EP0887088B1 - Verfahren und Anlage zur Behandlung von Asbestos enthaltenden absorbierenden Massen in Gasflaschen - Google Patents

Verfahren und Anlage zur Behandlung von Asbestos enthaltenden absorbierenden Massen in Gasflaschen Download PDF

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Publication number
EP0887088B1
EP0887088B1 EP98202155A EP98202155A EP0887088B1 EP 0887088 B1 EP0887088 B1 EP 0887088B1 EP 98202155 A EP98202155 A EP 98202155A EP 98202155 A EP98202155 A EP 98202155A EP 0887088 B1 EP0887088 B1 EP 0887088B1
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EP
European Patent Office
Prior art keywords
treatment
asbestos
process according
cylinder
basic solution
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.)
Expired - Lifetime
Application number
EP98202155A
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English (en)
French (fr)
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EP0887088A1 (de
Inventor
Gérard Debailleul
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Individual
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Individual
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Publication date
Priority claimed from BE9700553A external-priority patent/BE1011243A6/fr
Priority claimed from BE9800270A external-priority patent/BE1011867A6/fr
Application filed by Individual filed Critical Individual
Publication of EP0887088A1 publication Critical patent/EP0887088A1/de
Application granted granted Critical
Publication of EP0887088B1 publication Critical patent/EP0887088B1/de
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Classifications

    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/36—Detoxification by using acid or alkaline reagents
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/35—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by hydrolysis
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/40—Inorganic substances
    • A62D2101/41—Inorganic fibres, e.g. asbestos

Definitions

  • the present invention relates to a method of destruction of asbestos fibers contained in absorbent masses present inside acetylene gas cylinders.
  • the most common method is to cut the end bottles, to extract the absorbent mass in an area confined, pack said mass in regulatory bags and store the bags in appropriate landfills.
  • Metal is headed to the steel industry after a large rinse to remove particles adhering to metal. Rinsing water containing asbestos is discharged in the public circuit.
  • the other method is to introduce the bottles into ovens with a temperature above 1500 ° C.
  • the merger of metal and asbestos fibers is obtained there comes out a metal substrate and silica considered inert; this method is effective, but costly very high.
  • the bottle is destroyed.
  • asbestos-based waste either it is stored and is not destroyed, bringing pollution to the drainage system worn, or it is destroyed, but at great cost and without recovery.
  • the object of the present invention is to avoid these drawbacks and in particular to remove the absorbent masses containing asbestos out of metal bottles, preferably through their holes original, that is to say without destroying said bottles, or preventing their reuse.
  • the absorbent masses containing asbestos will only be in contact with the atmosphere.
  • a method for treating used gas cylinders, in particular acetylene gas, which have an original opening and in which are absorbent masses containing asbestos, comprising prior degassing of the bottle via said opening, with the formation of a depression in the bottle, formation of a concentrated basic solution having a temperature above 180 ° C.
  • This method advantageously makes it possible to attack the absorbent masses inside the bottles and thin them in situ. This allows their extraction without affecting the physical integrity of without endangering the environment by releasing dust containing asbestos.
  • This fluid mud can then be conducted, in a sealed manner vis-à-vis the external environment, in a known apparatus of the type described in the patent application international WO-A-97/00099. In this apparatus, the fibers asbestos and mineral fibers still suspended in the sludge liquids and already first attacked in the bottles themselves are attacked again and completely destroyed by a solution basic concentrated.
  • the installation placed on two trays, for example a maritime dimension of 20 feet, allows mobile treatment in situ on the gas storage area without special devices.
  • All the products resulting from this treatment are devoid of all asbestos fibers and other mineral fibers, personnel not be equipped with respiratory protection. All stages of processing can be carried out in a particularly closed circuit efficient and secure. No fiber can escape into the atmosphere, all the materials that can be reused and / or valued.
  • the fibers do not could not be released since the first operation destructive asbestos happens in the bottle itself, and that at when the material comes out of the bottle, the asbestos is in a silicate mud which does not allow fibers to be released in the atmosphere.
  • the aggression on the fibers is such that they do not could no longer cause pathology if introduced improbable in a respiratory circuit.
  • the method includes, prior to said introduction of basic solution, a degassing of the bottle by putting it in communication with a source of vacuum, through the opening.
  • the process comprises, after the treatment of the fluid mud, a separation of the latter into a recyclable liquid phase in the solution basic and in a recoverable solid phase.
  • the sentence liquid is thus recycled to the maximum, which significantly reduces any environmental pollution and lowers the cost of basic materials fresh necessary for the realization of the attack solution.
  • the sentence solid, totally free of asbestos fibers or mineral fibers can for example be recycled in silico-limestone compositions, usable in construction, or in the form of an adjuvant to clay intended for the manufacture of ceramic products.
  • the single figure schematically represents a installation for implementing the method according to the invention.
  • a basic solution preparation tank 1 capable of being heated by a heating element 2 to a temperature of the order of 160 ° C.
  • an agent for generating OH ions - in aqueous solution such as an alkaline or alkaline-earth base, in particular NaOH, is used.
  • NaOH flakes are for example stored in the silo 3 and supplied intermittently and known per se at the preparation tank 1. This is also connected in 4 to a source of water.
  • An outlet conduit 5 connects the bottom of the preparation tank 1 with a heating tank 6.
  • the valve 7 When the valve 7 is closed, the basic solution prepared is recycled to the top of the tank by a bypass 8, using a static mixer 9.
  • an element heating 10 In the heating tank 6 there is provided an element heating 10.
  • the basic solution is heated there for example to a temperature of the order of 260 ° C. under a vapor pressure of approximately 5 bars.
  • a series of gas cylinders 11 are maintained, head in bottom, in a template generally designated by the reference 12.
  • This template includes housings 13, one per bottle, in which bottles are retained by a removable plate 14 with smaller diameter perforations than the body of bottles and allowing passage of the heads 18 of the bottles to outside.
  • Each housing 13 can be fitted with a heat exchanger heat 15 to maintain the temperature inside the bottles at a sufficient level especially for degassing.
  • Template 12 can be supported on a frame not shown by an axis 16, so as to be able oscillate on this axis.
  • a motor 17 controls this oscillation movement in a known way.
  • Each flexible pipe 19 is connected to a branching with multiple channels, each closable by a valve 20 to 23 respectively.
  • the tank 6 is in communication with the bottles by a leads to attack solution 24 provided with a branch 25 towards each bottle and connected to valve 21 of the track branch multiple.
  • This multi-way branch is also connected to a gas pipe 26 through the valve 22 and to a mud pipe 27 through the valve 23.
  • the gas pipe 26 is connected to a vacuum pump 28, for example a water ring pump, via a trap cold 29.
  • the outlet of the pump 28 is connected to a recovery of water polluted with gas 30, which can then be evacuated by a pump 31 for treating wastewater, in particular filtering.
  • the mud conduits 27 are each connected to a slurry pump 32 which via the conduit 48 conducts the mass sludge absorbent to a reactor 33, via a three-way valve tracks 38 and a flexible hose 37.
  • the reactor 33 is mounted on an oscillating platform 34 supported by an axis 35 around which it is capable of tilting.
  • the tilting movement is generated in a known manner under the action of a system consisting of a hydraulic cylinder or pneumatic and connecting rods and generally designated by the reference 36.
  • the reactor is surrounded at least partially by a heating chamber 39 and it is mounted on the platform 34 so as to ability to rotate around its longitudinal axis under the action of a motor training 40.
  • the reactor is connected at 41 directly to a conduit feed coming for example from the preparation tank (at 42).
  • the three-way valve 38 also gives access to a outlet conduit 43 which leads to a phase separation device liquid and solid.
  • a phase separation device liquid and solid In the example illustrated, it is a filter press 44.
  • the solid cakes are collected in a collection bin 45 and the filtrate is recycled through recycling conduit 46 to a buffer tank 49, in turn in communication with the preparation tank 1, by a connecting duct 47.
  • the installation according to the invention operates in the manner next
  • the acetylene gas cylinders 11 are installed, open, in the housings 13 of the template 12 which is then closed by the plate 14.
  • a flexible pipe 19 is connected to the original opening of each cylinder and valves 20 and 22 of the multi-way branching are open, while the valves 21 and 23 are closed.
  • the pump 28 is started and a vacuum is thus removed from the residues of gas still contained in the bottles in a cold trap 29.
  • An aqueous acetone solution is recovered in the tank 30 to be then led to further use or treatment by the pump 31.
  • preparation tank 1 a basic solution concentrated attack is prepared. It is heated to a temperature from 160 to 240 ° C at a pressure of 2 to 10 bars and it has a NaOH molar concentration of 12.5.
  • the preparation solution is fed so discontinuous to the heating tank 6 in which it is brought to a temperature above 180 ° C., advantageously of the order of 190 to 270 ° C, preferably 260 ° C.
  • the solution attack is preferably maintained under a vapor pressure of 2.5 to 7 bars, advantageously of the order of 5 bars.
  • Valves 20 and 23 are then opened and the sludge fluidized are removed from the bottles using the mud pumps 32. It it is possible to envisage a succession of openings and closings alternating valves to clean the interior of the bottles with pressurized etching solution.
  • the sludge is then directed to reactor 33 which is supplied with basic solution of 35 molar concentration.
  • This solution can be formed from the basic solutions used for the attack and rinsing the bottles. It can also partially come from directly from the preparation tank 1.
  • the basic attack solution is under a pressure of 2 to 10 bars, advantageously 2.5 to 7 bars, and preferably 3 to 4 bars, and at a temperature above 180 ° C, advantageously of the order of 190 to 270 ° C, preferably 240 ° C.
  • the sludge is stirred in the reactor which is brought into rotation for example at 24 rpm around its longitudinal axis.
  • the contents of the reactor are then brought to the filter press 44 where the solid phase-liquid phase separation takes place.
  • the liquids are directed to the buffer tank 46 for a reheating and introduction into the preparation tank 1.
  • Solids from cakes removed from the filter press are directed to recovery treatments.
  • Recovery materials can be considered as raw materials in the two valuation systems by increased interstitial bonds and marked improvement in technical criteria of the various materials of these families. It is therefore of a raw material which has all its utility and therefore not of a second choice valuation as is often the case.

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  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Processing Of Solid Wastes (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Treating Waste Gases (AREA)

Claims (9)

  1. Verfahren zur Behandlung von verbrauchten Gasflaschen, insbesondere für Acetylen, welche eine Ursprungsöffnung aufweisen und in welchen sich Amiant enthaltende absorbierende Massen befinden, welches folgendes umfaßt:
    vorläufige Entgasung der Flasche mit Hilfe der Öffnung unter Bildung eines Unterdrucks in der Flasche,
    Herstellen einer konzentrierten basischen Lösung, die eine Temperatur von größer als 180 °C und einen Dampfdruck von 2,5 bis 7 bar aufweist,
    Zuführen dieser Lösung durch die Öffnung in das Innere einer jeden unter Unterdruck stehenden Flasche,
    erstes Angreifen der Amiant enthaltenden absorbierenden Massen im Inneren der geschlossenen Flasche durch die basische Lösung, bis zum Erhalt eines flüssigen Schlamms aus absorbierenden Massen, in dem sich Amiantfasem in Suspension befinden,
    Entfemen dieses flüssigen Schlamms über die Ursprungsöffnung und dessen Transport zu einem Behandlungsreaktor in einer abgedichteten Weise und
    Rückführen der Gasflaschen zu einer Wiederverwendung.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die konzentrierte, basische Lösung am Ende des Herstellungsschrittes einen Dampfdruck von 5 bar und eine Temperatur in der Größenordnung von 190 bis 270 °C, vorzugsweise 260 °C, aufweist.
  3. Verfahren nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass die Behandlung des entfernten flüssigen Schlamms in dem Reaktor ein zweites Angreifen dieses flüssigen Schlamms durch eine konzentrierte basische Lösung mit einem Dampfdruck von 2 bis 10 bar, vorzugsweise von 2,5 bis 7 bar, insbesondere von 3 bis 4 bar, und mit einer Temperatur von über 180 °C, vorzugsweise in der Größenordnung von 190 bis 270 °C, insbesondere von 240 °C, und ein Ausschütteln bis zur Erlangung einer Masse ohne Amiant umfasst.
  4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, dass die basische Lösung zur Behandlung des entfernten flüssigen Schlamms eine wässrige Lösung aus NaOH von 30 bis 40 Mol, vorzugsweise 35 Mol ist.
  5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass es das erste Angreifen von mehreren Flaschen gleichzeitig durch die basische Lösung und eine Behandlung der aus diesen Flaschen hervorgegangenen flüssigen Schlämme in einem gleichen Reaktor umfasst.
  6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass der als Folge vom ersten Angreifen in der Flasche erhaltene flüssige Schlamm frei von festen absorbierenden Massen ist.
  7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass es nach der Behandlung des flüssigen Schlamms ein Trennen dessen in eine rückführbare flüssige Phase in der basischen Lösung und in eine feste, verwertbare Phase umfasst.
  8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, dass die feste Phase in kalkhaltigen Siloco-Zusammensetzungen oder in der Form eines Aufbaumittels für Ton, das für keramische Produkte bestimmt ist, verwertbar ist.
  9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass es nach dem Entfernen des flüssigen Schlamms aus der Flasche ein zusätzliches Zuführen konzentrierter, basischer Lösung in das Innere einer jeden Flasche, ein abschließendes Waschen der Flasche und eine Behandlung der Waschlösung analog zu jener umfaßt, welche bei dem zuvor genannten flüssigen Schlamm eingesetzt wurde.
EP98202155A 1997-06-27 1998-06-25 Verfahren und Anlage zur Behandlung von Asbestos enthaltenden absorbierenden Massen in Gasflaschen Expired - Lifetime EP0887088B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
BE9700553A BE1011243A6 (fr) 1997-06-27 1997-06-27 Procede et installation de traitement des masses absorbantes contenant de l'amiante dans les bouteilles d'acetylene.
BE9700553 1997-06-27
BE9800270 1998-04-08
BE9800270A BE1011867A6 (fr) 1998-04-08 1998-04-08 Procede et installation de traitement de masses absorbantes contenant de l'amiante dans les bouteilles de gaz.

Publications (2)

Publication Number Publication Date
EP0887088A1 EP0887088A1 (de) 1998-12-30
EP0887088B1 true EP0887088B1 (de) 2003-10-01

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Application Number Title Priority Date Filing Date
EP98202155A Expired - Lifetime EP0887088B1 (de) 1997-06-27 1998-06-25 Verfahren und Anlage zur Behandlung von Asbestos enthaltenden absorbierenden Massen in Gasflaschen

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EP (1) EP0887088B1 (de)
AT (1) ATE250961T1 (de)
DE (1) DE69818552D1 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2950277B1 (fr) * 2009-09-23 2012-01-13 Air Liquide Procede pour eliminer un revetement present sur la surface d'un recipient de gaz

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1191237A (fr) * 1957-02-13 1959-10-19 Procédé et dispositif permettant d'enlever le contenu solide des bouteilles d'acétylène
DE4206647A1 (de) * 1992-03-03 1993-09-09 Solvay Umweltchemie Gmbh Recycling von asbesthaltigen acetylen-gasflaschen
AU5356494A (en) * 1992-10-08 1994-05-09 Cross-Link Technology Product and method for treating asbestos
JP3776935B2 (ja) * 1995-06-16 2006-05-24 ドバユール，ジェラール アスベストを含む廃棄物の処理方法およびプラント

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EP0887088A1 (de) 1998-12-30
DE69818552D1 (de) 2003-11-06
ATE250961T1 (de) 2003-10-15

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