SK261092A3 - Method of transformation of surpluses polluted with harmful substances on solid matter - Google Patents

Abstract

A method of converting contaminated, CaCl2-rich residues from flue gas purification is to be developed, which permits landfill disposal in solid form together with red mud. Furthermore, it should be possible additionally to immobilise further contaminated solids such as, for example, the primary slags and ashes from combustion installations, contaminated soils, sands from sand blasting, etc., in this material. The material produced should have adequate mechanical stability. The elutability of the contaminants present should be reduced to such an extent that safe surface deposition in landfills becomes possible. This object is achieved by the method according to the invention, having the features of the main claim. Advantageous embodiments of the method according to the invention can be found in the subclaims. As a solution, it is proposed that the method of converting contaminated residues from combustion installations, using red mud and cement into a solid, safely disposable form, comprises the following steps: a) mixing of CaCl2-rich residues, in particular from dry flue gas purification from combustion installations, together with red mud, cement and CaO to give a binder mixture, b) stirring the mixture with water to give a castable mass and c) casting and/or pressing the castable mass into mouldings or discharging the castable mass, for example by pumping, with subsequent solidification and setting to give solid bodies. l

Description

FIELD OF THE INVENTION The present invention relates to a method for converting combustion residues, gasses, polluted pollutants, using red sludge and cement and CaO to a solid, non-yawable form.

The state of the art

In industrial combustion plants, in particular when burning garbage bins in coal-fired power plants, considerable amounts of residual pollutants are eliminated. First of all, these are the residues of the purge fumes of such combustion plants. The eištäní waste gases are substantially of calcium especially _t ', chlorides and sulfates which have jir.é out pollutants contained in the combustion of the substance / trash popíípadé carbon / particular tčšké metals in concentrated form. Other residues of such combustion plants are slag and ash, in which pollutants are also mentioned. The residues fall off essentially in the form of a large surface. Therefore, the pollutants contained, in particular heavy metals and also calcium compounds, can be eluted with water in large widths. Such residues must therefore be stored as special waste in corresponding special compositions and burden existing small capacities there.

In order to be able to store these residues at the tip of landfill sites, the elimination of pollutants is substantially reduced.

This is achieved, for example, by converting the remainder of this kind of binder into solid molded bodies with sufficient mechanical stability and with as little surface as possible.

A method for consolidating residual flue gases is disclosed in DE 30 37 995. While the tail gas residues, which are essentially salified with calcium sulfate, are mixed with red kale®, cement, clays and coarse sand as well as small amounts of chloride. calcium. Leave to stand and then set to solidify without heat. However, according to the process proposed here, no residues can be processed which essentially consist of calcium chloride. When using such residues, the mixture would solidify under the above conditions during mixing, as CaClg would act as a strong cement reinforcement accelerator. On the basis of local flash stiffening, inhomogeneous bodies would be formed, which would not have a low stability in many cases. A sufficient reduction in the elutability of the pollutants is not achieved. As a result, it is hardly possible to combine the above-mentioned primary combustion with the remaining combustion.

It is an object of the present invention to provide a method which allows the residues of aural exhaust gases contaminated with SaCl 3-rich pollutants, together with red quenching, to be transferred to a defect-free material. Pale s® is intended to allow additional solids, such as primary Etruscan and ashes with tanning equipment, contaminated soils, sandblasting sands, etc., to be added to the material by polluting harmful substances. the material produced showed sufficient mechanical stability. The elucibility of the pollutants contained should be reduced to such an extent that it is possible to store the surface on the surface of the depots in a safe manner.

the inventive inventive

This object is solved according to the invention with the features of the main patent application. . A preferred embodiment of the method according to the invention results from the use of the invention. and business.

According to the method of the invention, it is first produced

about. CeO. This pseudobox is stirring up water on haotium,

time and after the river. & d very fast * The binder o.

In fact, even at very high proportions of fillers, up to 80 tines arise with surprise. The material has a high rheoharamic stability and low elutability of pollutants.

For the purpose of the present invention, it has its residual dry pollutant gases having a density of CaCl2 and CaSO2 ≥ 1.5. The CaCl 2 residue from the tail gas purification should be used advantageously for the production of the binder, so that the feedstocks are also at risk of moisture. If the feedstocks contain a high proportion of water and / or moisture, they may be heated. It is even more tolerable in the wetting process before the homogeneous mixing of the raw raw wines can be achieved until it is sufficiently homogeneous. It is conditional upon the action of CaCl 2 at the cementitious stage. In these cases, due to the non-heterogeneous distribution of the reactants, there is no localized, flash stiffening. As starting materials with a high moisture content are present, they should be dried prior to wetting. This is particularly true when using wet red sludge or residual wet scrubbing residues. Dry or dried starting squadrons may be mixed according to the invention in a blender of any kind. For low-moisture substance dispersions, if necessary, use a mixer with an imminent empire.

The weight of the dry emulsion composition is generally free. divisible in wide range. It has proven particularly advantageous to follow the expansion of the skin

A

- 40 # h30t * rest rich in. UaCl _o / as · dry material /

- 40> $ mass, red sludge

- 20> 6 masses, orient

- 20 0 mass. CaO

The content of cement and CaO can be at least partially stolen by hydraulically acting ash from U-tanning; or other? 3i hydraulic components such as puoolany, route, thuramontium. or blast furnace slag.

Where necessary, conventional modifiers or concrete additives, such as flame-retardants, fillers, thickeners, extruders or organic additives, can be mixed into the binder mixture or castable.

-5Addition of retarders. solidification to the used cewnt with © can positively affect the solidification behavior. For example, non-resinous resins, sugar, etc. are suitable. . late measures may be necessary, for example, to drank very high CaCl2 contents to avoid too rapid solidification of the CaCl2.

The binder mixture, produced by intensively mixing the barrels of churn, is mixed with water to the foundry. to another tip. The added amount of water is preferably adjusted so that the weight per m < 2 > of water to the dry composition of the binder 82 is between 0.5 to 1.5.

Below a weight ratio of 0.5, the mass (without the pif-plasticizer set) solidifies too fast. Above the 1 * 5 Exotion Ratio, the casting tip is too heavy. In this case, the well-hardening of the yelli will slow. At the same time, a small final strength is reached.

Saw with a small addition of water, the sixture is a rapidly decaying mass. 221 higher water content, the mixture behaves for a period of time as a thixotrope and solidifies after a few minutes after solsolting. After that the cement solidifies in a known manner.

Famous play of pure binder arable is poured or pressed xx and shaped bodies like blocks or stones. However, it can also be pumped into a large surface area immediately afterwards. and solidification in the air beside the heat. After solidification to deforging, the freckles are held in the leg for a few minutes to about 1 hour. After stiffening, the material exhibits mechanical stability and a very low elutant.

Additional solids to be removed, such as fillers, may be added to the process of the present invention, and the solids may be added to the binder composition or the castable composition to provide up to six times the dry weight of the binder composition. Such solid flying may be, for example, incineration cloves, contaminated blasting agents or even soil contaminated with heavy metals, eg coking plants, metallurgical plants or scrap yarns. fine Etruscan from freezing for incineration .. »

H’íäavken high proportions of such fillers. solidification in air at room temperature slows down significantly or is completely prevented. Only when the heat comes from outside does it become stiff. The heat supply is effected from the temperature of the fillers by mixing them to a temperature rather than heat. temperature up to 90 ° C. A further possibility is to rot the whole screen, filled with grease, after casting to a temperature of up to 9 ° C ·.

For example, if the fine slag is mixed to the temperature of the tinnitus, it is mixed into a mixture which, without the addition of Etruscan, solidifies even after 1 hour, even after 3 days at the end of the day of Fádnésai solidification. If the mildly Etruscan warm 35 ° C was almost equally oscillating, the solidification time was about 1 hour, increasing the amount of total energy required by increasing the proportion of filler.

The addition of menopause as well as an increase in the filler temperature can control this corresponding solidification and fusion behavior in the wide range and adapt it to any pH-

nr example p. It grows when the mixed mass is transported to denonia.

Even the material supplemented with binders shows sufficiently high mechanical stability after hardening. This is surprisingly true even at very high filler contents up to ΰθ $ h, based on wet total shit. The noise is so small that other pollutants present in the apparatus are so small that they may follow the storage of the material above the surface deposits.

The lost material (with or without fillers) may be subjected to a surface treatment, such as hydrophobization or set-off. lacquered sealed with mure, for example, to impregnate. by e-pulse from a eilicone resin. this will further reduce the elutability of the pollutants.

By means of the method according to the invention, it is possible to consolidate residues which are polluted by pollutants from combustion plants. When it comes to the treatment of the scrubbing residues, they result in a very high CaCl 2 content. The solids may bind to the solidified material 1 natural / burnt residues (e.g. slag) in high amounts. The solidification is carried out by addition of comont, CaO and red sludge. The strength of the ceilings significantly reduces the elutability of pollutants. The iron hydroxide content of the added sludge adds, at the same time, an additional absorbent for heavy metals in addition to the reducing agent for the metal ions, which is electrochemically more exaggerating and thus contributes further to the elimination of the pollutant pollutant. Therefore, the residues of the reinforced according to the invention can be deposited on top of the above-ground deposits, without exemplification.

However, the method according to the invention is explained in more detail by means of selected examples. way.

EXAMPLE 1 kg / well of aCl ₃ / C rich ₍ filter dust) is used

The 4 - 8 dry scrubber is operated by a waste incineration plant and about 45% by weight, CaCl 3 and by weight CaCl 3 with CaSO. about 2.6 s 1 were intensively mixed with 2 kg τ 'of dried red sludge (typical visa allocation Table 1) as well as with a sipée consisting of 1 kg cenenia and 1 kg Oe.O _e

used red sludge g

Clinical analysis /% hsoto dry matter / Al.Oo «· J »- * / f f * S C. c - 'ľJ e, -G \ · f-Γ '' 4 y. t'-IO " A 6-16 Ϊ1Ο ₂ o · c 4 ^iía 2 ^C /sl?.n./ 4-9 iva-O ______ 2 /roLp./ 0,5- 0,7 CaO / íígC 0.5 ° 4 losses? ííhéníiB 7-12 stfo velikcst grain? = 1 - 2.5 HB 5 ~ 5 liters of water were mixed into this dry sponge Because. that in this case, dry substances, must be used for mixing

llhovolná ľďíoiiačka.

The mass obtained in the process is liquid with mixing of from 10 to 20. The mass was poured into the corresponding molds into blocks. The IR solidification followed about 10 min. After the heat supply was complete. / apeciiic h.oin.o3t 300 aS 1000 $$ / gγ _g compressive strength r ·

500 kS / m “/ with grain, porous blast furnace Etruscan / pc1 dl © Dl® 4108 /. In order to determine the elutability of the pollutants according to DEV S 4 / Deutsches JŠinheitsverfahren zur tfaascr-, Abwasaer- over Schlavmntersucbizng / the blocks were of a thickness of 40 mm per line and 200 g ee were re-circulated in 2 liters of water 04 hc-din in the tank b rt / ir.in. At the same time, the fractions were just as true. The attempted fractions of hollow eihel were almost completely expanded, and the complete deforestation. hollow needles, performed concurrently and more extensively, show that the crossbones are predominantly d; Fields of Harvesting which can be expected even static®; The deposition corresponds to its own purpose when depositing aqueous, readily soluble, powders and / or pollutants.

The eluate thus obtained was filter-filtered for solids, and in the filtrate from (= mass of dissolved substances), the eluate was determined.

Zn, Cu, Cr, E i and Jb as?, That conductive elements, the filter dust used in the process was treated

Same as

Table 2 shows the pollutant contents found in the «filtered» eluate of pure filter dust and manufactured blooms ·

The eluate contents and / or the filter dust (b) were the product of the shaped bodies

residue 56.1 g / l U * 4 g / l • 31 -3.7 £ / l δ, δ g / i C č. <C01 rag / l d at 01 mg / l LN 7.1 m # r / l 0.1 mg / l it C, 3 6 ΣΤβ / 'Ι ú, 04 mg / l Cr <G, 01 mg / L <0.01 mg / L 11 4b, GI uig / l 24.01 mg / l Pb 91.0 iug / l 0 * 4 mg / L

10When evaluating the result it is necessary to take into account, inter alia. the following mechanisms of dissolution of the water-soluble salts

- cation hydrataoi

- formation of calcyl silicate-hydrate cement fusions

- formation of minerals from sodium hydroxide with Ca / 011 / _o contained in red sludge

adorbent fixation of dissolved ions on Fe (Oii) red sludge.

The residue from the dry cleaning of the flue gases is used

/ filter dust / corresponded to the following directional analysis- of: • CaO size 33,8 g materials. CaO free 3,5 λ materials. cl " 29,1 r materials. Sat ₄ ² “ £ 12.4 materials. F " 0.2 · 1 $ mass.

From these values it is possible to derive a mass porosity of CaCl2 with CaSO4 of about 2.6 s -1. Calcium is predominantly present in the form of readily soluble CaCl2. It is believed that heavy metals will be present predominantly in its readily soluble chloride form.

In the distribution of water with water, CaCl2 and metal chlorides, as well as the CaO contained in the mixture, also dissolve in the solution. In strong 'alkaline®. In the solution, some sparingly soluble metal hydroxides are formed which are absorbed by finely dispersed Fe / OH / red sludge on the one hand and built-in together with Fe / OE / into a rapidly forming crystal structure. As a result, CaCl 3 _is known to act as an extreme setting accelerator for new, more formed cementitious phases. The extent to which metal ions are bound to the new phases formed cannot be accurately measured.

That the alkali metal hydroxide-forming medium alone cannot be responsible for the retention capacity of the mixture is correlated with the eluate contents actually found in the solids eluate with the values expected for almost the? and the elution resulting therefrom if there was a mechanical embedded into the crystal structure alone.

In the cured body, the filter dust is present from about 25% of the total mass. in the case of the elongated mass of the filter sill and the cured mortars. should then the oluate mass exhibit about 25? content of filter dust eluate, Zn and Pb elements present in filter dust

néeh konoentraoíoh toto al © nepi and those: Zn lb In the filter dust eluate included / ® $ 100 / 7.1 mg / L 91.8 fflg / 1 full elution is expected / «25 t / 1.73 g / L 22.95 mg / 1 really found 0.1 mg / l C 4 mg / first redukoe eluevatelnoati 1 or 17.8 1 and 57 • 4

Since the pure filter dust eluate exhibits a pH of 12, the formation of filterable metal hydroxides in the cement / CaO / red sludge mixture cannot be combined with only one explanation of the retention capability, since the hydroxides would have to form equal in the form of the eluate of the pure filter. dust.

J-Example 2

Dry dry. 1 kg each in the example described

metals of filter dust raw materials, red sludge and sementia oement’u / CaC amé etruscan from ô 2.75 example

The mass supplemented with a filament, after 3 ônsch, and remained the taste of Im? N ?! 85 ° C to solidify euäárné • · ^s. (cement: CeO 1/1) together 18 kg

Also incinerators at temperature liters of water. íoiačr smčsi ί

is a

Even the room and the binder will correspond to the ratio of water / solid divided or multi-hour storage to a solid body.

in example 2, after the water has been separated,

C conquered by Etruscan. The pure binder mixture of Example 1 yields a batch of five grams at 200 grams of red sludge and a mixture of about 1800 grams contaminated by blasting with the same type of binder. It is obviously necessary to overcome the solidification cover necessary to overcome the threshold by using water with pM water. It is obvious that the ingredients of the mixture are mixed as a supplement, the pater on the op method; solidification after p reproducible · cray hla standing · «· ´ l´this fast fabric is a friable filter dust

Eone / CaO / dry / with them. 50 CC of warm sand not as pure binder cuts. Due to the stabilization of the leading energy, which assigns model ames to the use of heat-dissipating heat, many large amounts of hardened ebaorb ingredients are pressed in order to achieve heat rsc for the whole roe deer.

4 * i: i. labels;

4-0 kg rot to dry red sludge / moisture about 25 W kg of CoCl-containing filter flow, dry counting gases flow from the incinerator with 7.75 kg of free CaO

16.5 kg oen® ntu i

-1 333 kg of fly ash from coal combustion leading / from the purification of smokes 33 '.mu.g gas emissions Power plant /, Jevne slag / residue incineration plants / _t material that can be poured. Ca81-iucot. at a pose of 60 liters v.cly per fragrance dust, it has a CaSO ₄ content = 1.52.

To avoid premature compaction, it is then used to form a 0.3 m large block using an initial solidification. occurred during the sahodin. After about 20 hours of e given block í'orry · ?? and intensive drying ° C in Busara occurred atráéíla Tarja .-. Á Lelik kurtáčová - - ¹ · - - A'aCl on the surface of this. Vylou, 17 $. of the BaCl filter bucket introduced by the red surfactant sold by the hydrosorbent silicone emulsion and was rolled without any doubt.

BSÍ

Used f5.1tr? CaCl-, no

they also use a wet height with a non-aggressive casting of about 0.5 x 0.5 vibrators for concrete. 5 days of storage at 30 th water of about 10 & exclusion time Another layer of thinning corresponded to the penis containing CaClg and Ka from a plurality of sludge. Surface block is exposed to the weather. · * HALJ /

ki

The process according to the invention results in a suitable mixing of the lead stream; weaves, the htext lse viewed as problematic sbytky vedcueí piece «v.láštní Iru removal, ροι? οοί · ¹ small -'o uriOŽství ingredients to firm owes vylxťhování odílpevný's tčloeúm that accessible for nadycvrckcvá ukl.ádání pHčeraž they are put only a small number of. <? '. · rr bazpedhout in all dims 3 c hu can be worthwhile- because i- save high safety space dapcnif • robo-high waste ·

J “j-Since natural residues are subject to considerable rospinal fluctuations,

The examples may be viewed as mere model examples. In individual cases, optimizations within the framework may be desirable.

Claims (10)

P A T L w T O V E E A O Ϊ A method for converting pollutant residues from incineration plants using red sludge and x-ray to a solid, defect-free form, characterized in that the method comprises the following steps and / drying of CaClp-rich residues, in particular from dry cleaning the flue gases from epilating loads, together with the red sludge, cementer and CaO, we are mixed, b / mixed with the leads to the material to be treated, c / casting and / or molding the matter onto the shaped bars or raising the casting pits , for example, by pumping, rigid bodies and λ bindings, resulting in rigid bodies · 2. A method according to claim 1, wherein the CaClp rich residues have a weight ratio of CaClp to CaSO4 of at least 1.5. 3. A method according to any one of © pŤedcházejících to claim _t, characterized in that the mixture of the binder based on the dry proportion having the following composition: 20-40 / wt. 20 - 40 masses. 10 - 20% by weight. 10 - 20 masses. Residues rich in CaCl ₉ / ροδί tán as dry matter / Red sludge / calculated as dry matter / cement CaO. Method according to any one of the preceding claims, characterized in that the wet discharge of the substance is dried before mixing. Method according to one of the preceding claims, characterized in that part of the occupied cement and CaO binder mixture is replaced by coal ash or other hydraulic components. 6. A method according to any one of the preceding claims, characterized in that the binder mixes or the low-density binders add modifiers or additives to the concrete, such as, for example, plasticizers, retarders, thickeners, compression aids or organic additives. Method according to one of the preceding claims, characterized in that the ratio by weight of water to dry parts of the binder mixture is adjusted to between 0.5 and 1.5. Method according to one of the preceding claims, characterized in that other solids to be removed, such as fine Etruscan from waste incineration plants, contaminated blasting agents, contaminated soils, etc., are admixed with the binder mixture or casting material. . jeko plniva · Method according to claim 3, characterized in that the fillers are added in an amount of up to 6 times the dry weight of the binder mixture. Method according to either of Claims 3 and 9, characterized in that the fillers are heated to a temperature between room temperature and 90 ° C prior to the addition. 11. A method according to any one of claims 9 to 10, wherein: Λ w -17-, characterized in that all of the fillers filled with fillers are heated after casting, sintering or plotting; The temperature is up to 90 ° C. 1¼. Method according to one of the preceding claims, characterized in that the solid body produced after surface drying is subjected to a surface treatment such as, for example, a hydrophobic acid or a solution.