EP0008127B1 - Process for consolidating coal and/or rock in mines - Google Patents

Process for consolidating coal and/or rock in mines Download PDF

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Publication number
EP0008127B1
EP0008127B1 EP19790102934 EP79102934A EP0008127B1 EP 0008127 B1 EP0008127 B1 EP 0008127B1 EP 19790102934 EP19790102934 EP 19790102934 EP 79102934 A EP79102934 A EP 79102934A EP 0008127 B1 EP0008127 B1 EP 0008127B1
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Prior art keywords
added
chemical substance
magnesium oxide
dispersion
rock
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Expired
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EP19790102934
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German (de)
French (fr)
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EP0008127A1 (en
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Hans-Guido Dr. Klinkner
Günter Culmann
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Saarbergwerke AG
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Saarbergwerke AG
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Classifications

    • E—FIXED CONSTRUCTIONS
    • E21—EARTH DRILLING; MINING
    • E21D—SHAFTS; TUNNELS; GALLERIES; LARGE UNDERGROUND CHAMBERS
    • E21D9/00—Tunnels or galleries, with or without linings; Methods or apparatus for making thereof; Layout of tunnels or galleries
    • E21D9/001—Improving soil or rock, e.g. by freezing; Injections
    • E21D9/002—Injection methods characterised by the chemical composition used

Definitions

  • the invention relates to a method for solidifying coal and / or rock by injecting a hardening dispersion from a magnesium chloride solution, burnt magnesite, highly active magnesium oxide, bentonite and water.
  • a magnesia cement composition is known from US Pat. No. 2543959, which is mixed with more than 2.5% by weight of magnesium oxide obtained from seawater and with phosphates.
  • a disadvantage of this magnesia cement composition is that, despite the addition of phosphates, it shrinks on solidification. It is therefore not useful as a material for solidifying coal and / or rock, because due to the shrinkage during solidification too little pressure is created to force the dispersion into the finest cavities of the used rock.
  • the object of the invention is therefore to provide a method of the type mentioned at the outset in which the setting time of the dispersion is relatively short and in which the values for the adhesive strength of the dispersion continuously increase to the final value during the setting process.
  • Chemical substances suitable as retarding agents are, for example, borax, sodium sulfate, sodium fluoride, potassium permanganate and ammonium molybdate.
  • the setting retarders are added to the dispersion in an amount of up to 1% by weight. It is advantageous that the addition of the setting retarder shortens the setting time relatively, i.e. not proportionally to the proportion of active magnesium oxide added, that the values for the adhesive force continuously increase to the final value and that the values for the adhesive force of the cured dispersion are higher than without the addition of a retarder.
  • Highly active magnesium oxide is obtained by burning precipitated magnesium oxide. It improves the gluing ability of the dispersion and enables penetration into very thin gaps in the rock. A relatively quick hardening of the dispersion with highly active magnesium oxide also takes place at so-called cold operating points underground with a temperature below 20 ° C. The setting time is not reduced in proportion to the proportion of highly active magnesium oxide added.
  • the invention is explained in more detail on the basis of test results.
  • the materials used in the tests had the following properties: Technical magnesite contained approximately 86.4% by weight magnesium oxide in the chemical analysis; the technically concentrated magnesium chloride solution had a specific weight of 1.334 g / cm 3 ; highly active precipitated and burned magnesium oxide contained 99% by weight of MgO; the borax used as a retarding agent in the experiment was in the form of borax decahydrate.
  • the setting time corresponds to the time until the maximum temperature of the hardening dispersion is reached.
  • the adhesive strength of the hardening dispersion is measured as the shear strength of a glue joint between two unglazed tiles.
  • the setting time of the dispersion increases linearly with the proportion of borax added.
  • borax decahydrate increases the shear strength of the hardened dispersion and extends the setting time slightly.
  • magnesium chloride flakes can also be used analogously.
  • retarders are other boric acid salts, phosphates, fluorides, sulfates, permanganates and molybdates, whereby Na 2 S0 4 (sodium sulfate), NaB0 2 (sodium metaborate), Na 3 P0 4 .

Description

Die Erfindung bezieht sich auf ein Verfahren zum Verfestigen von Kohle und/oder Gestein durch Injizieren einer nach ihrem Eindringen erhärtenden Dispersion aus einer Magnesiumchloridlösung, gebranntem Magnesit, hochaktivem Magnesiumoxid, Bentonit und Wasser.The invention relates to a method for solidifying coal and / or rock by injecting a hardening dispersion from a magnesium chloride solution, burnt magnesite, highly active magnesium oxide, bentonite and water.

Derartige Verfahren werden besonders dort angewendet, wo tektonische Störungen den Strekkenvortrieb behindern bzw. in Abbaubetrieben Ausböschungen des Kohlestosses die Kohlegewinnung erschweren.Such methods are used in particular where tectonic disturbances impede the tunneling or in coal mining operations, the coal piles make it difficult to extract coal.

Voraussetzung für den praktischen Einsatz einer Injektionsdispersion untertage ist neben niedriger Viskosität und guter Verleimungsfähigkeit eine ausreichend lange Aushärtungszeit. Für bestimmte Anwendungsfälle werden dagegen Dispersionen benötigt, die relativ schnell aushärten. Die Aushärtungszeit kann bei einem aus der DE-B Nr. 2204281 bekannten Verfahren durch Veränderung des Verhältnisses der Anteile an Magnesiumchloridlösüng, Magnesiumoxid und Bentonitmehl weitgehend variiert werden. Bei einem bestimmten Mischungsverhältnis wird jedoch ein unterer Grenzwert für die Aushärtezeit erreicht, der nicht mehr unterschritten werden kann.Bekannt ist es aus «Glückauf Forschungshefte», Dezember 1976, Heft 6, S. 243 bis 245, durch Zusatz eines Anteils von 2,5 Gew.% hochaktivem Magnesiumoxid zu einer Mischung aus konzentrierter Magnesiumchloridlösung, gebranntem Magnesit und Bentonitmehl die Aushärtezeit der Dispersion weiter zu verkürzen und zugleich die sich nach kurzen Standzeiten einstellenden Festigkeitswerte zu verbessern. Nachteilig ist, dass bei Zugabe eines Anteils von mehr als 2,5 Gew.% hochaktivem Magnesiumoxid die Werte für die Klebkraft im Verlauf des Abbindevorgangs ein Minimum durchlaufen, um danach wieder anzusteigen.In addition to low viscosity and good gluing ability, a prerequisite for the practical use of an injection dispersion underground is a sufficiently long curing time. For certain applications, on the other hand, dispersions are required that harden relatively quickly. In a process known from DE-B No. 2204281, the hardening time can be largely varied by changing the ratio of the proportions of magnesium chloride solution, magnesium oxide and bentonite flour. With a certain mixing ratio, however, a lower limit for the hardening time is reached, which can no longer be fallen short of. It is known from “Glückauf Forschungshefte”, December 1976, Issue 6, pp. 243 to 245, by adding a proportion of 2.5 % By weight of highly active magnesium oxide to a mixture of concentrated magnesium chloride solution, burnt magnesite and bentonite flour to further shorten the hardening time of the dispersion and at the same time to improve the strength values which arise after short standing times. It is disadvantageous that when a proportion of more than 2.5% by weight of highly active magnesium oxide is added, the values for the adhesive force pass through a minimum in the course of the setting process, in order then to rise again.

Aus der US-PS Nr. 2543959 ist eine Magnesiazementmasse bekannt, welche mehr als 2,5 Gew.% aus Meerwasser gewonnenem Magnesiumoxid und mit Phosphaten versetzt wird. Nachteilig an dieser Magnesiazementmasse ist, dass an ihr trotz des Zusatzes von Phosphaten beim Erstarren ein Schwund auftritt. Sie ist daher als Material zum Verfestigen von Kohle und/oder Gestein nicht brauchbar, weil infolge des Schwindens beim Erstarren zu wenig Druck entsteht, um die Dispersion in die feinsten Hohlräume des gebrächen Gesteins zu drücken.A magnesia cement composition is known from US Pat. No. 2543959, which is mixed with more than 2.5% by weight of magnesium oxide obtained from seawater and with phosphates. A disadvantage of this magnesia cement composition is that, despite the addition of phosphates, it shrinks on solidification. It is therefore not useful as a material for solidifying coal and / or rock, because due to the shrinkage during solidification too little pressure is created to force the dispersion into the finest cavities of the used rock.

Aufgabe der Erfindung ist es daher, ein Verfahren der eingangs genannten Art zu schaffen, bei dem die Abbindezeit der Dispersion relativ kurz ist und bei dem die Werte für die Klebekraft der Dispersion während des Abbindevorgangs kontinuierlich bis zum Endwert ansteigen.The object of the invention is therefore to provide a method of the type mentioned at the outset in which the setting time of the dispersion is relatively short and in which the values for the adhesive strength of the dispersion continuously increase to the final value during the setting process.

Erfindungsgemäss wird dies dadurch erreicht, dass ein Anteil von mehr als 2,5 Gew.% an hochaktivem Magnesiumoxid beigemengt wird, und dass zusätzlich ein die Abbindung verzögernder chemischer Stoff zugesetzt wird.This is achieved according to the invention in that a proportion of more than 2.5% by weight of highly active magnesium oxide is added, and in addition a chemical substance which retards the setting is added.

Als Abbindeverzögerer geeignete chemische Stoffe sind beispielsweise Borax, Natriumsulfat, Natriumfluorid, Kaliumpermanganat und Ammoniummolybdat. Die Abbindeverzögerer werden der Dispersion in einer Menge bis zu 1 Gew.% zugesetzt. Vorteilhaft ist, dass sich durch den Zusatz des Abbindeverzögerers die Abbindezeit relativ, das heisst nicht proportional zum Anteil an zugesetztem aktivem Magnesiumoxid verkürzt, dass die Werte für die Klebekraft kontinuierlich bis zum Endwert ansteigen und dass die Werte für die Klebkraft der ausgehärteten Dispersion höher sind als ohne Zusatz von Abbindeverzögerer.Chemical substances suitable as retarding agents are, for example, borax, sodium sulfate, sodium fluoride, potassium permanganate and ammonium molybdate. The setting retarders are added to the dispersion in an amount of up to 1% by weight. It is advantageous that the addition of the setting retarder shortens the setting time relatively, i.e. not proportionally to the proportion of active magnesium oxide added, that the values for the adhesive force continuously increase to the final value and that the values for the adhesive force of the cured dispersion are higher than without the addition of a retarder.

Hochaktives Magnesiumoxid wird durch Brennen von gefälltem Magnesiumoxid erhalten. Es verbessert die Verleimungsfähigkeit der Dispersion und ermöglicht ein Eindringen in sehr dünne Spalten im Gestein. Eine relativ schnelle Aushärtung der mit hochaktivem Magnesiumoxid versetzten Dispersion erfolgt auch an sogenannten kalten Betriebspunkten untertage mit einer Temperatur unter 20°C. Die Abbindezeit wird nicht proportional zum Anteil an zugesetztem hochaktivem Magnesiumoxid herabgesetzt.Highly active magnesium oxide is obtained by burning precipitated magnesium oxide. It improves the gluing ability of the dispersion and enables penetration into very thin gaps in the rock. A relatively quick hardening of the dispersion with highly active magnesium oxide also takes place at so-called cold operating points underground with a temperature below 20 ° C. The setting time is not reduced in proportion to the proportion of highly active magnesium oxide added.

Die Erfindung wird anhand von Versuchsergebnissen näher erläutert. Die bei den Versuchen verwendeten Materialien hatten folgende Eigenschaften: Technischer gebrannter Magnesit enthielt bei der chemischen Analyse ca. 86,4 Gew.% Magnesiumoxid; die technisch konzentrierte Magnesiumchloridlösung hatte ein spezifisches Gewicht von 1,334 g/cm3; hochaktives gefälltes und gebranntes Magnesiumoxid enthielt 99 Gew.% MgO; das als Abbindeverzögerer im Versuch benutzte Borax lag in Form von Boraxdekahydratvor.The invention is explained in more detail on the basis of test results. The materials used in the tests had the following properties: Technical magnesite contained approximately 86.4% by weight magnesium oxide in the chemical analysis; the technically concentrated magnesium chloride solution had a specific weight of 1.334 g / cm 3 ; highly active precipitated and burned magnesium oxide contained 99% by weight of MgO; the borax used as a retarding agent in the experiment was in the form of borax decahydrate.

Die Abbindezeit entspricht der Zeit bis zum Erreichen der Maximaltemperatur der aushärtenden Dispersion. Die Klebkraft der erhärtenden Dispersion wird als Scherfestigkeit einer Leimfuge zwischen zwei unglasierten Kacheln gemessen.

Figure imgb0001
The setting time corresponds to the time until the maximum temperature of the hardening dispersion is reached. The adhesive strength of the hardening dispersion is measured as the shear strength of a glue joint between two unglazed tiles.
Figure imgb0001

Die Abbindezeit der Dispersion erhöht sich linear mit dem Anteil an zugesetztem Borax.

Figure imgb0002
Figure imgb0003
 The setting time of the dispersion increases linearly with the proportion of borax added.
Figure imgb0002
Figure imgb0003

Ein Zusatz eines geringen Anteils von Boraxdekahydrat erhöht die Scherfestigkeit der ausgehärteten Dispersion und verlängert die Abbindezeit geringfügig.The addition of a small proportion of borax decahydrate increases the shear strength of the hardened dispersion and extends the setting time slightly.

Anstelle von konzentrierter technischer Magnesiumchloridlösung können auch Magnesiumchloridflocken analog verwendet werden.Instead of concentrated technical magnesium chloride solution, magnesium chloride flakes can also be used analogously.

Weitere Abbindeverzögerer sind andere borsaure Salze, Phosphate, Fluoride, Sulfate, Permanganate und Molybdate, wobei Na2S04 (Natriumsulfat), NaB02 (Natriummetaborat), Na3P04. 12H20 (Trinatriumorthophosphat bzw. Natriumphosphat), NaF (Natriumfluorid), KMn04 (Kaliumpermanganat), (NH4)10Mo12041· 7H2O bzw. (NH4) 6Mo7O24·4H2O (NH4)2MoO4 (Ammoniummolybdat) eingehend erprobt wurden und sich ebenso wie Borax (Na2B40,) bzw. Boraxdekahydrat als geeignet erwiesen haben.Other retarders are other boric acid salts, phosphates, fluorides, sulfates, permanganates and molybdates, whereby Na 2 S0 4 (sodium sulfate), NaB0 2 (sodium metaborate), Na 3 P0 4 . 12H 2 0 (trisodium orthophosphate or sodium phosphate), NaF (sodium fluoride), KMn0 4 (potassium permanganate), (NH 4) 10 Mo 12 0 41 · 7H 2 O or (NH 4) 6 Mo 7 O 24 · 4H 2 O ( NH 4 ) 2 MoO 4 (ammonium molybdate) have been thoroughly tested and have proven to be suitable, as well as borax (Na 2 B 4 0,) or borax decahydrate.

Claims (14)

1. A process for consolidating coal and/or rock in mining by the injection of a dispersion which hardens after its entry and which comprises a magnesium chloride solution, calcined magnesite, highly-active magnesium oxide, bentonite and water, characterised in that an amount of more than 2.5% by weight of highly-active magnesium oxide is admixed and that, additionally, a chemical substance which retards setting is added.
2. A process as claimed in claim 1, characterised in that the chemical substance is added in an amount of up to 1 % by weight.
3. A process as claimed in claim 1 or 2, characterised in that a borate is added as the chemical substance.
4. A process as claimed in claim 3, characterised in that borax is added as the chemical substance.
5. A process as claimed in claim 1 or 2, characterised in that a sodium salt of a phosphoric acid is added as the chemical substance.
6. A process as claimed in claim 5, characterised in that sodium phosphate is added.
7. A process as claimed in claim 1 or 2, characterised in that a sulphate is added as the chemical substance.
8. A process as claimed in claim 7, characterised in that sodium sulphate (Na2S04) is added.
9. A process as claimed in claim 1 or 2, characterised in that a permanganate is added as the chemical substance.
10. A process as claimed in claim 9, characterised in that potassium permanganate (KMn04) is added as the chemical substance.
11. A process as claimed in claim 1 or 2, characterised in that a fluoride is added as the chemical substance.
12. A process as claimed in claim 11, characterised in that sodium fluoride (NaF) is added as the chemical substance.
13. A process as claimed in claim 1 or 2, characterised in that a molybdate is added as the chemical substance.
14. A process as claimed in one of claims 1 to 13, characterised in that the chemical substance is water-soluble and is added to the magnesium chloride solution.
EP19790102934 1978-08-12 1979-08-13 Process for consolidating coal and/or rock in mines Expired EP0008127B1 (en)

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DE2835451 1978-08-12
DE19782835451 DE2835451C2 (en) 1978-08-12 1978-08-12 Process for solidifying coal and / or rock in mining

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EP0008127A1 EP0008127A1 (en) 1980-02-20
EP0008127B1 true EP0008127B1 (en) 1982-04-14

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