CN101172195A - Purification treatment product of harmful gasand bottom ash deposited on bottom of incinerator or the like and purification treatment of the same - Google Patents
Purification treatment product of harmful gasand bottom ash deposited on bottom of incinerator or the like and purification treatment of the same Download PDFInfo
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- CN101172195A CN101172195A CNA2007101419224A CN200710141922A CN101172195A CN 101172195 A CN101172195 A CN 101172195A CN A2007101419224 A CNA2007101419224 A CN A2007101419224A CN 200710141922 A CN200710141922 A CN 200710141922A CN 101172195 A CN101172195 A CN 101172195A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D47/06—Spray cleaning
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- 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
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- 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
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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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- B01D53/78—Liquid phase processes with gas-liquid contact
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Abstract
The present invention discloses a castoff cleaning treatment method which is characterized in that: the water film-forming inorganic compound consisted of siloxane and silanol salt contacts with the inflamed gases and flying ash of the castoff to form film-forming dilatant becoming the combustion residue containing black smoke, effluvium, harmful gas and heavy metal, and at the same time, the castoff consisted of black smoke, effluvium, harmful gas and heavy metal which are seemed as the injurant and the public injurant are sealed and burnt for the seal cleaning treatment of the the injurant and the public injurant containing black smoke, effluvium, harmful gas and heavy metal.
Description
The application is that application number is 99100417.5, the applying date is on January 9th, 1999, denomination of invention is divided an application for the application for a patent for invention of " material for treatment of purifying and purifying treatment methods thereof such as pernicious gas and cinder at bottom of cremator ".
Technical field
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.
Background technology
On living environment, needless to say black smoke and the stench that produces during waste combustion is even the stripping of the harmful heavy metal that contains in the flying dust to the burning ash that jettisons and discharging and in the discharging of the bioxin of the strict restriction in Europe strict restriction has been arranged all.
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 everyone knows, 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,, also can produce bioxin even in delivering to the bag hose way, carry out cooling processing and washer processing.Therefore, carry out sorption with inorganic matter and mineral and handle, but residue thing and sorbent need processing again, handle fully, the complicated treatment technology and the equipment of great number also must be arranged for making.
In the residual ash of incineration residue, remaining harmful heavy metal jettisoned banketing of appointment after handling with chelating agent in the past and handle with burying, but because there is safety issue in the long-time stability deficiency of heavy metal chelate in addition.Particularly ， bioxin and heavy metal remain in wherein after concentrating in flying dust, handle very difficult fully with chelating agent.
In addition, because generation black smoke and stench bring influence to surrounding resident, the countermeasure of solution is to need expensive incinerator with small incinerator.Therefore wish to search out simple and cheap method.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 melting 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 does not have to filter the organic matter filter of black smoke and stench up to 200-800 ℃, after cooling processing or washer processing, perhaps with after various ceramic catalysts or the adsorbent processing cooling, is transported in the bag hose again.Thereby because device costs an arm and a leg, resistant to elevated temperatures inorganic filter device and the sorbing material that does not need to adopt post processing found in expectation.
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 carbamic 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 absorption method of calcium hydroxide effectively utilized for addressing this problem.But, even in this absorption method, bag hose or necessity because must the wherein remaining flying dust that contains heavy metal of filtration treatment.That is to say that in handling the emission gases process, need absorption that the flying dust that contains bioxin precursor and iron chloride and heavy metal is handled, the filter of effective catalyst of the decomposition of Dui bioxin and public hazards thing also needs post processing for re-using filter.
Summary of the invention
The present invention has considered each each side that relates to, use even provide in the middle port of discontinuous running, also be easy to reach remove and be regarded as the most inaccessible bioxin setting, 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, inferior inorganic 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 represents that silanol salting liquid of the present invention (LC) is heat-resisting inorganic matter, at 20 ℃, 250 ℃, 550 ℃, in the time of 960 ℃, in FT-IR analyzes, reduces the figure that demonstrates film forming 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 FT-IR of Fig. 1-4 observes and is illustrated in 780cm in analyzing
-1The time siloxanes exist, and 900,1000,2400-3800cm
-1The time silanol peak that exists.Aforesaid silanol salting liquid 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.
Silanol salting liquid of the present invention 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, can judge relatively that with the peak value difference of waterglass its crystallization speed is fast.In Fig. 5, the longitudinal axis is the absorption spectra cm of X line
2/ g, transverse axis are that wavelength is made target with Cu.The peak crystallization of aforementioned silanol salting liquid is very clear, and being illustrated in low temperature becomes solid phase precursor film forming, and this can explain if intumescent reason then appears in the adsorbed water evaporation.In fact, be that 50% liquid is coated on the iron plate with aforementioned 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 gelatinization then that disappears of heating-up temperature rising foaming and intumescing phenomenon, is coated with membranization later on.
Heating microscope with Japanese high-tech (ジ ヤ パ Application Ha イ テ Star 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 silanol salting liquid of the present invention (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.The colloid of silanol salting liquid of the present invention like this (LC) has played 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, silanol salting liquid of the present invention in order to comprise above-mentioned exhaust, must expand into the degree that is full of blast pipe.Because aforementioned silanol salting liquid becomes the film forming dilatant because of high-temperature exhaust air, thereby has the action effect of reaching the object of the invention.
The heating silanol, it is well-known that its H and OH dehydration become siloxanes, therefore thinks if heavy metal is arranged, will be combined into-Si-O-R (R is a metal) this moment.Silanol salting liquid of the present invention 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, has shown this fact.If as coating is coated hidden, so test material to be pulverized, heavy metal will inevitably stripping.But adopt the method that the test material pulverizing is experimentized, the result does not observe heavy metal stripping from the micro mist that solidifies minces 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.
Silanol salting liquid of the present invention is the colloid of 0.5-1 micron.Observe the FT-IR of above-mentioned Fig. 1-4, also do not disappear even temperature reaches 900 ℃ of hydroxyls.Fig. 7 represent aforementioned silanol salting liquid when the heated air temperature at 450 ℃, nozzle temperature makes the microphotograph of its powdered with spray dryer in the time of 180 ℃, present the foaming nodularization state of 50-80 micron-scale.Observe the schematic diagram of inferring of Fig. 6, if under the condition that excessive water exists, heat by high-temperature exhaust air, the colloid that film forming expands because of the gelling material on surface by deposited, gel adsorption moisture evaporation thinks that this is under the effect of filter the solid constituent of discarded object to be 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 catch 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.
Silanol salting liquid of the present 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 ℃ of 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 solidification shot-like particle 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 analysis result, can infer that aforementioned silanol salting liquid has the effect that reduces black smoke, catches the gas that causes stench.Even especially the Li salt of hydrochloric acid is caught Cl, also be difficult at low temperatures decompose.Can think that aforementioned silane alkoxide (Li salt) solution can effectively tackle the bioxin of PVC.
Pb content is maximum in the heavy metal of discarded object, therefore with it as model, in residual ash, contain Pb composition 500-2000ppm and contain 15, in the ash of 000ppm flying dust, according to the weight content of Pb wherein, mix the aforementioned silanol salting liquid of 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 silanol salting liquid in its 5% solution, and 900 ℃ are green after being heating and curing, and carry out dissolution test, chromium, and copper, the content of arsenic are all at 0.01ppm or following.Think that these heavy metals also are ions binding.
If spraying silanol salting liquid of the present invention in 200 ℃ or above high-temperature exhaust air, because instantaneous gel film forming and expanded foamization is thought wherein to have comprised black smoke and foul gas.Think that this presentation of results gel colloid has the effect of filter, 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 silanol salting liquid of the present invention, 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.The force feed of silanol salting liquid of the present invention, to spray, drip be necessary means.
The contact method of silanol salting liquid of the present invention and exhaust, no matter be in the exhaust that is sucked air-supply, to spray, or drip aforementioned silanol salting liquid, still on the contrary, high-temperature exhaust air is blown in the silanol salting liquid of the present invention 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.
In addition, the discarded object that contains organic matter or heavy metal, soil, moisture etc. can easily mix with silanol salting liquid of the present invention mutually.As above-mentioned, if combustion of organic matter, the silanol salting liquid of the present invention that has mixed will the film forming expansionization, thereby burning gases is comprised and catch the ash or the Cl gas of carbonization and gasification, play the effect that only makes the filter that steam passes through, mix with residual ash simultaneously.Simultaneously, if the silanol salting liquid of the present invention of spraying in exhaust as mentioned above then can be brought into play the purified treatment effect of the present invention that residual ash and gas purify simultaneously.
As mentioned above, will contain the exhaust residue deposit or the residual ash of silanol salting liquid of the present invention, 800 ℃ or more than, for example in rotary furnace, burn, even then wherein contain harmful heavy metal, after potteryization, also 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 inferior inorganic 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 then 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, aforementioned exhaust be blown in the silanol salting liquid of the present invention, 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 in this stage, just can stop the generation of bioxin, but does not have the filter that can at high temperature use.Silanol salting liquid of the present invention such as Fig. 1-4 is shown with hear resistance, colloid expanded foamization as shown in Figure 6, effect with the filter as the schematic diagram of Fig. 6, 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 are 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 silanol salting liquid of the present invention that is blown in the exhaust uses excessive water dilution, but silanol salting liquid of the present invention is at high temperature so not big than thermal change, and with excessive water coexistence, 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 ℃ the environment temperature that produces bioxin, therefore, think dangerous.But if 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.
Description of drawings
[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 that rock hand university entrusts MSU, 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 the film forming expansionization, 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 [Figure 91 0] 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.
Illustrate in greater detail the present invention by following embodiment.
Silanol saline solution of the present invention (LC) is not even heating is decomposed yet, and it dewaters gradually to 1000 ℃, and the process that will change siloxanes into is schemed (analysis result in eastern beautiful research center) expression with 20 ℃, 250 ℃, 550 ℃, 950 ℃ FT-IR among Fig. 1-4.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
* 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.
Embodiment 3
The solid constituent of silanol salting liquid of the present invention (LC-150) is 50%, proportion is 1.5, PH=12.2, its adsorption moisture is shown in table 2 in the diminishing amount of different temperature ranges, in addition, with the specific heat between 20-1200 ℃, thermal diffusion coefficient and thermal conductivity are shown in table 3 (ア グ ネ technique center assay value).Dehydration lasts till high temperature, and from normal temperature to 1000 ℃, it is not very greatly that specific heat, thermal diffusion coefficient, thermal conductivity change, and this shows, though LC-150 at high temperature temperature also be difficult to rise, can work as the heat absorbent of temperature of exhaust gas.If there is superfluous water to exist, then because synergy has the effect of heat absorption chilling.
[table 2]
Heating diminishing component analysis result
[table 3]
The insulating characteristics analysis result
Temperature specific heat thermal diffusion coefficient thermal conductivity
℃ Cal/g·℃ cm
2/S cal/cm·S·℃
20 0.2?0?0 0.00696 0.00203
300 0.36?3 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 450 ℃ of LPG gas temperatures, 180 ℃ of outlet temperatures to silanol saline solution of the present invention (LC-150) spray-drying.Because LC-150 is colloid and dilatancy is arranged,, the microphotograph of this foamed is shown in Fig. 7 so form the foam of 50-80 micron.Stabilizing agent and other compositions of its 20-50 weight portion and Ding Fa are added among the PVC, 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 vinyl chloride 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, result's (result of the test that Care MSU of committee of rock hand university obtains) is shown in Fig. 5.The result shows that LC-150 is made of dimer and trimer, and Fig. 5 has shown silanol salting liquid of the present invention (LC-150) 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 explanation silanol salting liquid of the present invention (LC-150) 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 cleans lens then and observes once more beyond the Great Wall, observes swelling and lasts till near 650 ℃, is cured as opal (afrodite) shape, is the malt sugar shape 800 ℃ or above plasticizing gelatinization then.The schematic diagram of Fig. 6 has been represented above-mentioned behavior.I.e. spraying during above-mentioned LC-150 in the smokejack of burning and gas-exhausting is appreciated that the instantaneous foamed of LC-150 and expands.Functioning efficiency height when the LC-150 foamed is full of the diameter of smokejack.Also can produce identical accumulation effect in the silanol salting liquid of the present invention 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, silanol salting liquid of the present invention (LC-150) 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
To contain the PbO that 2220mg/ rises flying dust assay value and with respect to the above-mentioned flying dust of 100 weight portions, mix the table 4 that is shown in of 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
Ash 100 100 100 ashes are provided by NKK
It is comprehensive to mix LC solid constituent 18 36 54 Prefectura de Kanagawa industries
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 above-mentioned 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
[table 6]
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 silanol salting liquid of the present invention (LC-140) that is mixed with 20 parts by volume/1m3 (50 times),, through spraying (e) above-mentioned LC dilute solution is blown in the side line (b) with high-pressure pump (d).LC-140 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 (f) 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 at 200Kg/cm
2Pressure under when beginning to be blown into LC liquid, then black smoke still is that stench all disappears in the exhaust steam (i).This work is finished according to the analysis of JIS pernicious gas analytic approach by (strain) steel pipe instrumentation.Delivery temperature is 260-350 ℃, and this moment, the easiest generation bioxin was reduced to 2.4-2.9ppm but swash from 250-1100ppm as the HCl that generates essential factor, was 200ngTEQ/Nm at steam outlet De bioxin
3, but mean value is 1.9ngTEQ/Nm
3
Do not use bag hose not use lime and sorbent in the present embodiment yet, purify hydrochloric acid with bioxin thereby 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 (g), 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 among Fig. 9,10 contains in a large number 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 silanol saline solution of the present invention (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 all mixed above-mentioned LC in discarded object and the exhaust, so reached every liter of Pb 0.01mg, Cd 0.01mg, Cr0.05mg, As 0.01mg 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 (d) 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 will produce black smoke and stench with the device of Figure 11 is pulled rubber, PVC plate and foamed styrene bits and is mixed and burn.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 LC 2%, if with every 1m
3The solution (solid constituent 20g) that burning tolerance is 1 liter is with expulsion pressure 100Kg/cm
2, 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.In 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 basin can not use for several times with abandoning.
The effect of invention
The present invention is because using the waterborne film-forming of speciallyying permit No. 2028203 the fair 7-14801 of spy number inorganic The solution of compound and succeeing.
Even silanol saline solution of the present invention is at normal temperatures also can film forming, so be not subjected to delivery temperature 200 The impact that changes between-800 ℃ still can produce the film forming swelling, and exhaust uptake is full of, and will contain has In the exhaust of evil gas and heavy metal is included in, play coolant exhaust temperature action and heat-resisting colloid filter Effect purifies inclusion simultaneously, only has harmless steam to eject.
Silanol saline solution of the present invention is alkali metal salt, and the effect that catches HCl is arranged, and, at high temperature become Become silica alcohol, owing to heavy metal oxygen combining power is arranged, when calcining, can stop the heavy metal that captures Stripping. Therefore, owing to can catch chlorination metal and the hydrochloric acid of bioxin precursor, have and prevent two Evil English is in the effect of possible trouble. Aforementioned silanol saline solution of the present invention must be according to Cl and heavy metal amount 1 Select the mixed solution amount between-300%, but consider that according to reaction equivalent above-mentioned silanol saline solution contains Solid constituent is that the 1-5 of heavy metal molecular weight doubly is necessary. In addition because blow to exhaust by device Thereby the increase air quantity, it is very difficult in fact to calculate mixing ratio, although keep reaction gas neutral or above Degree, but consider the thinning limit of solution, the limit of the amount of being blown in addition is because be the mixing of various key elements So must be confirmed by experiment.
The present invention can process the carbon of burning generation and the stench and the ash that contains heavy metal of organic-inorganic simultaneously, Can when processing stench and black smoke and heavy metal public hazards thing, prevent two of strictly restriction Evil English.
Claims (7)
1. 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, nuisance and public hazards thing contained in the burning gases to above-mentioned discarded object carry out while enclosed purification processing, described aquatic film forming inorganic compound is to make (1) metallic silicon, (2) borax, boric acid, sodium fluoride or inferior inorganic acid or its salt and (3) caustic potash, when the alkali metal hydroxide of caustic soda or causticity lithium reacts, in water or (2) borax, boric acid, in the solution of sodium fluoride or inferior inorganic acid or its salt, above-mentioned metal solid and above-mentioned alkali metal hydroxide are reacted, this reaction heat is being controlled at 50 ℃-100 ℃ with in interior, the proportion that makes product is 1.1 or above formation.
2. the purifying treatment method of the described discarded object of claim 1, wherein said inferior inorganic acid is phosphorous acid, nitrous acid, sulfurous acid or its salt.
3. the purifying treatment method of the described discarded object of claim 1 is characterized in that, above-mentioned contact is to realize by the above-mentioned waterborne film-forming inorganic compound of spraying in the burning gases of discarded object.
4. the purifying treatment method of each described discarded object of claim 1-3, 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, by this pressure atomization device above-mentioned waterborne film-forming inorganic compound of spraying, aspirate above-mentioned black smoke and stench and pernicious gas and heavy metal by the negative pressure that produce this moment.
5. the purifying treatment method of each described discarded object among the claim 1-3, 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 the residue thing that comprises above-mentioned black smoke and stench and pernicious gas and heavy metal therein.
6. the purifying treatment method of each described discarded object among the claim 1-3, it is characterized in that, above-mentioned waterborne film-forming inorganic compound 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.
7. the purifying treatment method of each described discarded object among the claim 1-3, it is characterized in that, with above-mentioned waterborne film-forming inorganic compound and the handled thing that seals the formation of above-mentioned nuisance and public hazards thing simultaneously, perhaps residual ash behind the waste combustion and flying dust mix, 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 |
|---|---|---|---|
| CNB991004175A Division 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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|---|---|
| CN101172195A true CN101172195A (en) | 2008-05-07 |
| CN101172195B CN101172195B (en) | 2012-06-06 |
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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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| 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 |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR100562512B1 (en) |
| CN (2) | CN101172195B (en) |
| TW (1) | TW414721B (en) |
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|---|---|---|---|---|
| KR100351673B1 (en) * | 1999-07-05 | 2002-09-10 | 한국과학기술원 | Apparatus for improvement of mixing and reaction in combustors |
| NL1029628C2 (en) * | 2005-07-27 | 2007-01-30 | Univ Delft Tech | Method for treating bottom ash. |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
1999
- 1999-01-08 TW TW088100218A patent/TW414721B/en active
- 1999-01-09 CN CN2007101419224A patent/CN101172195B/en not_active Expired - Fee Related
- 1999-01-09 CN CNB991004175A patent/CN100341605C/en not_active Expired - Fee Related
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|---|---|
| CN1226655A (en) | 1999-08-25 |
| KR100562512B1 (en) | 2006-03-21 |
| TW414721B (en) | 2000-12-11 |
| CN101172195B (en) | 2012-06-06 |
| KR19990067836A (en) | 1999-08-25 |
| CN100341605C (en) | 2007-10-10 |
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