WO2000029071A1 - Procede d'immobilisation non lessivable de composes molybdene dans un laitier - Google Patents

Procede d'immobilisation non lessivable de composes molybdene dans un laitier Download PDF

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Publication number
WO2000029071A1
WO2000029071A1 PCT/NL1999/000702 NL9900702W WO0029071A1 WO 2000029071 A1 WO2000029071 A1 WO 2000029071A1 NL 9900702 W NL9900702 W NL 9900702W WO 0029071 A1 WO0029071 A1 WO 0029071A1
Authority
WO
WIPO (PCT)
Prior art keywords
slag
molybdenum
immobilisation
leachable
bar
Prior art date
Application number
PCT/NL1999/000702
Other languages
English (en)
Inventor
Jan Pieter Lotens
Abraham Barend Van Der Giesen
Original Assignee
Droan B.V.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Droan B.V. filed Critical Droan B.V.
Priority to AU12974/00A priority Critical patent/AU758925B2/en
Priority to NZ51177999A priority patent/NZ511779A/xx
Priority to EP19990956350 priority patent/EP1131137A1/fr
Priority to CA 2351391 priority patent/CA2351391A1/fr
Priority to JP2000582114A priority patent/JP2002529358A/ja
Publication of WO2000029071A1 publication Critical patent/WO2000029071A1/fr
Priority to NO20012405A priority patent/NO20012405L/no

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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
    • A62D3/33—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by chemical fixing the harmful substance, e.g. by chelation or complexation
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/04—Working-up slag
    • 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
    • A62D2101/08—Toxic combustion residues, e.g. toxic substances contained in fly ash from waste incineration
    • 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
    • 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
    • A62D2101/43—Inorganic substances containing heavy metals, in the bonded or free state
    • 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
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the invention relates to a method for the non-leachable immobilisation of molybdenum compounds in a slag by melting and subsequently cooling waste streams containing iron and molybdenum compounds.
  • Molybdenum compounds are present in a number of fairly specific waste streams. Examples of these are fly ashes from WIIs (waste incineration installations) and fly ashes from the processing of chemical waste by means of incineration in, for example, rotary furnaces.
  • the source of the molybdenum is partly to be ascribed to corrosion of the installation used and partly present in the waste streams processed in said installations.
  • molybdenum is one of the elements that forms oxyanions and the compounds that contain these ions are usually highly soluble in water. This makes it more difficult to comply with the leaching requirements under the abovementioned Building Materials Order. This problem is virtually independent of the technical approach followed when processing the waste streams. Both in the case of cold immobilisation (mixing of waste streams with, for example, cement) and in the case of processing in the form of a melt (thermal immobilisation or pyrometallurgical treatment) it is repeatedly found that the leachability of molybdenum exceeds the standard laid down in the Building Materials Order. Said standard specified for molybdenum is a maximum emission value of 150 mg/m per 100 years.
  • the invention relates to a method as specified in the preamble, which is characterised in that the treatment temperature is above the liquidus temperature of the slag; - the oxygen pressure is adjusted to a value of between 10 " and 10 " bar, this can be achieved by setting a fuel to oxygen ratio such that a CO/CO2 ratio of 0.25 - 10 is obtained in the furnace gas; the thermodynamic activity of Fe(II) in the slag is >0.5; the Fe(III)/Fe(II) ratio in the slag is between 0.25 and 2; and - after tapping off, the resultant slag is cooled such that a solid solution with a spinel structure is obtained.
  • the operating temperature must preferably be 50 °C or more above the liquidus temperature of the slag;
  • the oxygen pressure is adjusted to a value of between 10 " and 10 * bar. This can be achieved, for example, by setting a fuel to oxygen ratio such that a CO/CO2 ratio of between 0.5 and 5 is obtained in the furnace gas;
  • the slag composition is adjusted such that the thermodynamic activity coefficient of Fe(II) in the slag is > 1. This can be achieved by careful composition of the mixture of materials to be melted.
  • the method by which the activity coefficients can be calculated is described, for example, in the following references:
  • the resultant slag is then tapped off and then slowly cooled. Said cooling must therefore not take place suddenly (as in a "quench"), because this prevents crystallisation.
  • crystallisation can take place by allowing the slag pots, in which the slag is present, to cool in air or by imposing a suitable cooling regime on the slag in a cooling oven.
  • the slag will be tapped off into large slag pots with a capacity of approximately 1 tonne and cooled in air for approximately 24 hours. Such a cooling procedure gives a cooling rate of, on average, approximately 60 K/hour.
  • a cooling rate of 10 - 200 K/hour, advantageously 40 to 80 K/hour, will be used. If such conditions are maintained, spinels are formed, which belong to the 2FeO.Mo ⁇ 2-Fe 3 O 4 series, in which molybdenum is very firmly bound, in view of the low degree of leaching.
  • Waste streams were melted in a smelter installation under reducing conditions.
  • the furnace of the smelter installation consisted of a cylindrical, water-cooled chamber, where some of the molten slag solidified as a thin layer on the wall and where the slag on the inside thereof ran down and was collected in a slag bath. Said slag bath was emptied with some regularity, the tapped slag being cooled in slag pots in the air. Said cooling took approximately 24 hours.
  • the furnace was further equipped with an oxy-fuel burner in which oil was burnt with technical grade oxygen. The feed was fed into the furnace through the flame. The off-gas was post-combusted and the acid components were then removed in a wet gas scrubber, after which the fly material was separated off.
  • magnesium hydroxide served to obtain the correct slag composition with the associated desired crystallisation behaviour.
  • the calculated liquidus temperature (this was the temperature at which the entire mixture was liquid) was 1250°C for both mixtures.
  • the calculated activity coefficient of the FeO was 1.4 and 1.2, respectively, in the given slag composition.
  • Mixture 1 was melted under a significantly higher oxygen pressure than mixture 2, the oxygen pressures being, respectively, 10 "5 and 10 “9 bar.
  • the temperature in the furnace was at least 1350°C.
  • composition of the slags as far as the relevant elements are concerned and that of the associated fly material are given in Table C below.
  • the volatilisation of the elements zinc and lead can be calculated from the results given in Table C. For mixture 1 these values are: 71% and 59%. For the test with mixture 2, these values are 93% and 81%. The higher volatilisation in the case of the test with mixture 2 is in line with the more highly reducing conditions which were imposed.
  • Leaching of molybdenum from the slag was determined in accordance with NEN 7343 as specified in the Building Materials Order.
  • the material is ground and screened for this leaching test.
  • the 4 mm screen fraction is introduced into a column, through which a nitric acid solution at pH 4 is passed. Seven samples are taken after a number of (specified) volumes have passed through.
  • the composition of the leached liquid is then determined and the concentrations determined are converted to obtain an emission, which is then compared with the standard. Further details relating to the leaching test are given in NEN 7343.
  • the ratio of the amount of molybdenum leached from the slags to the permitted standard is 7.6 for mixture 1 and 0.64 for mixture 2. It is thus clear that the slag that crystallises with the spinel magnetite (FeO. Fe 2 O 3 ), in which a solid solution of M0O2 is present, exhibits leaching of molybdenum that is distinctly lower than the standard. Consequently, as far as molybdenum leaching is concerned, such a slag can freely be used in the construction industry.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geology (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Toxicology (AREA)
  • General Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

L'invention concerne un procédé d'immobilisation non lessivable de composés molybdène dans un laitier, consistant à traiter des flux de déchets contenant du fer et du molybdène, dans des conditions de réduction, par exemple sous une pression d'oxygène comprise entre 10?-6 et 10-12¿ bars, de préférence entre 10?-7,5 et 10-9,5¿ bars, à une température se situant avantageusement 50 °C au-dessus de la température dite 'liquidus' du laitier, et selon une activité thermodynamique du Fe(II) dans le laitier supérieure à 0,5, le rapport entre Fe(III) et Fe(II) dans le laitier étant réglé pour se situer entre 0,25 et 2; puis à refroidir le laitier résultant, de manière à obtenir une solution solide de MoO¿2? dans une structure de spinelle, laquelle présente une valeur de lessivage très basse du molybdène. En raison de cette caractéristique, on peut utiliser de tels laitiers, par exemple, en tant que matériau dans l'industrie de la construction.
PCT/NL1999/000702 1998-11-18 1999-11-16 Procede d'immobilisation non lessivable de composes molybdene dans un laitier WO2000029071A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
AU12974/00A AU758925B2 (en) 1998-11-18 1999-11-16 Method for the non-leachable immobilisation of molybdenum compounds in a slag
NZ51177999A NZ511779A (en) 1998-11-18 1999-11-16 Method for the non-leachable immobilisation of molybdenum compounds in a slag
EP19990956350 EP1131137A1 (fr) 1998-11-18 1999-11-16 Procede d'immobilisation non lessivable de composes molybdene dans un laitier
CA 2351391 CA2351391A1 (fr) 1998-11-18 1999-11-16 Procede d'immobilisation non lessivable de composes molybdene dans un laitier
JP2000582114A JP2002529358A (ja) 1998-11-18 1999-11-16 スラグ中のモリブデン化合物の非滲出性固定のための方法
NO20012405A NO20012405L (no) 1998-11-18 2001-05-16 Fremgangsmåte for ikke-utlutbar immobilisering av molybdenforbindelser i en slagg

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL1010590A NL1010590C2 (nl) 1998-11-18 1998-11-18 Werkwijze voor het niet-uitloogbaar immobiliseren van molybdeenverbindingen in een slak.
NL1010590 1998-11-18

Publications (1)

Publication Number Publication Date
WO2000029071A1 true WO2000029071A1 (fr) 2000-05-25

Family

ID=19768165

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL1999/000702 WO2000029071A1 (fr) 1998-11-18 1999-11-16 Procede d'immobilisation non lessivable de composes molybdene dans un laitier

Country Status (8)

Country Link
EP (1) EP1131137A1 (fr)
JP (1) JP2002529358A (fr)
AU (1) AU758925B2 (fr)
CA (1) CA2351391A1 (fr)
NL (1) NL1010590C2 (fr)
NO (1) NO20012405L (fr)
NZ (1) NZ511779A (fr)
WO (1) WO2000029071A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1917209A1 (fr) * 2005-08-23 2008-05-07 Studsvik, Inc. Mineralisation de metaux alcalins, de soufre et d'halogenes
US20150007696A1 (en) * 2013-07-04 2015-01-08 Industry-Academic Cooperation Foundation, Yonsei University METHOD OF RECOVERING Fe FROM STEEL-MAKING SLAG

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2150130A1 (de) * 1970-10-07 1972-04-13 Kennecott Copper Corp Verfahren zur Gewinnung von Molybdaen
JPS6019092A (ja) * 1983-07-13 1985-01-31 Nec Corp 廃液の処理方法
EP0652032A1 (fr) * 1993-11-10 1995-05-10 Emc Services Procédé d'inertage de déchets par cristallisation
EP0724918A1 (fr) * 1994-08-15 1996-08-07 Shinmaywa Industries, Ltd. Procede et appareil de traitement de dechets contenant des metaux lourds

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2150130A1 (de) * 1970-10-07 1972-04-13 Kennecott Copper Corp Verfahren zur Gewinnung von Molybdaen
JPS6019092A (ja) * 1983-07-13 1985-01-31 Nec Corp 廃液の処理方法
EP0652032A1 (fr) * 1993-11-10 1995-05-10 Emc Services Procédé d'inertage de déchets par cristallisation
EP0724918A1 (fr) * 1994-08-15 1996-08-07 Shinmaywa Industries, Ltd. Procede et appareil de traitement de dechets contenant des metaux lourds

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 8511, Derwent World Patents Index; Class D15, AN 85-064552, XP002104438 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1917209A1 (fr) * 2005-08-23 2008-05-07 Studsvik, Inc. Mineralisation de metaux alcalins, de soufre et d'halogenes
EP1917209A4 (fr) * 2005-08-23 2008-12-03 Studsvik Inc Mineralisation de metaux alcalins, de soufre et d'halogenes
US20150007696A1 (en) * 2013-07-04 2015-01-08 Industry-Academic Cooperation Foundation, Yonsei University METHOD OF RECOVERING Fe FROM STEEL-MAKING SLAG
US9650688B2 (en) * 2013-07-04 2017-05-16 Industry-Academic Cooperation Foundation, Yonsei University Method of recovering Fe from steel-making slag

Also Published As

Publication number Publication date
EP1131137A1 (fr) 2001-09-12
NO20012405D0 (no) 2001-05-16
AU758925B2 (en) 2003-04-03
JP2002529358A (ja) 2002-09-10
AU1297400A (en) 2000-06-05
NZ511779A (en) 2003-01-31
NO20012405L (no) 2001-07-13
NL1010590C2 (nl) 2000-05-22
CA2351391A1 (fr) 2000-05-25

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