WO2000029071A1 - Method for the non-leachable immobilisation of molybdenum compounds in a slag - Google Patents
Method for the non-leachable immobilisation of molybdenum compounds in a slag Download PDFInfo
- 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
Links
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.
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NZ51177999A NZ511779A (en) | 1998-11-18 | 1999-11-16 | Method for the non-leachable immobilisation of molybdenum compounds in a slag |
EP19990956350 EP1131137A1 (en) | 1998-11-18 | 1999-11-16 | Method for the non-leachable immobilisation of molybdenum compounds in a slag |
JP2000582114A JP2002529358A (en) | 1998-11-18 | 1999-11-16 | Method for non-exudative fixation of molybdenum compounds in slag |
CA 2351391 CA2351391A1 (en) | 1998-11-18 | 1999-11-16 | Method for the non-leachable immobilisation of molybdenum compounds in a slag |
AU12974/00A AU758925B2 (en) | 1998-11-18 | 1999-11-16 | Method for the non-leachable immobilisation of molybdenum compounds in a slag |
NO20012405A NO20012405L (en) | 1998-11-18 | 2001-05-16 | Method for non-extinguishable immobilization of molybdenum compounds in a slag |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL1010590 | 1998-11-18 | ||
NL1010590A NL1010590C2 (en) | 1998-11-18 | 1998-11-18 | Method for the non-leachable immobilization of molybdenum compounds in a slag. |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000029071A1 true WO2000029071A1 (en) | 2000-05-25 |
Family
ID=19768165
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/NL1999/000702 WO2000029071A1 (en) | 1998-11-18 | 1999-11-16 | Method for the non-leachable immobilisation of molybdenum compounds in a slag |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP1131137A1 (en) |
JP (1) | JP2002529358A (en) |
AU (1) | AU758925B2 (en) |
CA (1) | CA2351391A1 (en) |
NL (1) | NL1010590C2 (en) |
NO (1) | NO20012405L (en) |
NZ (1) | NZ511779A (en) |
WO (1) | WO2000029071A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1917209A1 (en) * | 2005-08-23 | 2008-05-07 | Studsvik, Inc. | Mineralization of alkali metals, sulfur and halogens |
US20150007696A1 (en) * | 2013-07-04 | 2015-01-08 | Industry-Academic Cooperation Foundation, Yonsei University | METHOD OF RECOVERING Fe FROM STEEL-MAKING SLAG |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2150130A1 (en) * | 1970-10-07 | 1972-04-13 | Kennecott Copper Corp | Molybdenum recovery - from silicate slags esp slags from melting copper concentrates in reverberatory furnaces |
JPS6019092A (en) * | 1983-07-13 | 1985-01-31 | Nec Corp | Treatment of waste liquid |
EP0652032A1 (en) * | 1993-11-10 | 1995-05-10 | Emc Services | Process for steadying of waste by crystallization |
EP0724918A1 (en) * | 1994-08-15 | 1996-08-07 | Shinmaywa Industries, Ltd. | Heavy metal-containing waste treating process and apparatus |
-
1998
- 1998-11-18 NL NL1010590A patent/NL1010590C2/en not_active IP Right Cessation
-
1999
- 1999-11-16 JP JP2000582114A patent/JP2002529358A/en active Pending
- 1999-11-16 AU AU12974/00A patent/AU758925B2/en not_active Ceased
- 1999-11-16 EP EP19990956350 patent/EP1131137A1/en not_active Withdrawn
- 1999-11-16 NZ NZ51177999A patent/NZ511779A/en unknown
- 1999-11-16 CA CA 2351391 patent/CA2351391A1/en not_active Abandoned
- 1999-11-16 WO PCT/NL1999/000702 patent/WO2000029071A1/en active IP Right Grant
-
2001
- 2001-05-16 NO NO20012405A patent/NO20012405L/en unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2150130A1 (en) * | 1970-10-07 | 1972-04-13 | Kennecott Copper Corp | Molybdenum recovery - from silicate slags esp slags from melting copper concentrates in reverberatory furnaces |
JPS6019092A (en) * | 1983-07-13 | 1985-01-31 | Nec Corp | Treatment of waste liquid |
EP0652032A1 (en) * | 1993-11-10 | 1995-05-10 | Emc Services | Process for steadying of waste by crystallization |
EP0724918A1 (en) * | 1994-08-15 | 1996-08-07 | Shinmaywa Industries, Ltd. | Heavy metal-containing waste treating process and apparatus |
Non-Patent Citations (1)
Title |
---|
DATABASE WPI Section Ch Week 8511, Derwent World Patents Index; Class D15, AN 85-064552, XP002104438 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1917209A1 (en) * | 2005-08-23 | 2008-05-07 | Studsvik, Inc. | Mineralization of alkali metals, sulfur and halogens |
EP1917209A4 (en) * | 2005-08-23 | 2008-12-03 | Studsvik Inc | Mineralization of alkali metals, sulfur and halogens |
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 (en) | 2001-09-12 |
AU758925B2 (en) | 2003-04-03 |
NL1010590C2 (en) | 2000-05-22 |
NZ511779A (en) | 2003-01-31 |
AU1297400A (en) | 2000-06-05 |
NO20012405L (en) | 2001-07-13 |
CA2351391A1 (en) | 2000-05-25 |
NO20012405D0 (en) | 2001-05-16 |
JP2002529358A (en) | 2002-09-10 |
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