EP2428254B1 - Verfahren zur Behandlung von asbesthaltigem Material - Google Patents

Verfahren zur Behandlung von asbesthaltigem Material Download PDF

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Publication number
EP2428254B1
EP2428254B1 EP11175285A EP11175285A EP2428254B1 EP 2428254 B1 EP2428254 B1 EP 2428254B1 EP 11175285 A EP11175285 A EP 11175285A EP 11175285 A EP11175285 A EP 11175285A EP 2428254 B1 EP2428254 B1 EP 2428254B1
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EP
European Patent Office
Prior art keywords
asbestos
process according
milk whey
anyone
hydrothermal
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EP11175285A
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English (en)
French (fr)
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EP2428254A1 (de
Inventor
Giulia Balducci
Elisabetta Foresti
Marco Lelli
Isidoro Giorgio Lesci
Marco Marchetti
Filippo Pierini
Norberto Roveri
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Chemical Center Srl
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Chemical Center Srl
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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
    • A62D3/02—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by biological methods, i.e. processes using enzymes or microorganisms
    • 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
    • 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
    • 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
    • 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
    • A62D2203/00—Aspects of processes for making harmful chemical substances harmless, or less harmful, by effecting chemical change in the substances
    • A62D2203/02—Combined processes involving two or more distinct steps covered by groups A62D3/10 - A62D3/40

Definitions

  • the present invention relates to a process for treating an asbestos containing material so as to transform the asbestos itself and enable a possible reuse of the products deriving from said treatment.
  • Asbestos is the commercial name attributed to several natural minerals having a fibrous structure and belonging to the class of silicates. In modern times some of these minerals were widely used because of their excellent technological properties: they have good resistance to heat and fire, to the action of chemical and biological agents and to abrasion and wear, have high mechanical strength and good flexibility, easily bind with construction materials and have good sound absorbing and heat insulating properties. Because of all these properties and its low cost asbestos was widely used in industrial and building applications and manufactured components, in means of transport and in the domestic sphere. In particular, the raw fibre was processed in order to obtain various products adaptable to multiple uses. In these products, the asbestos fibres may either be free, or strongly or weakly bound.
  • brittle materials which can be crumbled by hand pressure alone due to the poor internal cohesion.
  • compact materials which can be crumbled into powder only with the aid of mechanical machinery.
  • the materials in a brittle matrix are undoubtedly the most dangerous, as the fibres can be dispersed into the air with extreme ease and thus inhaled. Asbestos in a compact matrix, given its nature, does not tend to release fibres and a hazardous situation may arise only if it is abraded, deteriorated or sawed.
  • ACM Asbestos Containing Materials
  • Asbestos has been undoubtedly most widely used in the building sector, in particular in the form of a composite of asbestos and cement, or so-called asbestos-cement.
  • asbestos was largely used as a coating on beams or floors, applied with spraying and spreading techniques.
  • the heat-resistant mixture was composed of varying percentages of asbestos and other materials (vermiculite, sand or cellulose fibres) and binding materials (gypsum and/or calcium carbonate): the result was a continuous layer, soft to the touch, of a colour varying from dark grey to white.
  • the main ACW transformation processes are based on chemical treatments relying on the action of acids and thermal and mechanochemical treatments, though recently biochemical and microbiological methods have been studied.
  • the waste is melted at temperatures of between 1300 and 1400°C together with particular additives, such as blast furnace slag or industrial sludge, forming a mixture with a high metal content.
  • the slag thus derived is crystallized at a controlled temperature: in this manner one obtains products with very high mechanical strength, particularly suitable as coating and protective surfaces in the building, mechanical and chemical industries.
  • lithification is based on melting ACW derived from the removal of insulation from railway carriages at a temperature of 1300-1400°C. Slow cooling brings about the crystallization of pyroxenes, olivine and iron oxides. The final result of the treatment is the production of inert materials, which can be recovered for a variety of applications.
  • Microbiological methods have also been developed for the transformation of asbestos using bacteria, in particular Lactobacillus casei and Lactobacillus plantarum (see for example the article by I.A. Stanik, K. Cedzy ⁇ ska, S. ⁇ kowska; Fresenius Environmental Bulletin, Vol. 15, Issue 7, pp.640-643 (2006 )).
  • the method is based on breaking down the crystalline layers of Brucite (magnesium-oxygen) present within the crystalline layers of Chrysotile as a consequence of the indirect metabolism of the bacterial cultures used.
  • the decomposition of crystalline layers seems to be due to the acidification of the reaction environment, thanks to the presence of metabolites secreted by the bacteria, which also include lactic acid.
  • the hypothesized reaction mechanism is achieved through a substitution of Mg 2+ ions by H + ions, which are present in great excess. The magnesium thus released reacts with the lactic acid present to form soluble salts.
  • the Applicant thus addressed the problem of devising and fine-tuning a process for treating asbestos containing materials under relatively mild conditions, which is able to combine efficacy with both ecological and economic sustainability.
  • the Applicant therefore judged it expedient to couple a thermal treatment to an acid treatment in which the asbestos containing material in a broken-down form is subjected to the action not of a common acidic chemical reagent, but rather of an acidic industrial waste product, i.e. milk whey, which, besides creating an acidic environment, contributes bacterial components believed to favour an attack on the material itself.
  • the asbestos is then inertized by means of a high-temperature, high-pressure hydrothermal process.
  • the present invention thus relates to a process for treating an asbestos containing material, comprising:
  • the milk whey is preferably exhausted milk whey.
  • the hydrothermal process is carried out at a pH value of from 1 to 7, more preferably from 2 to 6.
  • the asbestos containing material can be any product which includes asbestos in a fibrillar form, in brittle matrices or a cement matrix, or also compact polymeric matrices (generally synthetic or cellulosic polymers). If asbestos containing materials are used in compact non-cement matrices, a pre-treatment of the material which is capable of freeing the fibres from the matrix itself is preferably carried out, as is better illustrated below.
  • the asbestos containing material can be:
  • the aforesaid asbestos containing materials are generally delivered as waste to be disposed of, and in order to transport them safely they are preferably wrapped with a protective film, which is preferably made from a biodegradable polymer (e.g. starch derivatives, polylactic acid, polyhydroxyalkanoates).
  • a biodegradable polymer e.g. starch derivatives, polylactic acid, polyhydroxyalkanoates
  • the material to be treated is preferably kept wrapped in said film also during the grinding process, which is carried out in order to obtain said material in a broken-down form.
  • Grinding has the purpose of obtaining fragments of a size which can vary within wide margins, such as to render the material itself compatible with the specific equipment used for the subsequent steps and to increase the exchange surface and thereby reduce treatment times.
  • the size can therefore vary from micrometric dimensions to several centimetres, for example between 1 and 5 cm.
  • the grinding process can be carried out with various types of machinery, depending on the specific material to be treated.
  • the grinding step is carried out on the material immersed in a tank containing the milk whey. This prevents the asbestos fibres from being dispersed in the environment during grinding. Said grinding can preferably be achieved by means of diamond cutters, which are capable of working immersed in the milk whey.
  • the material to be treated comprises asbestos in a fibrillar form dispersed in a compact polymeric matrix (generally synthetic or cellulosic polymers, e.g. paper or cardboard), prior to the treatment with milk whey the asbestos containing material is preferably subjected to a thermal pre-treatment in order to cause combustion of the polymeric matrix and to release the asbestos fibrils.
  • a compact polymeric matrix generally synthetic or cellulosic polymers, e.g. paper or cardboard
  • milk whey As regards milk whey, as is known, the latter consists in the liquid part which separates from the curd as a result of the process of coagulation of the casein present in the milk. It is thus a by-product of the production of cheese or casein from milk. Whey can be considered as the aqueous phase of milk. This phase is formed by the whole of the substances dissolved in the water (including soluble proteins), irrespective of their molecular size, and by substances with low molecular weights.
  • the composition of milk whey is highly complex and mainly comprises water, lactose, protein, fats and vitamins. Thanks to the presence of large amounts of protein and other nutritionally valid compounds, milk whey is further used in various ways, in particular for the production of cheese and other milk derivatives.
  • the waste liquid phase which derives from this second processing is the so-called "exhausted milk whey", which is considered non-hazardous special waste.
  • Exhausted milk whey which is considered non-hazardous special waste.
  • Table a typical composition of exhausted milk whey is shown: Substances Present Average Amount (% by weight) Lactose 4.0 ⁇ 4.6 Protein 0.10 ⁇ 0.15 Fats 0.15 ⁇ 0.30 Salts 0.9 ⁇ 1.1 Organic acids 0.20 ⁇ 0.25 pH 3.5 ⁇ 5.2
  • exhausted milk whey can have a variable composition depending on the specific manufacturing processes carried out in the dairy, which differ from product a product and also show seasonal variability.
  • a particularly innovative and economically relevant aspect of the present invention is precisely that it provides a process which not only allows asbestos containing waste to be treated so as to render it no longer hazardous to health, but also enables the disposal of huge amounts of milk whey, and in particular exhausted milk whey, which represents a serious ecological problem for the dairy industry.
  • the cement matrix in which the asbestos may be englobed in the form of fibrils is gradually transformed, with the production of carbon dioxide, so as to release the asbestos fibrils, which remain suspended in the liquid inside the tank where the treatment is carried out.
  • At least one organic acid can be added to the milk whey, in particular lactic acid or oxalic acid, so as to bring the pH to a value of between 1 and 3.
  • the amount of milk whey used in the process according to the present invention can vary from 2 to 100 times by weight, preferably from 20 to 40, relative to the weight of the total material to be treated.
  • the treatment with milk whey is carried out under stirring for a time of from 12 to 120 hours, more preferably from 48 to 72 hours, at a temperature of from 20 to 90°C, more preferably from 30 to 50°C.
  • carbon dioxide is formed as a result of the action of the acidic environment on the carbonates present in the cement.
  • This step of the process is preferably carried out in a closed tank, so that the carbon dioxide formed can be collected and conveyed into a plant where it is used without being emitted into the atmosphere: for example, a plant for the production of natural gas or biogas or for the production of biopolymers (e.g. polyhydroxyalkanoates) using specific cell cultures.
  • the solid phase containing the asbestos is conveyed, for example by suction, into a hydrothermal reactor (preferably made of steel) where the hydrothermal treatment is carried out at a temperature of from 120°C to 250°C, preferably from 160°C to 200°C, and at a pressure of from 5 to 20 bar, preferably from 8 to 15 bar.
  • a hydrothermal reactor preferably made of steel
  • the hydrothermal process is preferably carried out at a pH value of from 1 to 7, more preferably from 2 to 6. If the pH of the solid phase is not sufficiently acidic for an optimal execution of the process, it is possible to add at least one organic acid, in particular lactic acid or oxalic acid, to the reaction medium so as to bring the pH to the desired value.
  • at least one organic acid in particular lactic acid or oxalic acid
  • the Applicant has found that excessively prolonging this step may lead to an unexpected increase in the concentration of asbestos fibres. This is attributable to the formation of Chrysotile crystals, mainly during the prolonged stages of the process and this to an insufficient transformation.
  • To prevent the crystallization of fibrous Chrysotile during the hydrothermal process it is preferable to add at least one aluminium and/or iron salt to the reaction bath. It is believed that such salts are able to favour, in the event of recrystallization of the asbestos during the treatment, the formation of lizardite and/or antigorite instead of the unwanted Chrysotile phase.
  • the hydrothermal treatment is preferably carried out for a time of from 12 to 168 hours, preferably from 72 to 100 hours, and preferably no longer than 120 hours.
  • the asbestos containing solid phase deriving from the first step of the process generally has water or, preferably, milk whey added to it, the latter being able to contribute the necessary amount of water.
  • At least one chelating agent selected for instance from among: oxalic acid, lactic acid, formic acid, or salts thereof.
  • the chelation of magnesium ions is believed to promote cleavage of the Chrysotile crystal planes. Once the structural order characterizing it has be broken down, the asbestos (and in particular Chrysotile) will no longer be capable of packing according to its distinctive basic structural units and undergo a phase change.
  • At least one chelating agent in this step could also be useful for extracting some important constituent and substituent elements of asbestos, such as, for example, magnesium, nickel and iron, which can be recovered, for example, by means of electrochemical processes.
  • the process according to the present invention leads to the obtainment of different byproducts, which can be individually used for a variety of purposes.
  • the following are obtained:
  • the mixture was kept under stirring at a temperature of 30°C for an overall time of 80 hours. At the end of this treatment the pH was 5.82.
  • the resulting solid phase after undergoing filtration, was placed in a hydrothermal reactor together with 60 mL of exhausted milk whey, at a temperature of 150°C and a pressure of between 7 and 9 bar for 72 hours.
  • the resulting sample contained some constituent elements of the cement matrix (calcium carbonate, quartz and anorthite), whereas the percentage by weight of asbestos fibres decreased considerably, from 12% in the untreated sample to 2% in the solid residue at the end of the treatment.
  • the resulting solid phase after undergoing filtration, was placed in a hydrothermal reactor together with 50 mL of exhausted milk whey, at a temperature of 190°C and a pressure of between 8 and 12 bar for 60 hours.
  • the resulting sample contained some constituent elements of the cement matrix (calcium carbonate, quartz and anorthite), whereas the percentage by weight of asbestos fibres decreased considerably, from 12% in the untreated sample to 5% in the solid residue at the end of the treatment.
  • the mixture was kept under stirring at a temperature of 40°C for an overall time of 48 hours. At the end of this treatment the pH was 6.45.
  • the resulting solid phase after undergoing filtration, was placed in a hydrothermal reactor together with 70 mL of exhausted milk whey, at a temperature of 200°C and a pressure of between 15 and 20 bar for 72 hours.

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  • Business, Economics & Management (AREA)
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  • General Chemical & Material Sciences (AREA)
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Claims (14)

  1. Verfahren zur Behandlung von asbesthaltigem Material, umfassend:
    Behandlung des Materials mit einer Molke, um eine saure Flüssigkeitsphase und asbesthaltige Festphase zu erhalten;
    Aussetzen der asbesthaltigen Festphase einem hydrothermischen Verfahren bei einer Temperatur von 120 °C bis 250 °C und bei einem Druck von 5 bar bis 20 bar.
  2. Verfahren nach Anspruch 1, wobei die Molke exhaustierte Molke ist.
  3. Verfahren nach einem der vorangehenden Ansprüche, wobei das hydrothermische Verfahren bei einem pH-Wert von 1 bis 7, vorzugsweise von 2 bis 6 durchgeführt wird.
  4. Verfahren nach einem der vorangehenden Ansprüche, wobei das asbesthaltige Material Asbest in fibrillärer Form, dispergiert in eine spröde Matrix oder eine Zementmatrix, oder alternativ in eine kompakte Polymermatrix umfasst.
  5. Verfahren nach einem der vorangehenden Ansprüche, wobei das asbesthaltige Material Asbest in fibrillärer Form, dispergiert in eine kompakte Polymermatrix, umfasst und wobei das Material vor dem Behandlungsschritt mit der Molke einer thermischen Vorbehandlung unterzogen wird, um die Verbrennung der Polymermatrix zu verursachen und die Asbestfibrillen freizugeben.
  6. Verfahren nach einem der vorangehenden Ansprüche, wobei das asbesthaltige Material zuvor einem Mahlschritt unterzogen wird.
  7. Verfahren nach Anspruch 6, wobei der Mahlschritt mit dem Material durchgeführt wird, das in einen die Molke enthaltenden Behälter eingetaucht ist.
  8. Verfahren nach einem der vorangehenden Ansprüche, wobei der Molke mindestens eine organische Säure zugesetzt wird, im Besonderen Milchsäure oder Oxalsäure, um einen pH-Wert von 1 bis 3 zu erhalten.
  9. Verfahren nach einem der vorangehenden Ansprüche, wobei die Molke in einer Menge von 2 bis 100 eingesetzt wird, vorzugsweise von 20 bis 40, mal Gewicht relativ zum Gewicht des zu behandelnden Materials.
  10. Verfahren nach einem der vorangehenden Ansprüche, wobei die Behandlung mit der Molke unter Rühren für einen Zeitraum von 12 bis 120 Stunden durchgeführt wird, vorzugsweise von 48 bis 72 Stunden, bei einer Temperatur von 20 bis 90 °C, vorzugsweise von 30 bis 50 °C.
  11. Verfahren nach einem der vorangehenden Ansprüche, wobei das hydrothermische Verfahren bei einer Temperatur von 160 °C bis 200 °C und bei einem Druck von 8 bis 15 bar durchgeführt wird.
  12. Verfahren nach einem der vorangehenden Ansprüche, wobei das hydrothermische Verfahren für einen Zeitraum von 12 bis 168 Stunden, vorzugsweise von 72 bis 100 Stunden, und weiter bevorzugt nicht länger als 120 Stunden durchgeführt wird.
  13. Verfahren nach einem der vorangehenden Ansprüche, wobei vor dem hydrothermischen Verfahren der asbesthaltigen Festphase Wasser oder vorzugsweise Molke zugesetzt wird.
  14. Verfahren nach einem der vorangehenden Ansprüche, wobei während des hydrothermischen Verfahrens mindestens ein Chelatbildner zugesetzt wird, der beispielsweise aus Folgendem ausgewählt wird: Oxalsäure, Milchsäure, Ameisensäure oder Salze davon.
EP11175285A 2010-07-30 2011-07-26 Verfahren zur Behandlung von asbesthaltigem Material Active EP2428254B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
ITMI2010A001443A IT1401495B1 (it) 2010-07-30 2010-07-30 Processo per il trattamento di un materiale contenente amianto

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EP2428254A1 EP2428254A1 (de) 2012-03-14
EP2428254B1 true EP2428254B1 (de) 2013-03-27

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ES (1) ES2419405T3 (de)
IT (1) IT1401495B1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3126624A1 (fr) 2021-09-09 2023-03-10 Centre National De La Recherche Scientifique (Cnrs) Procede de traitement d’un produit contenant de l’amiante

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015166359A1 (en) * 2014-04-29 2015-11-05 Lebsc S.R.L. Process for biochemical denaturation of an asbestos-containing material
FR3040317A1 (fr) * 2015-08-31 2017-03-03 Sadoun Alain Agissant Pour Le Compte De La Soc Valmater Sas En Cours De Creation Procede de reduction par voie biologique de la quantite de magnesium et/ou de fer d'un dechet d'amiante
WO2019064069A2 (en) * 2017-09-29 2019-04-04 Tullia Zucca CEMENT DESTRUCTION METHOD, MATERIAL CONTAINING ASBESTOS AND / OR OTHER MATERIAL MATERIAL THROUGH SIMULTANEOUS MATERIAL SUBMISSION TO CAVITATION AND ACIDIC CHEMICAL REACTION
EP3731978B1 (de) * 2017-12-27 2023-06-07 IGL Innovation Foundry S.r.l. Verfahren und anlage zur zerstörung der kristallstruktur von mineral- und handgefertigten fasern
WO2025109486A1 (en) * 2023-11-20 2025-05-30 Eco Insight S.R.L. Process for treating asbestos

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007032412A1 (ja) * 2005-09-13 2007-03-22 The Institute For Eco & Economy System Corporation ゼロエミッション型火力発電システムによる水熱固化体及びその製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3126624A1 (fr) 2021-09-09 2023-03-10 Centre National De La Recherche Scientifique (Cnrs) Procede de traitement d’un produit contenant de l’amiante
WO2023037081A1 (fr) 2021-09-09 2023-03-16 Centre National De La Recherche Scientifique (Cnrs) Procede de traitement d'un produit contenant de l'amiante

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ITMI20101443A1 (it) 2012-01-31
IT1401495B1 (it) 2013-07-26
EP2428254A1 (de) 2012-03-14
ES2419405T3 (es) 2013-08-20

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