SK57394A3 - Adsorbent material for removing pollutants - Google Patents

Adsorbent material for removing pollutants Download PDF

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Publication number
SK57394A3
SK57394A3 SK573-94A SK57394A SK57394A3 SK 57394 A3 SK57394 A3 SK 57394A3 SK 57394 A SK57394 A SK 57394A SK 57394 A3 SK57394 A3 SK 57394A3
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SK
Slovakia
Prior art keywords
adsorbent material
cement
granulate
porous
hydrophobized
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Application number
SK573-94A
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Slovak (sk)
Inventor
Hanns-Thomas Teubel
Original Assignee
Brunn Betonwerk
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Publication date
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Publication of SK57394A3 publication Critical patent/SK57394A3/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/32—Materials not provided for elsewhere for absorbing liquids to remove pollution, e.g. oil, gasoline, fat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28011—Other properties, e.g. density, crush strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3028—Granulating, agglomerating or aggregating
    • 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
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/1055—Coating or impregnating with inorganic materials
    • C04B20/1077—Cements, e.g. waterglass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/42—Materials comprising a mixture of inorganic materials

Abstract

Described is an adsorbent material for the removal of pollutants, in particular for the removal of petrol, synthetic or mineral oils, etc., the adsorbent material containing a porous material, which has been made water-repellent, in the form of a light aggregate, in particular a granulated round-pored material based on calcium silicate hydrate, absodan or zeolites. The adsorbent material also contains, in addition to additives designed to provide water-repellent properties, 1.5 to 10 % by wt. of cement.

Description

Vynález sa týka adsorpčného materiálu pre viazanie škodlivých látok, obzvlášť pre odstránenie benzínov, minerálnych alebo syntetických olejov alebo pod., ktorý obsahuje porézny hydrofobizovaný materiál.The invention relates to an adsorbent material for binding harmful substances, in particular for the removal of petrol, mineral or synthetic oils or the like, which comprises a porous hydrophobized material.

Doterajší stav technikyBACKGROUND OF THE INVENTION

Z DE-A1 38 00 873 je„porézne materiály ako hydrofobizovateľná krieda a takáto hydrofobizovaná krieda v zodpovedajúcej zrnitosti, obzvlášť vo forme najjemnejšej alebo strednej zrnitosti zapracovaná do zeminy, môžu podľa tohoto spôsobu odstraňovať z kvapalných a/alebo z prúdeniaschopných médií prinášajúce škodlivé látky. Podľa staršieho návrhu prihlasovateľky boli už emulzie typu olej vo vode navrhnuté na spracovanie do betónových tvárnic, v ktorom bolo ľahké plnivo. emulzia typu olej vo vode a cementu navzájom homogénne premiešané a spracované do betónu prípadne do betónových tvárnic. Podiel ľahkého plniva v takomto betóne prípadne betónovej tvárnici je obvykle nižší ako 10 hmôt. %, pričom v betónovej tvárnici sa používajú okrem uvedeného ľahkého plniva aj obvyklé stavebné látky, ako piesok, štrk alebo podobné.From DE-A1 38 00 873, "porous materials such as a hydrophobizable chalk and such a hydrophobized chalk in corresponding grain size, especially in the form of finest or medium grain size incorporated into the soil, can, according to this method, remove harmful substances from liquid and / or flowable media. According to the applicant's earlier proposal, oil-in-water emulsions have already been proposed for processing into concrete blocks in which the filler has been light. oil-in-water and cement emulsions mixed homogeneously and processed into concrete or concrete blocks. The proportion of lightweight filler in such concrete or concrete block is usually less than 10 masses. %, the usual building materials, such as sand, gravel or the like, are used in the concrete block in addition to the lightweight filler mentioned.

Podstata vynálezuSUMMARY OF THE INVENTION

Podstata vynálezu spočíva v získaní v úvode uvedeného druhu adsorpčného materiálu, ktorý je možné vyrobiť zvlášť jednoduchým spôsobom a ktorý je bezprostredne k dispozícii pre výrobu v sypkej forme bez nákladného mletia a podľa tohoto spôsobu môže nachádzať ľubovoľné použitie. Adsorpčný materiál v zmysle vynálezu sa môže použiť rovnakým spôsobom ako prídavná látka pri výrobe vopred zmiešaného betónu s požadovanými vlastnosťami na odstránenie benzínov, minerálnych alebo syntetických olejov alebo pod., a tiež bezprostredne ako adsorpčný prípadne filtračný materiál a tiež ako plnivo, pri ktorom sa uloží násyp materiálu do dna alebo do zodpovedajúceho filtra. Pre riešenie tejto úlohy sa osvedčil adsorpčný materiál v zmysle vynálezu v podstate tým, že porézny materiál je ľahké plnivo, s výhodou guličkový porézny materiál na báze hydrátu kremičitanu vápenatého, absodanu alebo zeolitov, a obsahuje popri hydrofobizačných prímesiach 1,5 až 10 hmôt. % cementu. Tým, že ľahké plnivo je popri hydrofobizačných prímesiach zamiešané s cementom, získa sa bezprostredne produkt, v ktorom zostáva v podstate zachovaná granulometria pôvodne pridaného ľahkého plniva. Nadbytočné množstvo vody sa viaže s cementom bez toho, aby pritom prichádzalo k podstatnému zhrudkovaniu a aglomerácii, pričom sa dosiahne také celkové granulometrické zloženie, pri ktorom maximálna veľkosť zrna zodpovedá najviac 3 až 4-násobku maximálnej veľkosti zrna pôvodného granulátu. Tým je možné zabezpečiť obzvlášť ľahký, slabo tečúci prípadne sypký materiál, pri ktorom môžu byť vypustené tiež nákladné kroky sušenia po výrobe bez toho, aby hrozilo nebezpečenstvo zhrudkovania východiskového materiálu. S výhodou je maximálna veľkosť zrna granulátu s 15 mm, obzvlášť 5 mm .SUMMARY OF THE INVENTION The object of the present invention is to provide a type of adsorbent material which can be produced in a particularly simple manner and which is readily available for production in bulk form without costly milling and which can be used in any desired manner. The adsorbent material according to the invention can be used in the same way as the additive in the production of pre-mixed concrete with the desired properties for removing gasoline, mineral or synthetic oils or the like, and also immediately as an adsorption or filtering material and also as a filler. filling the material into the bottom or corresponding filter. In order to solve this problem, the adsorbent material according to the invention has proved to be essentially that the porous material is a lightweight filler, preferably a spherical porous material based on calcium silicate hydrate, absodan or zeolites, and contains 1.5-10 wt.% In addition to hydrophobic impurities. % cement. By mixing the light filler with the cement in addition to the hydrophobic admixtures, a product is obtained immediately in which the granulometry of the initially added light filler is essentially maintained. Excess water is bound to the cement without substantial agglomeration and agglomeration, resulting in a total granulometric composition in which the maximum grain size corresponds to at most 3 to 4 times the maximum grain size of the original granulate. This makes it possible to provide a particularly light, lightly flowing or free-flowing material in which expensive drying steps after production can also be omitted without the risk of the starting material being crumbled. Preferably the maximum grain size of the granulate is 15 mm, in particular 5 mm.

Zatiaľ čo prídavok od 1,5 do 10 hmôt. % cementu predovšetkým zabezpečuje, že nie je potrebné obávať sa zhrudkovania porézneho materiálu pri výrobe adsorpčného materiálu, môže takéto množstvo cementu v postupe už postačovať k tomu, aby sa vyrobil bezprostredne na mieste pridaním prímesí ďalšieho kameniva, ako napr. piesku alebo štrku a s prídavkom vody miestny betón.While the addition of 1.5 to 10 masses. In particular,% cement ensures that there is no need to worry about the porosity of the porous material in the production of the adsorbent material, such an amount of cement in the process may already be sufficient to be produced immediately on site by adding admixtures of additional aggregates such as. sand or gravel and with the addition of water local concrete.

Stabilita proti napadnutiu hubami., ako aj zlepšené zachytáva3 nie benzínov, minerálnych alebo syntetických olejov alebo pod. sa dá zabezpečiť tým, že hydrofobizovaný granulát dodatočne obsahuje 2 až 10 hmôt. %, výhodne 3 až 5 hmôt. % železitého farbiva, najmä čierny oxid železitý.Stability against fungal attack as well as improved entrapment of gasoline, mineral or synthetic oils or the like. This can be ensured by the fact that the hydrophobized granulate additionally contains 2 to 10% by weight. %, preferably 3 to 5 wt. % ferric dye, in particular black iron oxide.

Adsorpčný materiál podľa vynálezu možno bezprostredne po výrobe zabaliť a obalové jednotky naplnené granulátom, napríklad vrecia, sa môžu ľahko dopravovať, pričom sypná hustota hydrofobizovaného a s cementom zmiešaného granulátu je 0,5 až 0,7 g/cm , najmä 0,58 g/cm až 0,65 g/cm . Najmä takáto sypná hustota má za následok, že bežné obalové jednotky, napríklad 100-litrové vrecia, sú transportovateľné bez pomoci mechanizácie.The adsorbent material according to the invention can be packaged immediately after manufacture and the packing units filled with granulate, for example sacks, can be easily transported, the bulk density of the hydrophobized and cement-mixed granulate being 0.5 to 0.7 g / cm, especially 0.58 g / cm up to 0.65 g / cm. In particular, such a bulk density results in conventional packaging units, such as 100 liter bags, being transportable without the aid of mechanization.

Spôsob výroby takéhoto adsorpčného materiálu podľa vynálezu sa vyznačuje hlavne tým, že porézne ľahké plnivo sa pomieša v suspenzii oleja vo vode s 3 až 12 hmôt. % mastných kyselín a/alebo voskami kyseliny karboxylovej, prípadne s prídavkom parafínu a vody a zmieša sa s 1,5 až 10 hmôt. % cementu a následne sa zmes zabalí. Prídavkom cementu pri zmiešavaní porézneho ľahkého plniva so suspenziou oleja vo vode sa súčasne so želanou hydrofobizáciou ľahkého plniva dosiahne viazanie prebytočnej vody. Pri tomto viazaní sa uvoľňuje teplo a toto hydratačné teplo spôsobuje rýchle sušenie hydrofobizovaného produktu, ktorý sa týmto môže bezprostredne a bez nákladných krokov sušenia baliť do vhodných obalových jednotiek. Pritom sa môže zmiešať granulát a suspenzia v hmotnostnom pomere od 1,5 do 3:1a výhodne v pomere 2 1, pričom sa spolu s cementom môže pridať dodatočne farbivo.The process for the production of such an adsorbent material according to the invention is characterized in particular by mixing the porous lightweight filler in an oil-in-water suspension of 3 to 12% by weight. % of fatty acids and / or carboxylic acid waxes, optionally with the addition of paraffin and water, and mixed with 1.5 to 10 wt. % cement, and then the mixture is packaged. By adding cement when mixing the porous light filler with the oil-in-water suspension, the excess water is bound together with the desired hydrophobization of the light filler. This binding releases heat and this hydration heat causes rapid drying of the hydrophobized product, which can be packaged in suitable packaging units immediately and without costly drying steps. The granulate and the suspension can be mixed in a weight ratio of 1.5 to 3: 1 and preferably in a ratio of 2 l, whereupon a colorant can be added together with the cement.

Použije sa ľahké plnivo, výhodne so sypnou hustotou od 0,4 do 0,5 g/cm3, najmä 0,42 do 0.45 g/cm3, a po zmiešaní so suspenziou oleja vo vode ako aj s cementom vznikne bezprostredneA lightweight filler is used, preferably with a bulk density of from 0.4 to 0.5 g / cm 3 , in particular from 0.42 to 0.45 g / cm 3 , and forms immediately after mixing with the oil-in-water slurry as well as with the cement.

O produkt so sypnou hustotou od asi 0,5 do 0,7 g/cm a najmä 0,58 g/cm3 do 0,65 g/cm3.A product with a bulk density of from about 0.5 to 0.7 g / cm 3, and in particular 0.58 g / cm 3 to 0.65 g / cm 3 .

Takto vyrobený adsorpčný materiál podľa vynálezu je vhodný najmä na zachytávanie chlórovaných uhľovodíkov a môže sa bezprostredne použiť ako predčisťovací filter napríklad v chemických čistiarňach. Adsorpčný materiál je rovnako vhodný pre čistenie odpadných vôd, ako prostriedok viažuci olej na súši i na mori, ako prídavná látka do betónu, ako plnivo, ako napr. výplň do špár a ako filter v odlučovači benzínu alebo podobne. Granulometri a adsorpčného materiálu podľa vynálezu umožňuje týmto široké rôznorodé využitie, pričom v neposlednom rade treba mať na zreteli aj použitie pri nasledujúcej výrobe betónu in situ.The adsorbent material thus produced according to the invention is particularly suitable for the capture of chlorinated hydrocarbons and can be used immediately as a pretreatment filter, for example in chemical treatment plants. The adsorbent material is also suitable for waste water treatment, as an oil-binding agent on land and at sea, as an additive to concrete, as a filler, such as e.g. cushion filling and as a filter in a gasoline separator or the like. The granulometer and adsorbent material according to the invention thus allow for a wide variety of applications, and last but not least, the use in subsequent production of concrete in situ must also be taken into account.

Claims (8)

PATENTOVÉ NÁROKYPATENT CLAIMS 1. Adsorpčný materiál pre viazanie škodlivých látok, najmä pre zachytávanie benzínov, minerálnych alebo syntetických olejov alebo podobných, obsahujúci porézny hydrofobizovaný materiál, vyznačujúci sa tým, že porézny materiál je lahké plnivo, najmä guličkový porézny materiál, na báze hydrátu kremičitanu vápenatého, absodanu alebo zeolitov, a popri hydrofobizačných prísadách obsahuje 1.5 do 10 hmôt. % cementu.Adsorbent material for binding harmful substances, in particular for the capture of petrol, mineral or synthetic oils or the like, comprising a porous hydrophobized material, characterized in that the porous material is a lightweight filler, in particular a spherical porous material, based on calcium silicate hydrate, zeolites, and, in addition to the hydrophobizing additives, contains 1.5 to 10 wt. % cement. 2. Adsorpčný materiál podľa nároku 1. vyznačujúci sa tým, že maximálna veľkosť zrna granulátu je s 15 mm, výhodneAdsorbent material according to claim 1, characterized in that the maximum particle size of the granulate is s 15 mm, preferably .........^.„5.mm.... ................. ^. „5.mm .... ........ 3. Adsorpčný materiál podľa nároku 1 alebo 2, vyznačujúci sa tým, že hydrofobizovaný granulát obsahuje prídavok 2 až 10 hmôt. %, s výhodou 3 až 5 hmôt. % železitého farbiva, najmä čierneho oxidu železitého.Adsorbent material according to claim 1 or 2, characterized in that the hydrophobized granulate contains an addition of 2 to 10% by weight. %, preferably 3 to 5 wt. % ferric dye, in particular black iron oxide. 4. Adsorpčný materiál podľa nároku 1, 2 alebo 3, vyznačujúci sa tým, že sypná hustota hydrofobizovaného a cementom upraveného granulátu je 0,5 až 0,7 g/cm^, výhodne 0,58 až 0,65 g/cm^ .Adsorbent material according to claim 1, 2 or 3, characterized in that the bulk density of the hydrophobized and cement-treated granules is 0.5 to 0.7 g / cm 2, preferably 0.58 to 0.65 g / cm 2. 5. Spôsob výroby granulátu podľa jedného z nárokov 1 až 4, vyznačujúci sa tým, že porézne ľahké plnivo sa pomieša v suspenzii oleja vo vode s 3 až 12 hmôt. % mastných kyselín a /alebo voskami kyseliny karboxylovej, prípadne s prídavkom parafínu a vody a zmieša sa s 1,5 až 10 hmôt. % cementu a následne sa zmes zabalí.Method for producing a granulate according to one of claims 1 to 4, characterized in that the porous lightweight filler is mixed in an oil-in-water suspension with 3 to 12% by weight. % of fatty acids and / or carboxylic acid waxes, optionally with the addition of paraffin and water, and mixed with 1.5 to 10 wt. % of the cement, and then the mixture is packaged. 6. Spôsob podľa nároku 5, vyznačujúci sa tým, že granulát a suspenzia sa zmiešajú v hmotnostnom pomere od 1,5 až 3:1, výhodne 2 : 1.Method according to claim 5, characterized in that the granulate and the suspension are mixed in a weight ratio of 1.5 to 3: 1, preferably 2: 1. 7. Spôsob podľa nároku 5 alebo 6. vyznačujúci sa tým, že farbivo sa použije spolu s cementom.Method according to claim 5 or 6, characterized in that the colorant is used together with the cement. 8. Spôsob podľa nároku 5,6 alebo 7, vyznačujúci sa tým, že sa pridá ľahké plnivo so sypnou hustotou od 0,4 do 0,5Method according to claim 5,6 or 7, characterized in that a lightweight filler with a bulk density of 0.4 to 0.5 is added.
SK573-94A 1992-09-21 1993-09-21 Adsorbent material for removing pollutants SK57394A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT187492 1992-09-21
PCT/AT1993/000146 WO1994006555A1 (en) 1992-09-21 1993-09-21 Adsorbent material for removing pollutants

Publications (1)

Publication Number Publication Date
SK57394A3 true SK57394A3 (en) 1994-11-09

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EP (1) EP0619759A1 (en)
CZ (1) CZ119694A3 (en)
HU (1) HUT68268A (en)
SK (1) SK57394A3 (en)
WO (1) WO1994006555A1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE202010011640U1 (en) * 2010-08-20 2011-11-21 Rehau Ag + Co. dry mortar
RU2481282C1 (en) * 2011-12-29 2013-05-10 Юлия Алексеевна Щепочкина Mixture for producing porous aggregate

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* Cited by examiner, † Cited by third party
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JPS56100883A (en) * 1980-01-16 1981-08-13 Chiyoda Kagaku Kenkyusho:Kk Oil absorbing agent
JPS6020985A (en) * 1983-07-15 1985-02-02 Wakaba Kagaku Kk Composition for disposal of oil
JPS6051651A (en) * 1983-08-31 1985-03-23 株式会社トクヤマ Manufacture of formed body
DE3717848A1 (en) * 1987-05-27 1988-12-08 Rwk Rhein Westfael Kalkwerke Inorganic material and process for the production thereof
JPH041242A (en) * 1990-04-18 1992-01-06 Nippon Steel Corp Production of oil-absorbing aggregate from zeolite and the like and oil-absorbing aggregate prepared therewith
JP3192653B2 (en) * 1990-08-30 2001-07-30 美智子 遠藤 How to solidify waste tempura oil
JPH04219185A (en) * 1990-12-18 1992-08-10 Nippon Steel Corp Oil absorptive aggregate and production thereof
SK279844B6 (en) * 1991-01-09 1999-04-13 Heidemarie Gattinger Process for the production of concrete blocks and plates

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CZ119694A3 (en) 1994-12-15
EP0619759A1 (en) 1994-10-19
WO1994006555A1 (en) 1994-03-31
HU9401367D0 (en) 1994-09-28
HUT68268A (en) 1995-06-28

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