CA2123129A1 - Process for the exploitation of brown coal fly ash - Google Patents
Process for the exploitation of brown coal fly ashInfo
- Publication number
- CA2123129A1 CA2123129A1 CA 2123129 CA2123129A CA2123129A1 CA 2123129 A1 CA2123129 A1 CA 2123129A1 CA 2123129 CA2123129 CA 2123129 CA 2123129 A CA2123129 A CA 2123129A CA 2123129 A1 CA2123129 A1 CA 2123129A1
- Authority
- CA
- Canada
- Prior art keywords
- fraction
- process according
- particles
- fine fraction
- fine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
- C04B18/08—Flue dust, i.e. fly ash
- C04B18/081—Flue dust, i.e. fly ash from brown coal or lignite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B9/00—General arrangement of separating plant, e.g. flow sheets
- B03B9/04—General arrangement of separating plant, e.g. flow sheets specially adapted for furnace residues, smeltings, or foundry slags
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/132—Waste materials; Refuse; Residues
- C04B33/135—Combustion residues, e.g. fly ash, incineration waste
- C04B33/1352—Fuel ashes, e.g. fly ash
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Civil Engineering (AREA)
- Processing Of Solid Wastes (AREA)
- Fertilizers (AREA)
- Carbon And Carbon Compounds (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
Abstract
Abstract The invention relates to a process for the exploitation of brown coal ash, in particular electro-static precipitator ash arising in the dry state, to form building materials, in which a coarse fraction having a particle size lower limit about > 500 µm is first mechan-ically separated off, the remaining fraction having a particle size upper limit about < 500 µm is used for the production of brickworks products as such or as the very fine fraction thereof with contents having a particle size < about 100 µm which is mechanically separated off from a fine fraction containing essentially fine quartz sand, while the fine fraction is used for the production of building materials requiring quartz sand, is required, at least the majority of the coal particles, coke part-icles and wood particles still contained in the fractions being mechanically removed.
Description
f , ~ flLE, ~I THIS AMENDrD
? T~3~ TRANSLATloN 2 ~ 2 312 9 Proce3 for the ¢xploitation of brown coal fly a~h The i~vention relato~ to a proceRs for the sxploitation of brown coal ash, in part~cular electro-static ~recipitator a~h arising i~ t~a dry ~tatP, to ~or~
building materials.
Owing to the type o~ tho fu~l and differe~ce~ in the ~iring proce~s, bit~minou~ coal a~he~ a~d brown coal ashe~ differ not only in their gQneral chemical a~d mineralogical composition, but al80 in their ~tructure.
Portio~s ~u~ed in a roughly vi~reou~ mann~r, ~uch a~
occur relatively frequently in the caso o~ bituminous coal ashes from bit~;nous coal fired in the medium and high t~mperature ra~ge, ar~ encountered to a considerably lessQr Qxtent in the ca~e of brown coal ashe~
Since brown coal ashes arise in considerable quant~ties, ~ariou~ attempts have been made to e~ploit these in order to a~oid dumping in land~ . It ii3 thu~
known to U8~ brown coal ashes in co~bination with the brown ~oal ~lue gas de3ulphurization gyp~um lik~wii~e 20 ari~ y as stabilizer ~or the eu~lro~mentally n2utral ~illins of pits and ope~ cast mines.
The u~e of brown coal ~ly ashes, which arii~e in the Rhinalil~d brown coal ar~a in an iEnount o~ approxi-mately 5 million t/year, q ~ p~ .~.,~
:'` 21 2~2 in the production of sand-lime bricks, in contrast, has proved to be com-pletely unsuitable, as can be seen from U. Wittneben "Moglichkeiten zur Reduzierung des Kalk- und Energiebedarfs bei der Kalksandsteinherstellung durch den Zusatz von Flugasche Potential methods for reducing the lime and energy requirements in sand-lime brick production by the addition of fly ash ", Bundesverband Kalksandsteinindustrie e.V., 1987, in particu-lar Fig. 2.
Although the use of brown coal fly ash in the production of sand-lime bricks with the attainment of relatively good strength values is also disclosed by DE-A-4 039 091, this ash is an ash very rich in free lime which brings with it, as a result, a corresponding chemical binding capacity. However, such an ash arises in very small quantities so that no significant reduction of the amounts of brown coal ash to be landfilled can be achieved by this method.
The object of the invention is to create a process of the type mentioned at the outset which permits brown coal ashes to be used in -~
large quantities for the production of high-grade building materials. ;~
This object is achieved in that a coarse fraction (II) having a particle size lower limit in the range of about 200 to 500 um is first mechanically separated off, the remaining fraction (I) having a respec-tive particle size upper limit is used for the production of brickworks products as such or as the very fine fraction (III) thereof with contents having a particle size upper limit in the range of about 40 to 100 um which is mechanically separated off from a fine fraction (IV) containing essentially fine quartz sand, while the fine fraction (IV) is used for the production of building materials requring quartz sand, if required, mechanically at least the majority of the coal particles, coke particles and wood particles still contained in the fractions (I, III, IV) so used being removed.
Further developments of the invention are to be taken from the description below and the subclaims.
The invention is described in more detail below with reference to the accompanying figures.
Fig. 1 shows a flow diagram relating to the exploitation of brown coal ash.
Figs. 2 to 5 show flow diagrams relating to the exploitation of certain fractions from the flow diagram of Fig. 1.
8rown coal ash generally arises for the most part as dry elec-trostatic precipitator ash and to a lesser extent as wet as ash.
212;~1~9 - ~ æ
", Electro~tatic 12r~cipitator ash fro~ the fir~t 35 ~lectrostatic preclpitator ~tage (abou~ 90~6 by w~ight o~
th~ ~ slQctrostatic precipitator aE~h) ~?redomi~a~tly l~o aontai~ th~ largex- ~ized asl~ co~ itue:~ts, while the Qlectrostatic preciE~itator ash of a secoILd, a~d ii~
re~uirQd, a thi rd elecéroatatic precipitator Btage~ ar~
:
? T~3~ TRANSLATloN 2 ~ 2 312 9 Proce3 for the ¢xploitation of brown coal fly a~h The i~vention relato~ to a proceRs for the sxploitation of brown coal ash, in part~cular electro-static ~recipitator a~h arising i~ t~a dry ~tatP, to ~or~
building materials.
Owing to the type o~ tho fu~l and differe~ce~ in the ~iring proce~s, bit~minou~ coal a~he~ a~d brown coal ashe~ differ not only in their gQneral chemical a~d mineralogical composition, but al80 in their ~tructure.
Portio~s ~u~ed in a roughly vi~reou~ mann~r, ~uch a~
occur relatively frequently in the caso o~ bituminous coal ashes from bit~;nous coal fired in the medium and high t~mperature ra~ge, ar~ encountered to a considerably lessQr Qxtent in the ca~e of brown coal ashe~
Since brown coal ashes arise in considerable quant~ties, ~ariou~ attempts have been made to e~ploit these in order to a~oid dumping in land~ . It ii3 thu~
known to U8~ brown coal ashes in co~bination with the brown ~oal ~lue gas de3ulphurization gyp~um lik~wii~e 20 ari~ y as stabilizer ~or the eu~lro~mentally n2utral ~illins of pits and ope~ cast mines.
The u~e of brown coal ~ly ashes, which arii~e in the Rhinalil~d brown coal ar~a in an iEnount o~ approxi-mately 5 million t/year, q ~ p~ .~.,~
:'` 21 2~2 in the production of sand-lime bricks, in contrast, has proved to be com-pletely unsuitable, as can be seen from U. Wittneben "Moglichkeiten zur Reduzierung des Kalk- und Energiebedarfs bei der Kalksandsteinherstellung durch den Zusatz von Flugasche Potential methods for reducing the lime and energy requirements in sand-lime brick production by the addition of fly ash ", Bundesverband Kalksandsteinindustrie e.V., 1987, in particu-lar Fig. 2.
Although the use of brown coal fly ash in the production of sand-lime bricks with the attainment of relatively good strength values is also disclosed by DE-A-4 039 091, this ash is an ash very rich in free lime which brings with it, as a result, a corresponding chemical binding capacity. However, such an ash arises in very small quantities so that no significant reduction of the amounts of brown coal ash to be landfilled can be achieved by this method.
The object of the invention is to create a process of the type mentioned at the outset which permits brown coal ashes to be used in -~
large quantities for the production of high-grade building materials. ;~
This object is achieved in that a coarse fraction (II) having a particle size lower limit in the range of about 200 to 500 um is first mechanically separated off, the remaining fraction (I) having a respec-tive particle size upper limit is used for the production of brickworks products as such or as the very fine fraction (III) thereof with contents having a particle size upper limit in the range of about 40 to 100 um which is mechanically separated off from a fine fraction (IV) containing essentially fine quartz sand, while the fine fraction (IV) is used for the production of building materials requring quartz sand, if required, mechanically at least the majority of the coal particles, coke particles and wood particles still contained in the fractions (I, III, IV) so used being removed.
Further developments of the invention are to be taken from the description below and the subclaims.
The invention is described in more detail below with reference to the accompanying figures.
Fig. 1 shows a flow diagram relating to the exploitation of brown coal ash.
Figs. 2 to 5 show flow diagrams relating to the exploitation of certain fractions from the flow diagram of Fig. 1.
8rown coal ash generally arises for the most part as dry elec-trostatic precipitator ash and to a lesser extent as wet as ash.
212;~1~9 - ~ æ
", Electro~tatic 12r~cipitator ash fro~ the fir~t 35 ~lectrostatic preclpitator ~tage (abou~ 90~6 by w~ight o~
th~ ~ slQctrostatic precipitator aE~h) ~?redomi~a~tly l~o aontai~ th~ largex- ~ized asl~ co~ itue:~ts, while the Qlectrostatic preciE~itator ash of a secoILd, a~d ii~
re~uirQd, a thi rd elecéroatatic precipitator Btage~ ar~
:
2 1 ~ 9 very finely di~ided.
Electrostatic precipitator ash contains quartz sand, heated clay mineral~, which generally together make up about 70 to 90% by weight, ~nd proportions of lime, 0ulphate, other alu~anate aQd fsrritic portion~ and ~itreous particle~ together with coal particles, coke particles and wood particle~.
The fine and very fina portions ha~i~g a particle size Upper limit o~ about ~ 500 ~m, preferably about 10~ 300 ~m, in particular about ~ 200-250 ~m are mechani-cally 3~parated off, in particular screened of~, i~ a ir8t Btep a~ fraction I from a fraction II having par~
ticles of a particle ~ize lower limit about ~ 500 ~m, preferably a~out ~ 300 ~, and in particular about 15~ 200-250 ~, principally containing relati~ely coarse quartz sand a~d relati~ely coar~e ooal particles, coke particles and wood particle~, and prinoipally con~aining, a~ a result of the separatio~ in the range up to the particle size specified, ine quartz sand and clay mineral con3titu~ts, and i~ addition other aluminate, ~erritic, lime-containing a~d sulphate constituents, and in addition a fine raction o~ coal particles, coke particles and wood particles. In particular, only the brown coal 1y ash from a ir~t electrostatic precipitator stage i8 subjected to the ~eparation and the fraction I separated o~f i3 processed together with or without the brown coal fly a3h arising in ~urther elec-trostatic precipitator stage3, which generally es~en-tially pri~cipally co~prise very ~inely di~ided clay mineral con~tituents.
The fraction I is subjec~ed to a fur~her mechanical separation which i8 orientated according to what exploitation i8 plan~ed for the fractions then ,:
obtained.
35~enerally, a further mechanical sQparatio~, ~or exa~ple, by acreening or sifting re~ult~ i~ a ~raction III (very fi~e fraction) haYi~g a particle 8ize upper lLmit ~ about 100 ~m, i~ par~icular ~ ~bout 40-70 ~m a~d ;~
a fraction I~ (~in~ ~ract~on) ha~ing a particla ~ize ~ 2~23~9 lower limit ~ about 100 ~m, in particular ~ about40-70 ~. The ~raction III chi~fly contains heatQd clay minerals and, apart from 8mall proportiona of the co~-stituents li~ted abo~e, also still contain~ in small amounts very fine portlons of coal particle~, coke parti¢les and wood particles which can be separated o~, if required, to obtain a fraction VII virtually compris-ing heated clay minerals and a fraction VI~I comprising combu3tible rQsidues, a~d ca~ therefore bs used as such or in the ~o~m of fraction ~II for brickworks products.
Fraction IIX e~sentially contains, in particular, the brown-staining portions.
: If required, the electro3tatic precipitator a~h of the ~econd and, if re~uired, other electrostatic precipitator gtago~ can be added to the fraction III and further proces~ed with this, since these principally contain very finely di~ided heated clay mi~erals.
The ~raction IV which principally contain~
corresponding quartz ~and a~d a 8mall portion o~ the remaining substances o~ ~raction I, but is essentially frae ~rom clay mineral~, i8 suitable in particular ~or u~e in the productio~ of calciu~ hydrosilicate-bonded building materials such as sand-lime bricks, cellular-expa~ded concrete block3 or the like, sincQ, in the quartz sand obtained i~ this manner, the silica is activated in the autocla~ing appropriately ~or calcium hydrosilicate ormation, 80 that, in comparison with normal ~uartz sand from a deposit, shorter autoclaving times result and/or lower prea3ures can b2 Qmployed.
If the fraction IV wa~ pre~erably obtainad by siftin~, the content of coal particle~, coke particles and wood particles i8 g~nerally 80 low that this fraction can be used a~ such. ~owever, if t~i~ cont~nt i highor, the~e particle~ must bQ ~eparated of~, fo~ example ~y ~i~ti~g.
T~e com~uetible ~ter~al i8 A~parated of~ from t~e r~maining fractiou II, in particular, by ~ifting, preferably air claasi~ication, but other separation mathod~ which expedl~tly cxploit the grea~ differ~n~e in ~. ~
r ~ 2 l 2 ~ ~1 2 9 "~
specific gra~ity between the coal particles, coke par-ticle~ and wood particles and the other aon~titua~t~ of fractio~ II can al~o be used. The resulti~g fractio~ V is essentially ao~os~d of guartz sand. Tha other ~raction VI arising is composed o~ combustible material and can be returnsd, if required, into the combustion circulation.
The quartz sand th~s obtained of the fraction V, just aa that o~ fraction IV, can therefore be u~ed ~or the production of calcium hydro~ilicate-bonded moulded articles ~uch as sand-lime bricks or the like. To produce the latter, guartz sand, lime ~nd water are mixed together, the mixture a~ter slaking in a reactor is pres~ed on a ~and-lime brick pres~ at a pres~ura in the order o~ magnitude of 15 to 20 N/m~2 and abo~e to ~i~a moulded articles and thc moulded articles are autocla~ed under ~aturatad s~eam at a temparature of about 200C for 3 to 8 h. A~ a result, whitiRh to ligh grey moulded articles, for axa~ple masonry bricks, ca~ be producad as a 801id brick or as ca~ity brick with a pattern o hole~, without natural quartz sand depo~it~ ha~ing to be drawn on or dumping i~ landfill~ having to be carri~d out, but at the same time the operation3 can be carried out more energetically and expediently (~korter autocla~ing tim~s and/or lower prQs~ures) than in the con~entional sand-lime brick i~dustry.
Calcium hydro~ilicate-bonded lightweightbuilding materials can also be produaed ~rom the ~uartz ~and obtained and ground, cf. Figs. 4 and 5. Thu~, accordi~g to Fig. 4, c~llular-~xpa~ded concret~ ca~ be produc~d from grou~d guaxtz sa~d, llm~ (CaO), Portland cem~nt, water and a gaa releaser (Al powdex), the ~tarting matQrials bei~g met2red and mixed a~d the ~ixture being chars~d into moulds, ga bubbles bQi~g ge~rated ~y t~e ga~ releaser which make ~he mlxtura porous. Cutti~g the solidified porou3 cak~ and autocla~ing the~ follow, with su~eque~t stacki~g, storago and pac~ing.
I~ accordan~ with Fig~ S, calcium hydrosilicat~-bo~dQd lightweight buildi~g materials can be produc~d from th~ quartz ~and obtaLnod a~d grou~d, hydrated lim~, - 2~312~
Portland cement, water, foam and a rapid binder, in which a pr~fabricated ~o~, for example a surfacta~t ~oam, i8 added to the raw mixturs comprising guartz sa~d, Portland cem~nt, h~drat@d lime and wa~er and the greQn brick ~trength neces~ary ~or handling, stacking and introducing in~o an autoclave i achieved via a special inorganic, heat-activatable rapid bindar (e.g. according to EP-B-O 119 662 or 0 151 452, which compri3es, ~or example, high-alumina cem2nt, citric anhydride, plaster of Pari~ a~d gyp~um a~hydrita in the pre~ence of hydrated lime) added to tha raw mixture, in particular, shortly before mouldlng. The raw mixture i~ continuously formed into a column in a aontinuous casting unit, and during this, ~ubjected to a heat treatment, for exa~ple, in a high-frequency fi~ld. ~fter cutting t~e green brick~, autoclaving, stacking, storing ~nd packing are carried out.
~ owever, the quartz ~a~d can also be proces~ed together with cement to give lightwe~ght building materials such a~ moulded articles of cellular-expa~ded concrete, in which the porosity ~lacuna] by adding a prefabricated foam, such a~ a aur~actant foam or protein foam, the green bricks produced from the starting mixture likewisQ being autoclaved with the advantag2s already described above.
I~ required, the products listed above, which can be produced ~rom the quartz sa~d obtainad, can al80, for example, be coloured red, which can be achieved by adding red mud ~rom tha aluminlum production, pre~erably i~ a~
amount o 1 to ~% by weight, to the raw mixture, or by adding other highly-colouri~g mlneral additive~.
The guartz sand obtai~ed, dependi~g on th~
d~sired bulk den~ity o~ the lightw~ight buildi~g mat~rials, can be ground to a fine~es~ ha~i~g a 8peci~ic suxface area according to Blain~ of about 1500 to 4000 c~2/gO
In addition, thi~ guaxtz sa~d can b~ u~ed o~ the building mate~ial Rid~ as ~ine and for mortars, plaster3, concret~s ~nd the like or ~18~ as foundry ~a~d, 2 ~ . 2 ~
drying o~ the ~and~ a8 i8 nece~sary in the case of sand~
from ~atural depo~it~ which are normally earth-~oi~t, i.e. have a moi~ture of up to 5% by weigh , being dis-pen~ed with.
S ~owever, fractio~ I can alao be ~eparated, ror example, by si~ting in such a ~anner that the coal particles, coke particl98 and wood particles are e~sen-tially removed a~, for example, comhustible fraction X
and a ~raction XX remain~ o~er which esse~tially com-prises quartz Rand and clay minerals. The fraction IX can likewise be used for bricXworks products.
~ o~ventional brickworks products are relevant here such a backing brick~, clinker, paving setts and the like, for which ~ractions I and IX are ~uitable in particular, but fractio~s III and VII are not excluded, and porous lightweight bricks which are produ~ed, in - particular, from fractions IIl a~d VII. If required, mixtures of the~e fractions ca~ also be used.
To produce green bricks for co~ertional ~rick products, which ars canventionally produced by kneading and extrusion, in accordance with Fig. 2, after metering and mixing with lean material (sands, 81ag8~, any addi-tives and ~lux (the alkali content o~ which produces a lower required firing temperature and which is to be added at about 1 to ~% by weight of soda, up to about 10~
by weight of pumice powder, alkali-rich mineral dusts or slurries (e.g. the abovementioned red mud or swarfs) up to about 10~ by wQight of grou~d waste ~lass and up to about 10% by weight of clays, if required, alternati~ely to be added i~ a mixture) an earth-moi~t pr~sing comp-o~ition can be produced by addition o~ about 5 to 7% by w~ight o moisture, which presaing compositio~ i~ shaped by sub~equ~nt prQ8~i~g in portio~R on a pre~ such a~ a sa~d-li~e brick pr~ss, i.e. with pr~sing pre~sures in the order of m~g~itudQ o~ 15 to 20 N/m~2 a~d aboY~, ~o give i~harently stable green bricks and a~ t~n fired~
~ this case, brick~ such a~ sand~ bricks cæn be provided as solid bricks or as ca~ity bricks ha~i~y a~
appropriate pattern o~ hole~
~ ~ 2 ~ 2 ~
~ ef~re firing, the green bricks are dried, pozzolanic portion~ of tha brow~ coal ash, which react in the earth-moist environment with lime likewise present in ~mall amountQ in a strengthening manner, contributing to the fact that the green brick~ do not di~integrate. Since such pozzol ~ic portion~ are g~erally prc~ent in ~mall amou~tJ, no bonding agent i~ generally neces~ary. ~ow-ever, i~ requixed, about 1 to 2% by weight of water gla~
can also be added a~ bonding agent.
The opportunity i~ primarily offered here o~
exploiting waste glaRq which, appropriately ground, can be add d a~ f lux .
~ owe~er, corresponding porous lightwaight build-ing material~ such as ~iyhtweight bricks, can al~o be produced by adding, after muxing a ~qlurry of the fraction I, III, VII and/or IX, le~n material, if required fl~x a~d water, additionally water and a prefabricated surfactant fOEm or protein oam and thuq making the raw ~ixture porous. The green brick ~trength i~ effected by adding an appropriate inorganic haat-acti~atable rapid binder (as mentionQd above) ensuring early strength, to the raw mixture made porou~ before or ater storage thereof in an appropriate ~es~el. The raw mixture i8 then cast in a continuou~ extrusion u~it and heated during its pa~sage, ~or example, by high-requency haati~g, 80 that the rapid binder is acti~ated and the strand solidifie~
which is th~n sliced into inherently st~ble green brick~
which are stacked, dried and fired. A~y additiv~s such as liguefierR or the like can be added to the raw mixture or the slurry.
Becau~e of insufficie~t plasticity of the h~ated clay minerals of the fractio~s I, I~I, VII and I~, in ~uch brickworka product~, in co~tra~t to produc~s which are produced by unheated clays, o~ly a v~ry 81i~h~
hri~kage occurs, i.e. shrinkag~ o~ firing and drying are ~ery low, ~harp edges and good di~nsional stability r~ult.
The fractio~s I, III, VII and I~ can also ~ u~ed a~ lean mat~rial~ ~or conv~tie~al brickworks produ~ta.
2 ~312~
; _ 9 In addition, the fractions VII a~d IX can be u~ed a~ an additi~e with pozzol~nic effect i~ bonding building materials containin~ l~me and PortlAnd c~mant.
Moreo~er, ~eparating off the ~ery fine con-stitue~t~ and the coal particles, cok0 partiales and woodparticles, for example by screening and si~ting, prevents variations in the a~h co~position. Separating o~f and ren~wed fe~ding of the coal particl~, coke particle~ and wood particle~ to the combu~tio~ produces a corre0-pGndingly improved fuel utilization.
The w~t ash, after dryi~g, can be subjeat0d together with the fly ash to the mechanical ~eparation~
pro~ided.
Electrostatic precipitator ash contains quartz sand, heated clay mineral~, which generally together make up about 70 to 90% by weight, ~nd proportions of lime, 0ulphate, other alu~anate aQd fsrritic portion~ and ~itreous particle~ together with coal particles, coke particles and wood particle~.
The fine and very fina portions ha~i~g a particle size Upper limit o~ about ~ 500 ~m, preferably about 10~ 300 ~m, in particular about ~ 200-250 ~m are mechani-cally 3~parated off, in particular screened of~, i~ a ir8t Btep a~ fraction I from a fraction II having par~
ticles of a particle ~ize lower limit about ~ 500 ~m, preferably a~out ~ 300 ~, and in particular about 15~ 200-250 ~, principally containing relati~ely coarse quartz sand a~d relati~ely coar~e ooal particles, coke particles and wood particle~, and prinoipally con~aining, a~ a result of the separatio~ in the range up to the particle size specified, ine quartz sand and clay mineral con3titu~ts, and i~ addition other aluminate, ~erritic, lime-containing a~d sulphate constituents, and in addition a fine raction o~ coal particles, coke particles and wood particles. In particular, only the brown coal 1y ash from a ir~t electrostatic precipitator stage i8 subjected to the ~eparation and the fraction I separated o~f i3 processed together with or without the brown coal fly a3h arising in ~urther elec-trostatic precipitator stage3, which generally es~en-tially pri~cipally co~prise very ~inely di~ided clay mineral con~tituents.
The fraction I is subjec~ed to a fur~her mechanical separation which i8 orientated according to what exploitation i8 plan~ed for the fractions then ,:
obtained.
35~enerally, a further mechanical sQparatio~, ~or exa~ple, by acreening or sifting re~ult~ i~ a ~raction III (very fi~e fraction) haYi~g a particle 8ize upper lLmit ~ about 100 ~m, i~ par~icular ~ ~bout 40-70 ~m a~d ;~
a fraction I~ (~in~ ~ract~on) ha~ing a particla ~ize ~ 2~23~9 lower limit ~ about 100 ~m, in particular ~ about40-70 ~. The ~raction III chi~fly contains heatQd clay minerals and, apart from 8mall proportiona of the co~-stituents li~ted abo~e, also still contain~ in small amounts very fine portlons of coal particle~, coke parti¢les and wood particles which can be separated o~, if required, to obtain a fraction VII virtually compris-ing heated clay minerals and a fraction VI~I comprising combu3tible rQsidues, a~d ca~ therefore bs used as such or in the ~o~m of fraction ~II for brickworks products.
Fraction IIX e~sentially contains, in particular, the brown-staining portions.
: If required, the electro3tatic precipitator a~h of the ~econd and, if re~uired, other electrostatic precipitator gtago~ can be added to the fraction III and further proces~ed with this, since these principally contain very finely di~ided heated clay mi~erals.
The ~raction IV which principally contain~
corresponding quartz ~and a~d a 8mall portion o~ the remaining substances o~ ~raction I, but is essentially frae ~rom clay mineral~, i8 suitable in particular ~or u~e in the productio~ of calciu~ hydrosilicate-bonded building materials such as sand-lime bricks, cellular-expa~ded concrete block3 or the like, sincQ, in the quartz sand obtained i~ this manner, the silica is activated in the autocla~ing appropriately ~or calcium hydrosilicate ormation, 80 that, in comparison with normal ~uartz sand from a deposit, shorter autoclaving times result and/or lower prea3ures can b2 Qmployed.
If the fraction IV wa~ pre~erably obtainad by siftin~, the content of coal particle~, coke particles and wood particles i8 g~nerally 80 low that this fraction can be used a~ such. ~owever, if t~i~ cont~nt i highor, the~e particle~ must bQ ~eparated of~, fo~ example ~y ~i~ti~g.
T~e com~uetible ~ter~al i8 A~parated of~ from t~e r~maining fractiou II, in particular, by ~ifting, preferably air claasi~ication, but other separation mathod~ which expedl~tly cxploit the grea~ differ~n~e in ~. ~
r ~ 2 l 2 ~ ~1 2 9 "~
specific gra~ity between the coal particles, coke par-ticle~ and wood particles and the other aon~titua~t~ of fractio~ II can al~o be used. The resulti~g fractio~ V is essentially ao~os~d of guartz sand. Tha other ~raction VI arising is composed o~ combustible material and can be returnsd, if required, into the combustion circulation.
The quartz sand th~s obtained of the fraction V, just aa that o~ fraction IV, can therefore be u~ed ~or the production of calcium hydro~ilicate-bonded moulded articles ~uch as sand-lime bricks or the like. To produce the latter, guartz sand, lime ~nd water are mixed together, the mixture a~ter slaking in a reactor is pres~ed on a ~and-lime brick pres~ at a pres~ura in the order o~ magnitude of 15 to 20 N/m~2 and abo~e to ~i~a moulded articles and thc moulded articles are autocla~ed under ~aturatad s~eam at a temparature of about 200C for 3 to 8 h. A~ a result, whitiRh to ligh grey moulded articles, for axa~ple masonry bricks, ca~ be producad as a 801id brick or as ca~ity brick with a pattern o hole~, without natural quartz sand depo~it~ ha~ing to be drawn on or dumping i~ landfill~ having to be carri~d out, but at the same time the operation3 can be carried out more energetically and expediently (~korter autocla~ing tim~s and/or lower prQs~ures) than in the con~entional sand-lime brick i~dustry.
Calcium hydro~ilicate-bonded lightweightbuilding materials can also be produaed ~rom the ~uartz ~and obtained and ground, cf. Figs. 4 and 5. Thu~, accordi~g to Fig. 4, c~llular-~xpa~ded concret~ ca~ be produc~d from grou~d guaxtz sa~d, llm~ (CaO), Portland cem~nt, water and a gaa releaser (Al powdex), the ~tarting matQrials bei~g met2red and mixed a~d the ~ixture being chars~d into moulds, ga bubbles bQi~g ge~rated ~y t~e ga~ releaser which make ~he mlxtura porous. Cutti~g the solidified porou3 cak~ and autocla~ing the~ follow, with su~eque~t stacki~g, storago and pac~ing.
I~ accordan~ with Fig~ S, calcium hydrosilicat~-bo~dQd lightweight buildi~g materials can be produc~d from th~ quartz ~and obtaLnod a~d grou~d, hydrated lim~, - 2~312~
Portland cement, water, foam and a rapid binder, in which a pr~fabricated ~o~, for example a surfacta~t ~oam, i8 added to the raw mixturs comprising guartz sa~d, Portland cem~nt, h~drat@d lime and wa~er and the greQn brick ~trength neces~ary ~or handling, stacking and introducing in~o an autoclave i achieved via a special inorganic, heat-activatable rapid bindar (e.g. according to EP-B-O 119 662 or 0 151 452, which compri3es, ~or example, high-alumina cem2nt, citric anhydride, plaster of Pari~ a~d gyp~um a~hydrita in the pre~ence of hydrated lime) added to tha raw mixture, in particular, shortly before mouldlng. The raw mixture i~ continuously formed into a column in a aontinuous casting unit, and during this, ~ubjected to a heat treatment, for exa~ple, in a high-frequency fi~ld. ~fter cutting t~e green brick~, autoclaving, stacking, storing ~nd packing are carried out.
~ owever, the quartz ~a~d can also be proces~ed together with cement to give lightwe~ght building materials such a~ moulded articles of cellular-expa~ded concrete, in which the porosity ~lacuna] by adding a prefabricated foam, such a~ a aur~actant foam or protein foam, the green bricks produced from the starting mixture likewisQ being autoclaved with the advantag2s already described above.
I~ required, the products listed above, which can be produced ~rom the quartz sa~d obtainad, can al80, for example, be coloured red, which can be achieved by adding red mud ~rom tha aluminlum production, pre~erably i~ a~
amount o 1 to ~% by weight, to the raw mixture, or by adding other highly-colouri~g mlneral additive~.
The guartz sand obtai~ed, dependi~g on th~
d~sired bulk den~ity o~ the lightw~ight buildi~g mat~rials, can be ground to a fine~es~ ha~i~g a 8peci~ic suxface area according to Blain~ of about 1500 to 4000 c~2/gO
In addition, thi~ guaxtz sa~d can b~ u~ed o~ the building mate~ial Rid~ as ~ine and for mortars, plaster3, concret~s ~nd the like or ~18~ as foundry ~a~d, 2 ~ . 2 ~
drying o~ the ~and~ a8 i8 nece~sary in the case of sand~
from ~atural depo~it~ which are normally earth-~oi~t, i.e. have a moi~ture of up to 5% by weigh , being dis-pen~ed with.
S ~owever, fractio~ I can alao be ~eparated, ror example, by si~ting in such a ~anner that the coal particles, coke particl98 and wood particles are e~sen-tially removed a~, for example, comhustible fraction X
and a ~raction XX remain~ o~er which esse~tially com-prises quartz Rand and clay minerals. The fraction IX can likewise be used for bricXworks products.
~ o~ventional brickworks products are relevant here such a backing brick~, clinker, paving setts and the like, for which ~ractions I and IX are ~uitable in particular, but fractio~s III and VII are not excluded, and porous lightweight bricks which are produ~ed, in - particular, from fractions IIl a~d VII. If required, mixtures of the~e fractions ca~ also be used.
To produce green bricks for co~ertional ~rick products, which ars canventionally produced by kneading and extrusion, in accordance with Fig. 2, after metering and mixing with lean material (sands, 81ag8~, any addi-tives and ~lux (the alkali content o~ which produces a lower required firing temperature and which is to be added at about 1 to ~% by weight of soda, up to about 10~
by weight of pumice powder, alkali-rich mineral dusts or slurries (e.g. the abovementioned red mud or swarfs) up to about 10~ by wQight of grou~d waste ~lass and up to about 10% by weight of clays, if required, alternati~ely to be added i~ a mixture) an earth-moi~t pr~sing comp-o~ition can be produced by addition o~ about 5 to 7% by w~ight o moisture, which presaing compositio~ i~ shaped by sub~equ~nt prQ8~i~g in portio~R on a pre~ such a~ a sa~d-li~e brick pr~ss, i.e. with pr~sing pre~sures in the order of m~g~itudQ o~ 15 to 20 N/m~2 a~d aboY~, ~o give i~harently stable green bricks and a~ t~n fired~
~ this case, brick~ such a~ sand~ bricks cæn be provided as solid bricks or as ca~ity bricks ha~i~y a~
appropriate pattern o~ hole~
~ ~ 2 ~ 2 ~
~ ef~re firing, the green bricks are dried, pozzolanic portion~ of tha brow~ coal ash, which react in the earth-moist environment with lime likewise present in ~mall amountQ in a strengthening manner, contributing to the fact that the green brick~ do not di~integrate. Since such pozzol ~ic portion~ are g~erally prc~ent in ~mall amou~tJ, no bonding agent i~ generally neces~ary. ~ow-ever, i~ requixed, about 1 to 2% by weight of water gla~
can also be added a~ bonding agent.
The opportunity i~ primarily offered here o~
exploiting waste glaRq which, appropriately ground, can be add d a~ f lux .
~ owe~er, corresponding porous lightwaight build-ing material~ such as ~iyhtweight bricks, can al~o be produced by adding, after muxing a ~qlurry of the fraction I, III, VII and/or IX, le~n material, if required fl~x a~d water, additionally water and a prefabricated surfactant fOEm or protein oam and thuq making the raw ~ixture porous. The green brick ~trength i~ effected by adding an appropriate inorganic haat-acti~atable rapid binder (as mentionQd above) ensuring early strength, to the raw mixture made porou~ before or ater storage thereof in an appropriate ~es~el. The raw mixture i8 then cast in a continuou~ extrusion u~it and heated during its pa~sage, ~or example, by high-requency haati~g, 80 that the rapid binder is acti~ated and the strand solidifie~
which is th~n sliced into inherently st~ble green brick~
which are stacked, dried and fired. A~y additiv~s such as liguefierR or the like can be added to the raw mixture or the slurry.
Becau~e of insufficie~t plasticity of the h~ated clay minerals of the fractio~s I, I~I, VII and I~, in ~uch brickworka product~, in co~tra~t to produc~s which are produced by unheated clays, o~ly a v~ry 81i~h~
hri~kage occurs, i.e. shrinkag~ o~ firing and drying are ~ery low, ~harp edges and good di~nsional stability r~ult.
The fractio~s I, III, VII and I~ can also ~ u~ed a~ lean mat~rial~ ~or conv~tie~al brickworks produ~ta.
2 ~312~
; _ 9 In addition, the fractions VII a~d IX can be u~ed a~ an additi~e with pozzol~nic effect i~ bonding building materials containin~ l~me and PortlAnd c~mant.
Moreo~er, ~eparating off the ~ery fine con-stitue~t~ and the coal particles, cok0 partiales and woodparticles, for example by screening and si~ting, prevents variations in the a~h co~position. Separating o~f and ren~wed fe~ding of the coal particl~, coke particle~ and wood particle~ to the combu~tio~ produces a corre0-pGndingly improved fuel utilization.
The w~t ash, after dryi~g, can be subjeat0d together with the fly ash to the mechanical ~eparation~
pro~ided.
Claims (16)
1. Process for the exploitation of brown coal ash, in particu-lar electrostatic precipitator ash arising in the dry state, to form building materials, characterized in that a coarse fraction (II) having a particle size lower limit in the range of about 200 to 500 µm is first mechanically separated off, the remaining fraction (I) having a respec-tive particle size upper limit is used for the production of brickworks products as such or as the very fine fraction (III) thereof with contents having a particle size upper limit in the range of about 40 to 100 µm which is mechanically separated off from a fine fraction (IV) containing essentially fine quartz sand, while the fine fraction (IV) is used for the production of building materials requiring quartz sand, if required, mechanically at least the majority of the coal particles, coke particles and wood particles still contained in the fractions (I, III, IV) so used being removed.
2. Process according to Claim 1, characterized in that the coarse fraction, fine fraction and/or very fine fraction (I, II, III, IV) are produced by sieving.
3. Process according to Claim 1 or 2, characterized in that the fine fraction and the very fine fraction (III, IV) are separated from each other by sifting.
4. Process according to one of Claims 1 to 3, characterized in that the coal particles, coke particles and wood particles are separated off by sifting.
5. Process according to one of Claims 1 to 4, characterized in that the coarse fraction (II) is separated off with a particle size lower limit about > 350 µm, in particular about > 200 to 250 µm.
6. Process according to one of Claims 1 to 5, characterized in that the very fine fraction (III) is separated off with a particle size upper limit about < 40 to 70 µm.
7. Process according to one of Claims 1 to 6, characterized in that the brown coal fly ash from a first electrostatic precipitator stage is subjected to the separation and the very fine fraction (III) separated off in this case is processed together with the brown coal fly ash aris-ing in further electrostatic precipitator stages.
8. Process according to one of Claims 1 to 7, characterized in that the coarse fraction and/or fine fraction (II, IV) essentially freed from coal particles, coke particles and wood particles is processed together with lime and/or cement with pressing of moulded articles and autoclaving of the moulded articles to give calcium hydrosilicate-bonded moulded articles.
9. Process according to one of Claims 1 to 7, characterized in that the coarse fraction and/or fine fraction (II, IV) essentially freed from coal particles, coke particles and wood particles are ground together with lime or hydrated lime and/or cement and a prefabri-cated foam or a pore-forming agent with autoclaving to give moulded articles of cellular-expanded concrete or calcium hydrosilicate-bonded moulded articles having pores.
10. Process according to Claim 9, characterized in that inherently stable green bricks are produced by adding a heat-activatable rapid bonder leading to solidi-fication and passing through the raw mixture formed through a continuous extrusion unit heating the raw mixture and then dividing the column.
11. Process according to one of Claims 8 to 10, characterized in that the composition to be shaped, formed with the coarse fraction and/or fine fraction (II, IV) is coloured with a mineral colouring additive, preferably in an amount of 1 to 5% by weight.
12. Process according to one of Claims 1 to 7, characterized in that the fine fraction (IV), essentially freed from coal particles, coke particles and wood particles, is used as fine sand for mortars, plasters, concretes or as casting sand.
13. Process according to one of Claims 1 to 7, characterized in that the remaining fraction (I) and/or the very fine fraction (III), is required after mechanical removal of the coal particles, coke particles and wood particles, after wetting with about 5 to 7% by weight of moisture and mixing with additives necessary for the production of brickworks products, is shaped by pressing to give moulded articles which are fired.
14. Process according to one of Claims 1 to 7, characterized in that the mixture produced from the remaining fraction (I) and/or the very fine fraction (III) and from additive necessary for the production of brickworks products is made porous with prefabricated form, from which, using a heat-activatable rapid bonder leading to solidification, a column is produced in a heatable continuous extrusion unit, which column is divided into inherently stable green bricks which are fired.
15. Process according to Claim 13 or 14, charac-terized in that ground waste glass in an amount of up to about 10% by weight is added to the mixture produced from the remaining fraction (I) and/or the very fine fraction (III) and the additives.
16. Process according to one of Claims 1 to 7, characterized in that the remaining fraction (I) and/or the very fine fraction (III), after removing the coal constituents, coke constituents and wood constituents, is used as an additive with pozzolanic effect in lime- and Portland cement-containing matrices.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4139644.8 | 1991-12-02 | ||
| DE4139644A DE4139644C1 (en) | 1991-12-02 | 1991-12-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2123129A1 true CA2123129A1 (en) | 1993-06-10 |
Family
ID=6446054
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2123129 Abandoned CA2123129A1 (en) | 1991-12-02 | 1992-12-02 | Process for the exploitation of brown coal fly ash |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0615518B1 (en) |
| JP (1) | JPH07505822A (en) |
| AT (1) | ATE124673T1 (en) |
| CA (1) | CA2123129A1 (en) |
| CZ (1) | CZ134494A3 (en) |
| DE (2) | DE4139644C1 (en) |
| DK (1) | DK0615518T3 (en) |
| ES (1) | ES2077445T3 (en) |
| HU (1) | HUT73591A (en) |
| SK (1) | SK64094A3 (en) |
| WO (1) | WO1993011083A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9790703B1 (en) | 2016-08-16 | 2017-10-17 | Go Team CCR LLC | Methods of utilizing coal combustion residuals and structures constructed using such coal combustion residuals |
| US9988317B2 (en) | 2016-08-16 | 2018-06-05 | Go Team CCR LLC | Structures constructed using coal combustion materials |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE168364T1 (en) * | 1996-01-13 | 1998-08-15 | Pro Mineral Ges | METHOD FOR PRODUCING BRICK MOLDS |
| DE102005033454A1 (en) * | 2005-07-18 | 2007-01-25 | Construction Research & Technology Gmbh | Use of an organic additive for the production of aerated concrete |
| DE102010009373A1 (en) * | 2010-02-25 | 2011-08-25 | SRZ Schutzrechte Verwaltungs-GmbH, 90571 | Composition of a shaped body for use as an insulating board, method for its production and insulation board |
| FI127649B (en) * | 2016-10-31 | 2018-11-30 | Upm Kymmene Corp | Method for processing fly ash |
| EP3943464A1 (en) | 2019-10-10 | 2022-01-26 | Khan, Abbas | A novel lightweight ceramic sand formulation from lignite fly ash and method of preparation thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL199385A1 (en) * | 1977-07-05 | 1979-01-29 | Ts Osrodek Badawczo Rozwo | METHOD OF PRODUCTION OF CELLULAR CONCRETE |
| ES482923A1 (en) * | 1979-07-27 | 1979-12-01 | Monfort Herrera Alfredo | Manufacturing a plastering material |
| GB2061241B (en) * | 1979-08-28 | 1983-02-16 | Central Electr Generat Board | Bricks containing pulverised fuel ash and their manufacture |
| DD242609A1 (en) * | 1985-11-13 | 1987-02-04 | Karl Marx Stadt Energie | METHOD FOR USING BROWN COIL FILTER BAG AS A HYDRAULIC BINDER |
-
1991
- 1991-12-02 DE DE4139644A patent/DE4139644C1/de not_active Expired - Fee Related
-
1992
- 1992-12-02 DE DE59202830T patent/DE59202830D1/en not_active Expired - Fee Related
- 1992-12-02 ES ES92924649T patent/ES2077445T3/en not_active Expired - Lifetime
- 1992-12-02 CA CA 2123129 patent/CA2123129A1/en not_active Abandoned
- 1992-12-02 EP EP19920924649 patent/EP0615518B1/en not_active Expired - Lifetime
- 1992-12-02 DK DK92924649T patent/DK0615518T3/en active
- 1992-12-02 CZ CZ941344A patent/CZ134494A3/en unknown
- 1992-12-02 HU HU9401509A patent/HUT73591A/en unknown
- 1992-12-02 SK SK640-94A patent/SK64094A3/en unknown
- 1992-12-02 JP JP5509831A patent/JPH07505822A/en active Pending
- 1992-12-02 WO PCT/EP1992/002788 patent/WO1993011083A1/en not_active Application Discontinuation
- 1992-12-02 AT AT92924649T patent/ATE124673T1/en not_active IP Right Cessation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9790703B1 (en) | 2016-08-16 | 2017-10-17 | Go Team CCR LLC | Methods of utilizing coal combustion residuals and structures constructed using such coal combustion residuals |
| US9988317B2 (en) | 2016-08-16 | 2018-06-05 | Go Team CCR LLC | Structures constructed using coal combustion materials |
| US10301223B2 (en) | 2016-08-16 | 2019-05-28 | Go Team CCR LLC | Beneficial use structures |
Also Published As
| Publication number | Publication date |
|---|---|
| CZ134494A3 (en) | 1995-02-15 |
| JPH07505822A (en) | 1995-06-29 |
| SK64094A3 (en) | 1994-11-09 |
| DE4139644C1 (en) | 1993-04-22 |
| ES2077445T3 (en) | 1995-11-16 |
| WO1993011083A1 (en) | 1993-06-10 |
| EP0615518A1 (en) | 1994-09-21 |
| HUT73591A (en) | 1996-08-28 |
| EP0615518B1 (en) | 1995-07-05 |
| DE59202830D1 (en) | 1995-08-10 |
| ATE124673T1 (en) | 1995-07-15 |
| HU9401509D0 (en) | 1994-09-28 |
| DK0615518T3 (en) | 1995-10-02 |
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