanol saline solution LC of 10 weight %, be mixed into the waste combustion thing, above-mentioned jetting fluid is the dilution that the LC of mixing 5% (solid constituent 2.5%) forms, be forced into 50K, as embodiment 11 is described, burn.Because the two all mixes discarded object and exhaust mutually with LC, so reached every liter of Pb0.01mg, Cd0.01mg, Cr0.05mg, As0.01mg or the following desired value of soil discarded object a reference value.Imperceptible and can't see the generation of stench and black smoke.
Embodiment 14
The flying dust that produces in melting furnace contains Pb17,000ppm (Xin Rinan provides).The above-mentioned solid constituent of adding 240% is 60% LC-150 in flying dust, mixes, and calcines 1 hour for 900 ℃ in electric furnace.According to the dissolution test result of No. the 13rd, Environmental Agency's bulletin, at 0.01ppm or following.
Figure 11 is the incinerator schematic diagram that the present invention uses.Chimney place at general incinerator (a) connects chimney side line (b), be blown into LC dilution (c) with high-pressure pump to this chimney side line (b) by injection nozzle (e), drop into stillpot (f) then, steam (g) becomes harmless, tasteless, colourless gas, the deposit buildup thing is calcining in rotation kiln (h), and its effluent (ⅰ) is the stable type valuables.
The electricity that produces black smoke and stench can be pulled rubber, PVC plate and the mixing of foamed styrene bits with the device of Figure 11 burns.Because directly burning, insufferable black smoke and stench can not carry out burning around producing.Solution in the basin (c) of said apparatus is adjusted into the solution (solid constituent 1%) that contains LC2%, if 1 liter the solution (solid constituent 20g) that will be equivalent to every 1m3 burning tolerance is with expulsion pressure 100Kg/cm2, be blown in the exhaust and take fire then imperceptible around black smoke and stench.Piling up the inner black mud that is surrounded by carbon in the stillpot.To other ready basin, above-mentioned 400 ℃ exhaust is blown in the above-mentioned basin (c) by the pipe guiding, instantaneous time bubbling expansionization, stench disappears, and does not have black smoke in the steam of discharge.Disappear above-mentioned even burning polyester coating, black smoke and stench also resemble, have only steam to produce.Solution in the storage bucket can not use for several times with abandoning.
The present invention is because of the solution that uses the waterborne film-forming inorganic compound of speciallyying permit No. 2028203 the fair 7-14801 of spy number is succeedd.The silanol saline solution that the present invention uses, even at normal temperatures also can film forming, so the influence that not changed between 200-800 ℃ by delivery temperature still can produce the film forming swelling, exhaust uptake is full of, in the exhaust that will contain pernicious gas and heavy metal is included in, play the effect of coolant exhaust temperature action and heat-resisting colloid filter, purify inclusion simultaneously, have only harmless steam to eject.Aforementioned silanol saline solution of the present invention is an alkali metal salt, and the effect of catching HCl is arranged, and, at high temperature become silica alcohol, because heavy metal and oxygen have adhesion, so when calcining, can stop the heavy metal stripping that captures.Therefore, owing to can catch the chlorination metal and the hydrochloric acid of bioxin precursor, have and prevent to produce effect and the effect of bioxin in possible trouble.Aforementioned silanol saline solution of the present invention must be selected the mixed solution amount according to Cl and heavy metal amount between 1-300%, but considers that according to the reaction equivalent solid constituent that above-mentioned silanol saline solution contains is that the 1-5 of heavy metal molecular weight doubly is necessary.Thereby in addition because increase air quantity to the exhaust air-supply by device, in fact it is very difficult to calculate the cooperation ratio, though keep reaction gas in neutral or above degree, considers the thinning limit of solution, the limit of the amount of being blown in addition is so because be that the mixing of various key elements must be confirmed by experiment.
The present invention can handle the carbon of burning generation and the stench and the ash that contains heavy metal of organic-inorganic simultaneously, particularly prevent to produce and strictness to limit the De bioxin, by exhaust is handled, make and handle stench and black smoke and heavy metal public hazards thing simultaneously and become possibility.
Claims (9)
1. material for treatment of purifying, it is characterized in that, the burning gases of waterborne film-forming inorganic compound that is made of siloxanes and silane alkoxide and the bazardous waste that contains black smoke and stench and heavy metal, flying dust are contacted, form the film forming dilatant, become the combustion residue thing that comprises black smoke and stench and pernicious gas and heavy metal therein, thus simultaneously will be as above-mentioned black smoke and stench and the pernicious gas and the heavy metal sealing of nuisance and public hazards thing.
2. material for treatment of purifying, it is characterized in that, the waterborne film-forming inorganic compound that is made of siloxanes and silane alkoxide is mixed with the residual ash of piling up in the incinerator bottom of burning waste, form the mixture of residual ash and waterborne film-forming inorganic compound, thereby obtain being overlayed on the combustion residue thing on surface, simultaneously with nuisance and the sealing of public hazards thing by the film of above-mentioned waterborne film-forming compound.
3. claim 1 or 2 described handled things is characterized in that, claim 1 or 2 described films by the waterborne film-forming inorganic compound are overlayed on the combustion residue thing on surface or both mixtures at 800 ℃ or above temperature lower calcination.
4. the purifying treatment method of discarded object, it is characterized in that, the waterborne film-forming inorganic compound that is made of siloxanes and silane alkoxide is contacted with the burning gases and the flying dust of discarded object, form the film forming dilatant, become the combustion residue thing that comprises black smoke and stench and pernicious gas and heavy metal therein, the discarded object that black smoke and stench and pernicious gas and heavy metal constituted that seals simultaneously as nuisance and public hazards thing is burnt, handle simultaneously the nuisance that contains thing etc. of the black smoke that generates and stench and pernicious gas and heavy metal and public hazards thing are carried out enclosed purification.
5. the purifying treatment method of the described discarded object of claim 4 is characterized in that, above-mentioned contact is to be realized by the waterborne film-forming inorganic compound that siloxanes and silanol constitute by spraying in the burning gases of discarded object.
6. the purifying treatment method of the described discarded object of claim 5, it is characterized in that, when above-mentioned waterborne film-forming inorganic compound is contacted with the burning gases of discarded object, on flue or attraction side line, the pressure atomization device is installed, spraying water-based film forming inorganic compound aspirates above-mentioned black smoke and stench and pernicious gas and heavy metal by the negative pressure that produce this moment.
7. the purifying treatment method of the described discarded object of claim 4, it is characterized in that, when above-mentioned waterborne film-forming inorganic compound is contacted with the burning gases of discarded object, in above-mentioned waterborne film-forming inorganic compound, be blown into 200 ℃ or above above-mentioned waste combustion gas, become and comprise the residue thing that above-mentioned black smoke and stench and pernicious gas and heavy metal contain thing therein.
8. the purifying treatment method of discarded object, it is characterized in that, the waterborne film-forming inorganic compound that is made of siloxanes and silane alkoxide is contacted with the residual ash of piling up in the incinerator bottom of burning discarded object, form the film forming dilatant, handle nuisance and public hazards thing with enclosed purification.
9. the purifying treatment method of the described discarded object of claim 4-8, it is characterized in that, the handled thing of above-mentioned nuisance and public hazards thing will be sealed simultaneously, perhaps above-mentioned waterborne film-forming inorganic compound is mixed with the residual ash and the flying dust of burning behind the waste combustion, make its potteryization 800 ℃ or above heating, prevent the stripping of nuisance and public hazards thing.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3533498 | 1998-01-10 | ||
| JP35334/98 | 1998-01-10 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN1226655A true CN1226655A (en) | 1999-08-25 |
| CN100341605C CN100341605C (en) | 2007-10-10 |
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| CN2007101419224A Expired - Fee Related CN101172195B (en) | 1998-01-10 | 1999-01-09 | Purification treatment product of harmful gas and bottom ash deposited on bottom of incinerator or the like and purification treatment method thereof |
| CNB991004175A Expired - Fee Related CN100341605C (en) | 1998-01-10 | 1999-01-09 | Method and materials for treatment of purifying harmful gases and cinders at bottom of cremator |
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| CN2007101419224A Expired - Fee Related CN101172195B (en) | 1998-01-10 | 1999-01-09 | Purification treatment product of harmful gas and bottom ash deposited on bottom of incinerator or the like and purification treatment method thereof |
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| KR (1) | KR100562512B1 (en) |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101252998B (en) * | 2005-07-27 | 2010-12-08 | 代尔夫特工业大学 | Method for treating bottom ash |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100351673B1 (en) * | 1999-07-05 | 2002-09-10 | 한국과학기술원 | Apparatus for improvement of mixing and reaction in combustors |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4381716A (en) * | 1978-06-05 | 1983-05-03 | Hastings Otis | Insulating apparatus and composite laminates employed therein |
| JPS56159454A (en) * | 1980-05-15 | 1981-12-08 | Kuraray Co | Flexible sheet like refractory building material |
| AU634962B2 (en) * | 1988-06-10 | 1993-03-11 | Kohmix Co., Ltd. | Water-Soluble, film-forming inorganic compounds |
| JPH06277438A (en) * | 1993-03-23 | 1994-10-04 | Idemitsu Kosan Co Ltd | Gas separation membrane and production thereof |
| NO301272B1 (en) * | 1995-05-19 | 1997-10-06 | Norsk Hydro As | Process for chlorine gas purification |
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1999
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- 1999-01-09 CN CN2007101419224A patent/CN101172195B/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101252998B (en) * | 2005-07-27 | 2010-12-08 | 代尔夫特工业大学 | Method for treating bottom ash |
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| TW414721B (en) | 2000-12-11 |
| CN100341605C (en) | 2007-10-10 |
| KR100562512B1 (en) | 2006-03-21 |
| CN101172195B (en) | 2012-06-06 |
| KR19990067836A (en) | 1999-08-25 |
| CN101172195A (en) | 2008-05-07 |
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