CA1297502C - Process for chemical stabilization of heavy metal bearing dusts and sludges, such as eaf dust - Google Patents
Process for chemical stabilization of heavy metal bearing dusts and sludges, such as eaf dustInfo
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- CA1297502C CA1297502C CA 569828 CA569828A CA1297502C CA 1297502 C CA1297502 C CA 1297502C CA 569828 CA569828 CA 569828 CA 569828 A CA569828 A CA 569828A CA 1297502 C CA1297502 C CA 1297502C
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/0427—Dry materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/18—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mixtures of the silica-lime type
-
- 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
- C22B7/006—Wet processes
-
- 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
- C22B7/02—Working-up flue dust
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00767—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes
- C04B2111/00784—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes for disposal only
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- 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
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S106/00—Compositions: coating or plastic
- Y10S106/01—Fly ash
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Structural Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Civil Engineering (AREA)
- Processing Of Solid Wastes (AREA)
- Treatment Of Sludge (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Gasification And Melting Of Waste (AREA)
- Constitution Of High-Frequency Heating (AREA)
- Catching Or Destruction (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Fire-Extinguishing Compositions (AREA)
- Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
- Detergent Compositions (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
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- Bidet-Like Cleaning Device And Other Flush Toilet Accessories (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
This invention is directed to a process for the chemical stabili-zation of heavy metal bearing dusts and sludges. A preferred use for such process is the treatment of dust from an electric arc furnace (EAF). In the production of steel by the electric arc furnace process, a by-product thereof is the generation of EAF dust. Such dust, by virtue of the pres-ence of such elements as cadmium, hexavalent chromium and lead, is classi-fied as hazardous waste by U.S. Environmental Protection Agency (EPA). The present invention is directed to a process for the chemical stabilization of the inorganic EAF dust to render the hazardous constituents thereof virtually immobile. Such process is based on the pozzolanic reaction of materials containing anhydrous alumino-silicates which, in the presence of lime, water and chemicals, adsorb and/or physically entrap the heavy metals present in EAF dust into a calcium-alumino-silicate matrix.
This invention is directed to a process for the chemical stabili-zation of heavy metal bearing dusts and sludges. A preferred use for such process is the treatment of dust from an electric arc furnace (EAF). In the production of steel by the electric arc furnace process, a by-product thereof is the generation of EAF dust. Such dust, by virtue of the pres-ence of such elements as cadmium, hexavalent chromium and lead, is classi-fied as hazardous waste by U.S. Environmental Protection Agency (EPA). The present invention is directed to a process for the chemical stabilization of the inorganic EAF dust to render the hazardous constituents thereof virtually immobile. Such process is based on the pozzolanic reaction of materials containing anhydrous alumino-silicates which, in the presence of lime, water and chemicals, adsorb and/or physically entrap the heavy metals present in EAF dust into a calcium-alumino-silicate matrix.
Description
Backgroun(l of the Inver.~ og The present invcntlon, a process for the chemical stabilization . ¦ of heavy metal dusts and sludges, has partlcular utllity for the steel ! ¦ industry, where control of furnace emissions are necessary. While this 5 I inventior has broad application in the stabili~ation of heavy metals, it ¦ will be described in detail by lts preferred use or appllcatlon.
The basic or domlnant steelmaking practice followed today in the ¦ domestic and foreign steel industry ls the basic oxygen process. Such ) ¦ process utilizes molten pig iron as the basic charge to the furnace, which 10 ¦ thereafter is refined and alloyed as requiréd. This process requires the ready avallablllty of molten pig iron, produced by blast furnaces~
¦ Where molten pig lron is not available, and/or for the production of certain specialty grades of steel, an electric arc furnace (~AF) process l is followed. In a typical E~F process, solid charge ingredients including 15 ¦ raw scrap, limestone, burnt lime, iron ore and ferro alloy additives, are placed in the top-charge furnace unit. A conventional furnace unit is ¦ equipped with (l) a roof lift and swing arrangement which permits the roof ¦ to swing aside when cold scrap is charged into the furnace; (2) a rocker and rail tilting type arrangement which permits the furnace to tllt forward 20 1 for tapping and backward for slagging; (3) a system for additlons through l the furnace roof; and (4) evacuation systems for the removal of dust ) ¦ generated during the steelmaking cycle.
The electrodes are supported by electrode arms and clamps, and l pro~ect from overhead down through the furnace roof. The electrodes are 25 1 automatlcally controlled by an electro-mechanlcal positioning mechanism.
¦ An electric arc surging between the electrodes and scrap produces heat which melts the charge and refines the steel. The molten steel is tapped, typically at about 3000F, into a ladle and cast into blooms or poured into ingot molds.
I ~97S~Z
¦ In such ~ process, particulate emlssi~s are generated during (1) ¦ charging of scrap, (2) eapplng of furnaces, (3) pneumatic injection of additives, t4) oxygen blowing and (5) meltdown/refining periods. This particulate, EAF dust ls collected ln baghouses. Even though carefully monltored landfills have been used to minlmlze the problems associated with EAF dust, the EPA has determined that such inorganic dust constitutes a hazardous waste. More specifically, EAF dust ls currently classified as EPA Hazardous Waste No. K061 (emlssion control dust/sludge from the primary production of steel in electrlc furnaces) and, accordingly, must be managed as a hazardous waste.
As a result of this determination, the assignee hereof has actlvely pursued various methods for managing EAF dust. The present . invention is the result of this pursuit, and comprises a chemical stabili-zation process which renders the hazardous constituents in the dust virtu-ally immobile. Such process is based on the pozzolanic reaction of materials containlng anhydrous alumino-silicates which, in the presence of lime, water and chemicals, adsorb and/or physically entrap the heavy metals present in EAF dust into a calcium-alumino-silicate matrix, thereby render-ing them essentlally immobile. The process, and the results achieved - 20 thereby, will be described in greater detail in the specifications which follow.
,) Summary of the Invention The present lnvention is directed to a chemical stabilization process which in lts preferred embodiment ls adapted for electric arc furnace (EAF) dust whereby the hazardous constituents ln the dust are rendered virtually immobile. The process ls based on the pozzolanic reaction of materlals containing anhydrous alumlno-silicates which, in the ..,.
presence of lime, water and chemicals, adsorb and/or physically entrap the heavy metals present in EAF dust into a calcium-alumino-silicate matrix.
In one of several methods for chemical stabilization, the process includes mixing of the EAF dust with lime kiln dust, fly ash and hydrated lime to produce a blend having an available alkalinity of 9-9.5%. After dry mixing, an aqueous solution containing ferrous hydroxide and calcium sulfate, produced by mixing ferrous sulfate hepta-hydrate, calcium hydroxide and water, and adjusted to a pH ofabout 7, is added to the dry mix. Such mixture is then added to the mixing vessel and thoroughly mixed. The resulting blend, containing about one-third by weight of EAF dust, having been rendered non-hazardous, may be suitably transported to a disposal site.
The FIGURE is a graphic representation of data demonstrating the advantages achieved by this invention to significantly reduce the EPTT leachable lead concentration of an EAF dust chemically stabilized by the practice of this invention.
The present invention is directed primarily to a chemical stabilization process for the treatment of hazardous waste, such as the dust generated by an electric arc furnace (EAF) process. This process is based on the pozzolanic reaction of materials containing anhydrous alumino-silicates which, in the presence of lime, water and chemicals, adsorb and/or physically entrap the heavy metals present in EAF dust into a calcium- alumino-silicate matrix, thereby rendering them essentially immobile. The reaction ultimately produces a relatively impermeable concrete-like solid waste.
~i 1297S~2 To appreciate the contributions of this invention, it may be helpful to review the standards which have been developed under the direction of the U~S. Environmental Protection Agency (EPA). The EPA has determined that lead, cadmium and chromium are the constituents of concern for EAF
dust, and has set the following maximum Extractive Procedure Toxicity Test (EPTT) leachate concentration limits for delisting a hazardous material, i.e. less than six times drinking water standard (6XDWS):
Lead 0.30 mg/l Cadmium 0.06 mg/1 Chromium 0.30 mg/1 Based on years of experience with the operation of an electric furnace shop, EPTT results for EAF dust, when untreated, are typically:
Lead 139 mg/l Cadmium 1.7 mg/l Chromium 0.9 mg/l Based on the EPA mandate to effectively manage the hazardous EAF dust, an extensive investigation was undertaken to develop a system to stabilize the hazardous waste and render it virtually immobile. The present invention is the result of such investigation. EPTT of EAF dust, when subjected to the chemical stabilization process of this invention, will exhibit a significantly reduced hazardous constituent level, before and after an extended cure time, on the order of:
Lead 0.02 mg/l Cadmium 0.02 mg/l Chromium 0.07 mg/l In this practice of this invention, the chemicals utilized herein include:
~2975~2 - Fly ash, the major constituents being SiO2 and - Lime dust, the major constituent being CaO
- Hydrated lime, the major constituent being Ca(OH)2 - Ferrous sulfate hepta-hydrate, While the proportions of such chemicals may vary over a limited range, as set forth hereinafter, a relationship for practicing this process is one where, by approximate weight %, the ingredients include EAF dust (35), fly ash (6), lime kiln dust (15), ferrous sulfate hepta-hydrate ~10), hydrated lime (6) and water ~28).
Using such proportions, the process involves the following steps:
lS 1. Nixing of EAF dust, lime kiln dust, fly ash and hydrated lime, for approximately 1 to 2 minutes. If necessary, the hydrated lime may be varied to insure a blend having an available alkalinity of between 9 and 9.5%.
The basic or domlnant steelmaking practice followed today in the ¦ domestic and foreign steel industry ls the basic oxygen process. Such ) ¦ process utilizes molten pig iron as the basic charge to the furnace, which 10 ¦ thereafter is refined and alloyed as requiréd. This process requires the ready avallablllty of molten pig iron, produced by blast furnaces~
¦ Where molten pig lron is not available, and/or for the production of certain specialty grades of steel, an electric arc furnace (~AF) process l is followed. In a typical E~F process, solid charge ingredients including 15 ¦ raw scrap, limestone, burnt lime, iron ore and ferro alloy additives, are placed in the top-charge furnace unit. A conventional furnace unit is ¦ equipped with (l) a roof lift and swing arrangement which permits the roof ¦ to swing aside when cold scrap is charged into the furnace; (2) a rocker and rail tilting type arrangement which permits the furnace to tllt forward 20 1 for tapping and backward for slagging; (3) a system for additlons through l the furnace roof; and (4) evacuation systems for the removal of dust ) ¦ generated during the steelmaking cycle.
The electrodes are supported by electrode arms and clamps, and l pro~ect from overhead down through the furnace roof. The electrodes are 25 1 automatlcally controlled by an electro-mechanlcal positioning mechanism.
¦ An electric arc surging between the electrodes and scrap produces heat which melts the charge and refines the steel. The molten steel is tapped, typically at about 3000F, into a ladle and cast into blooms or poured into ingot molds.
I ~97S~Z
¦ In such ~ process, particulate emlssi~s are generated during (1) ¦ charging of scrap, (2) eapplng of furnaces, (3) pneumatic injection of additives, t4) oxygen blowing and (5) meltdown/refining periods. This particulate, EAF dust ls collected ln baghouses. Even though carefully monltored landfills have been used to minlmlze the problems associated with EAF dust, the EPA has determined that such inorganic dust constitutes a hazardous waste. More specifically, EAF dust ls currently classified as EPA Hazardous Waste No. K061 (emlssion control dust/sludge from the primary production of steel in electrlc furnaces) and, accordingly, must be managed as a hazardous waste.
As a result of this determination, the assignee hereof has actlvely pursued various methods for managing EAF dust. The present . invention is the result of this pursuit, and comprises a chemical stabili-zation process which renders the hazardous constituents in the dust virtu-ally immobile. Such process is based on the pozzolanic reaction of materials containlng anhydrous alumino-silicates which, in the presence of lime, water and chemicals, adsorb and/or physically entrap the heavy metals present in EAF dust into a calcium-alumino-silicate matrix, thereby render-ing them essentlally immobile. The process, and the results achieved - 20 thereby, will be described in greater detail in the specifications which follow.
,) Summary of the Invention The present lnvention is directed to a chemical stabilization process which in lts preferred embodiment ls adapted for electric arc furnace (EAF) dust whereby the hazardous constituents ln the dust are rendered virtually immobile. The process ls based on the pozzolanic reaction of materlals containing anhydrous alumlno-silicates which, in the ..,.
presence of lime, water and chemicals, adsorb and/or physically entrap the heavy metals present in EAF dust into a calcium-alumino-silicate matrix.
In one of several methods for chemical stabilization, the process includes mixing of the EAF dust with lime kiln dust, fly ash and hydrated lime to produce a blend having an available alkalinity of 9-9.5%. After dry mixing, an aqueous solution containing ferrous hydroxide and calcium sulfate, produced by mixing ferrous sulfate hepta-hydrate, calcium hydroxide and water, and adjusted to a pH ofabout 7, is added to the dry mix. Such mixture is then added to the mixing vessel and thoroughly mixed. The resulting blend, containing about one-third by weight of EAF dust, having been rendered non-hazardous, may be suitably transported to a disposal site.
The FIGURE is a graphic representation of data demonstrating the advantages achieved by this invention to significantly reduce the EPTT leachable lead concentration of an EAF dust chemically stabilized by the practice of this invention.
The present invention is directed primarily to a chemical stabilization process for the treatment of hazardous waste, such as the dust generated by an electric arc furnace (EAF) process. This process is based on the pozzolanic reaction of materials containing anhydrous alumino-silicates which, in the presence of lime, water and chemicals, adsorb and/or physically entrap the heavy metals present in EAF dust into a calcium- alumino-silicate matrix, thereby rendering them essentially immobile. The reaction ultimately produces a relatively impermeable concrete-like solid waste.
~i 1297S~2 To appreciate the contributions of this invention, it may be helpful to review the standards which have been developed under the direction of the U~S. Environmental Protection Agency (EPA). The EPA has determined that lead, cadmium and chromium are the constituents of concern for EAF
dust, and has set the following maximum Extractive Procedure Toxicity Test (EPTT) leachate concentration limits for delisting a hazardous material, i.e. less than six times drinking water standard (6XDWS):
Lead 0.30 mg/l Cadmium 0.06 mg/1 Chromium 0.30 mg/1 Based on years of experience with the operation of an electric furnace shop, EPTT results for EAF dust, when untreated, are typically:
Lead 139 mg/l Cadmium 1.7 mg/l Chromium 0.9 mg/l Based on the EPA mandate to effectively manage the hazardous EAF dust, an extensive investigation was undertaken to develop a system to stabilize the hazardous waste and render it virtually immobile. The present invention is the result of such investigation. EPTT of EAF dust, when subjected to the chemical stabilization process of this invention, will exhibit a significantly reduced hazardous constituent level, before and after an extended cure time, on the order of:
Lead 0.02 mg/l Cadmium 0.02 mg/l Chromium 0.07 mg/l In this practice of this invention, the chemicals utilized herein include:
~2975~2 - Fly ash, the major constituents being SiO2 and - Lime dust, the major constituent being CaO
- Hydrated lime, the major constituent being Ca(OH)2 - Ferrous sulfate hepta-hydrate, While the proportions of such chemicals may vary over a limited range, as set forth hereinafter, a relationship for practicing this process is one where, by approximate weight %, the ingredients include EAF dust (35), fly ash (6), lime kiln dust (15), ferrous sulfate hepta-hydrate ~10), hydrated lime (6) and water ~28).
Using such proportions, the process involves the following steps:
lS 1. Nixing of EAF dust, lime kiln dust, fly ash and hydrated lime, for approximately 1 to 2 minutes. If necessary, the hydrated lime may be varied to insure a blend having an available alkalinity of between 9 and 9.5%.
2. Adding to said mixture an aqueous solution having a pH of about 7 and made from water, ferrous sulfate ; hepta-hydrate and calcium hydroxide.
3. Blending for approximately 10 minutes to yield a viscous paste-like material, which when cured with time, i.e., hours, produces an impermeable concrete-like solid waste. The hardening process may continue for a period of several weeks~ or longer.
In the development of this invention, it was discovered that a key feature thereof was the presence of ferrous ions. Nuch of the earlier work was conducted using `\~ ..
.
12~7S02 laboratory or pilot trials of ferrous sulfate hepta-hydrate, the preferred practice outlined above. However, the source of such ferrous ions need not be so clinically clean, but may, for example, be derived from such industrial sources as waste pickle liquor, a waste by-product in the steelmaking process. The suitability of such a source for the ferrous ions renders this invention particularly noteworthy. That is, this invention can make productive use of a waste by-product to render the constituents of a hazardous waste virtually immobile.
The FIGURE is a graphic illustration showing the unexpected advantages gained through the inclusion of ferrous ions in the practice of this invention. The Figure shows the effect of EP Toxicity leachate pH on Pb concentration of chemically stabilized EAF dust, both with and without ferrous ions. The upper curve represents data in which the ferrous ions were omitted from the aqueous solution. While a distinct advantage was achieved by controlling the pH thereof to a range of about 9 to 10, the concentration of Pb was significantly above that of material made with aqueous solution containing ferrous ions, as represented in the data of the lower curve.
Data, to be presented hereinafter, indicate that as little as 0.2%, by weight, of ferrous ions can be effective to reduce the lead concentration, as well as cadmium and chromium levels, to acceptable EPA standards.
To demonstrate the effectiveness of this process to detoxify EAF dust, twenty-one (21) randomly selected samples were tested. The results thereof, insofar as the hazardous elements cadmium, chromium and lead are concerned, are listed in TABLES I and II (before and after curing~.
~Z~7S~)2 TABLE I
EP TOXICITY T,:STS( ) for Cd, Cr, Pb _ (before curing) Constituent (mg/1) 5 Sample Chromlum Identlfic~tionCadmium (Total) Lead A < 0.02 < 0.05 < 0.01 B < 0.02 < 0.05 0.02 C < 0.02 C 0.05 0.02 10 D < 0.02 < 0.05 0.03 E < 0.02 C 0.05 0.02 F < 0.02 < 0.05 < 0.01 ) G < 0.02 < 0.05 0.01 H < 0.02 < 0.05 < 0.01 15 I < 0.02 < 0.0S 0.01 J < 0.02 < 0.05 0.03 K < 0.02 < 0.05 0.02 L < 0.02 < 0.05 0.01 M < 0.02 < 0.05 0.02 20 N 0.02 < 0.05 0.03 O < 0.02 0.05 ^0.02 P < 0.02 < 0.05 < 0.01 Q < 0.02 0.12 < 0.01 R < 0.02 0.16 < 0.01 25 S < 0.02 0.13 C 0.01 T < 0.02 0.13 ~ 0.01 U < 0.02 < 0.05 < 0.01 Average(2) 0.02 0.07 0.02 ( ) All EP Toxicity tests and resultant extract analyses were performed in accordance with procedures outllned under 40 CFR 261, Appendices II and ( ) Less than signs were omitted in computation of averages.
,) ~3 . .. TABLE II 1 Z 9 ~50~
EP TOXICITY TESTS( ) for Cd, Cr, Pb .~. (after curing) Constituent (mg/1) 5 Sample Chromlum . IdentlficationCadmium (Total) ead A ~ 0.02 ~ 0.08 0.03 B 0.03 < 0.05 0.03 C < 0.02 ~ ~.05 0.02 D C 0.02 < 0.05 0.02 E 0.02 < 0.05 0.02 F < 0.02 < 0.05 < 0.01 .. G < 0.02 0.07 0.02 0.02 < 0.05 0.02 I 0.03 < n.os < O.
J C 0.02 ` 0.14 < 0.01 (0.03) (0.07) (0.03) R C 0.02 0.17 < 0.01 ( < 0.02) (0.05) (0.02) L < 0.02 0.07 .< 0.01 M < 0.02 C 0.16 < 0.01 . (0.03) (0.07) (0.01) N 0.02 0.05 < 0.01 ( < 0.02) (0.06) (0.01) O < 0.02 0.09 0.01 P < 0.02 0.06 0.03 . (0.02) (0.05) (0.01) . O~ < 0.02 0.06 0.04 (0.02) (0.05) (0.02) 30 R < 0.02 0.05 0.03 S < 0.02 0.06 0.02 .
T ~ 0.02 0.06 0.03 . U < 0.02 0.09 0.03 Average( ) 0.02 0.07 0.0Z
.` 35 (1) All EP Toxicity tests and resultant extract analyses were performed in .J accordance with procedures outlined under 40 CFR 261, Appendices II. and III. EP Toxicity tests for samples J, K, M, N, P and Q were done . on separate portions of cured material ground to pass through 9.5 mm and 0.149 mm sieves. Results for portions passed through a 0.149 mm sieve are shown in parenthesis. All other results are for samples . ground to pass through a 9.5 mm sieve.
( ) Less t n signs were omlt~ed In comp~ta~1On of averages.
.
_ g _ ~r: ' '~
~297S02 In addition to, and in support of, the EP Toxicity tests reported in TABLES I and II, a multiple extraction procedure was performed on six (6) samples to quantify the long term leaching characteristic of EAF dust chemically stabilized by the process of this invention. The multiple extraction procedure used was based on a procedure submitted to the U.S. EPA by Stablex Corporation and cited in the Federal Reqister Notice of November 22, 1982, page 52687.
The results are reported in TABLE III.
TABLE III
MULTIPLE EXTRACTION PROCEDURE FOR Cd, Cr, Pb (after curing, day 1 and day 9) Sample A B D E
Constituent : .
(mg/l) Day 1 Day 9 Day 1 Day 9 ~ ~ Day 1 Day 9 Cadmium < 0.02 < 0.02 ~ 0.02 < 0.02 < 0.02 C 0.02 C 0.02 ~ 0.02 15 Chromium 0.08< 0.05< 0.05 < 0.05< 0-05 < 0-05< 0.05 ~ 0.05 Lead 0.010.020.01 0.01 0.01 0.01 0.01 Ø02 G
Constituent (mg/l)Day 1 Day 9 Day 1 Day 9 Cadmium< 0.02 < 0.02 < Q.02 < 0.02 Chromium< 0.05 < 0.05 CO.05 < 0.05 Lead0.01 0.01 0.01 0.01 20 The results show no significant increase in the hazardous constituents concentration at the conclusion of the nine day test period.
~z97502 While the foregoing represents a preferred embodiment, and the results to be achieved by this invention, variations in the proportions of the chemicals have been used to achieve comparable results. For example, in blending the EAF dust, lime kiln dust, fly ash and hydrated lime it is desirable to have an available alkalinity of between 9 and 9.5% CaO.
- 10a -,,.~
However, tests have shown that effective results can be achieved with an available alkalinity of between about 6.9 and 11.5% CaO. A series of tests were conducted varying either the % CaO of the dry blend or the pH of the ferrous ion solution. The results of such tests are reported in TABLE IV.
'~;~;'`' o X ~ ~ 1297S02 El 3 In rD ~ ~a "
c~ ~ co A A /\ :~ u~
~ o o o ~
,2, ,~, A A t~
~ ~ ~o o o o o~ ~ I
,, Cr~ o I -D~
~ ~ .
~g~ D A /\ A ,_ C C C~ o o o ~ o I
,, o~ o~ !
A
.' ~ ~ i - :~ c ~ /~ A A ~ ' ~~ rt D~ .
C ~ . ~3 I
n 1 ~n ~ ~ t~ Ik~ ~Ir /\ ~t~l !
o 0,~ i~ o c '- A A A ,_ I :~
.. . .
' ' ~n o ~ I
.
i . o A A ~ l ~
~D O O O . ~ ~
,, ,, ~ o Vl _ -: ~ A , , ,~
,., C/~ o o o ~
,," . Ul ~ ~ ~ o _ ,. j~.. .
~ o ~ o 0 0 Ir ' :' '' o A A A
:: ~ o o o 3 , . . V~ ~ I o ~ _ ~, - .
/\ A o~ o Iz -. -?~ N ~ ¦ _ ^, 1297S(;~Z
Water is added for consistency to insure flowability of the mixture. One skilled in the art could readily determine that quantity of water to be added to the mixture. Since mixing may be automatic, or even manual, one can easily determine the amount of water needed to achieve a thorough but flowable mixture for the manner and total quantity to be mixed. From TABLE V, the percentage of water varied between about 17.5% (Sample P') to about 28.9% (Sample T').
While Samples Q', R', T', V', W', and X' represent samples from practices within the scope of this invention, particular attention is drawn to the comparison of Samples U', V' and W'. In U', without the addition of ferrous ions, the constituent levels for Pb and Cr were well above the levels to be achieved by the chemical stabilization process of this invention even though these levels may be less than the required (6XDWS) for delisting. In V', with the addition of less than 1% by weight ferrous ions, the levels of Pb and Cr were significantly reduced. In W', by doubling the amount of ferrous ions, Pb and Cr levels were furthered reduced.
While the presence of ferrous ions has a clear demonstrated impact on the successful practice of this invention, there is an obvious leveling off as the quantity increases. For example, in X', the weight % of ferrous ions was about 3Ø However, the constituent levels for Pb, Cd and Cr varied very little from W'. Accordingly, the upper limit for the ferrous ions is dictated more by economics and effects on pH, rather than results.
All of the above test samples listed in TABLE V
were prepared on the basis of first combining the dry materials, i.e. EAF dust, lime kiln dust, fly ash, hydrated \~
izg750~
lime and ferrous sulfate hepta hydrate followed by mixing with water for consistency. However, based on experience and knowledge in selecting the various constituents, it is possible to mix all desired constituents in a single batch mixing operation.
Finally, the efficiency of the process from the dual standpoint of controlling toxicity and cost of operations, dictates that as much EAF dust be treated as practical. It has been shown that the EAF dust may comprise approximately 65% by weight.
In the development of this invention, it was discovered that a key feature thereof was the presence of ferrous ions. Nuch of the earlier work was conducted using `\~ ..
.
12~7S02 laboratory or pilot trials of ferrous sulfate hepta-hydrate, the preferred practice outlined above. However, the source of such ferrous ions need not be so clinically clean, but may, for example, be derived from such industrial sources as waste pickle liquor, a waste by-product in the steelmaking process. The suitability of such a source for the ferrous ions renders this invention particularly noteworthy. That is, this invention can make productive use of a waste by-product to render the constituents of a hazardous waste virtually immobile.
The FIGURE is a graphic illustration showing the unexpected advantages gained through the inclusion of ferrous ions in the practice of this invention. The Figure shows the effect of EP Toxicity leachate pH on Pb concentration of chemically stabilized EAF dust, both with and without ferrous ions. The upper curve represents data in which the ferrous ions were omitted from the aqueous solution. While a distinct advantage was achieved by controlling the pH thereof to a range of about 9 to 10, the concentration of Pb was significantly above that of material made with aqueous solution containing ferrous ions, as represented in the data of the lower curve.
Data, to be presented hereinafter, indicate that as little as 0.2%, by weight, of ferrous ions can be effective to reduce the lead concentration, as well as cadmium and chromium levels, to acceptable EPA standards.
To demonstrate the effectiveness of this process to detoxify EAF dust, twenty-one (21) randomly selected samples were tested. The results thereof, insofar as the hazardous elements cadmium, chromium and lead are concerned, are listed in TABLES I and II (before and after curing~.
~Z~7S~)2 TABLE I
EP TOXICITY T,:STS( ) for Cd, Cr, Pb _ (before curing) Constituent (mg/1) 5 Sample Chromlum Identlfic~tionCadmium (Total) Lead A < 0.02 < 0.05 < 0.01 B < 0.02 < 0.05 0.02 C < 0.02 C 0.05 0.02 10 D < 0.02 < 0.05 0.03 E < 0.02 C 0.05 0.02 F < 0.02 < 0.05 < 0.01 ) G < 0.02 < 0.05 0.01 H < 0.02 < 0.05 < 0.01 15 I < 0.02 < 0.0S 0.01 J < 0.02 < 0.05 0.03 K < 0.02 < 0.05 0.02 L < 0.02 < 0.05 0.01 M < 0.02 < 0.05 0.02 20 N 0.02 < 0.05 0.03 O < 0.02 0.05 ^0.02 P < 0.02 < 0.05 < 0.01 Q < 0.02 0.12 < 0.01 R < 0.02 0.16 < 0.01 25 S < 0.02 0.13 C 0.01 T < 0.02 0.13 ~ 0.01 U < 0.02 < 0.05 < 0.01 Average(2) 0.02 0.07 0.02 ( ) All EP Toxicity tests and resultant extract analyses were performed in accordance with procedures outllned under 40 CFR 261, Appendices II and ( ) Less than signs were omitted in computation of averages.
,) ~3 . .. TABLE II 1 Z 9 ~50~
EP TOXICITY TESTS( ) for Cd, Cr, Pb .~. (after curing) Constituent (mg/1) 5 Sample Chromlum . IdentlficationCadmium (Total) ead A ~ 0.02 ~ 0.08 0.03 B 0.03 < 0.05 0.03 C < 0.02 ~ ~.05 0.02 D C 0.02 < 0.05 0.02 E 0.02 < 0.05 0.02 F < 0.02 < 0.05 < 0.01 .. G < 0.02 0.07 0.02 0.02 < 0.05 0.02 I 0.03 < n.os < O.
J C 0.02 ` 0.14 < 0.01 (0.03) (0.07) (0.03) R C 0.02 0.17 < 0.01 ( < 0.02) (0.05) (0.02) L < 0.02 0.07 .< 0.01 M < 0.02 C 0.16 < 0.01 . (0.03) (0.07) (0.01) N 0.02 0.05 < 0.01 ( < 0.02) (0.06) (0.01) O < 0.02 0.09 0.01 P < 0.02 0.06 0.03 . (0.02) (0.05) (0.01) . O~ < 0.02 0.06 0.04 (0.02) (0.05) (0.02) 30 R < 0.02 0.05 0.03 S < 0.02 0.06 0.02 .
T ~ 0.02 0.06 0.03 . U < 0.02 0.09 0.03 Average( ) 0.02 0.07 0.0Z
.` 35 (1) All EP Toxicity tests and resultant extract analyses were performed in .J accordance with procedures outlined under 40 CFR 261, Appendices II. and III. EP Toxicity tests for samples J, K, M, N, P and Q were done . on separate portions of cured material ground to pass through 9.5 mm and 0.149 mm sieves. Results for portions passed through a 0.149 mm sieve are shown in parenthesis. All other results are for samples . ground to pass through a 9.5 mm sieve.
( ) Less t n signs were omlt~ed In comp~ta~1On of averages.
.
_ g _ ~r: ' '~
~297S02 In addition to, and in support of, the EP Toxicity tests reported in TABLES I and II, a multiple extraction procedure was performed on six (6) samples to quantify the long term leaching characteristic of EAF dust chemically stabilized by the process of this invention. The multiple extraction procedure used was based on a procedure submitted to the U.S. EPA by Stablex Corporation and cited in the Federal Reqister Notice of November 22, 1982, page 52687.
The results are reported in TABLE III.
TABLE III
MULTIPLE EXTRACTION PROCEDURE FOR Cd, Cr, Pb (after curing, day 1 and day 9) Sample A B D E
Constituent : .
(mg/l) Day 1 Day 9 Day 1 Day 9 ~ ~ Day 1 Day 9 Cadmium < 0.02 < 0.02 ~ 0.02 < 0.02 < 0.02 C 0.02 C 0.02 ~ 0.02 15 Chromium 0.08< 0.05< 0.05 < 0.05< 0-05 < 0-05< 0.05 ~ 0.05 Lead 0.010.020.01 0.01 0.01 0.01 0.01 Ø02 G
Constituent (mg/l)Day 1 Day 9 Day 1 Day 9 Cadmium< 0.02 < 0.02 < Q.02 < 0.02 Chromium< 0.05 < 0.05 CO.05 < 0.05 Lead0.01 0.01 0.01 0.01 20 The results show no significant increase in the hazardous constituents concentration at the conclusion of the nine day test period.
~z97502 While the foregoing represents a preferred embodiment, and the results to be achieved by this invention, variations in the proportions of the chemicals have been used to achieve comparable results. For example, in blending the EAF dust, lime kiln dust, fly ash and hydrated lime it is desirable to have an available alkalinity of between 9 and 9.5% CaO.
- 10a -,,.~
However, tests have shown that effective results can be achieved with an available alkalinity of between about 6.9 and 11.5% CaO. A series of tests were conducted varying either the % CaO of the dry blend or the pH of the ferrous ion solution. The results of such tests are reported in TABLE IV.
'~;~;'`' o X ~ ~ 1297S02 El 3 In rD ~ ~a "
c~ ~ co A A /\ :~ u~
~ o o o ~
,2, ,~, A A t~
~ ~ ~o o o o o~ ~ I
,, Cr~ o I -D~
~ ~ .
~g~ D A /\ A ,_ C C C~ o o o ~ o I
,, o~ o~ !
A
.' ~ ~ i - :~ c ~ /~ A A ~ ' ~~ rt D~ .
C ~ . ~3 I
n 1 ~n ~ ~ t~ Ik~ ~Ir /\ ~t~l !
o 0,~ i~ o c '- A A A ,_ I :~
.. . .
' ' ~n o ~ I
.
i . o A A ~ l ~
~D O O O . ~ ~
,, ,, ~ o Vl _ -: ~ A , , ,~
,., C/~ o o o ~
,," . Ul ~ ~ ~ o _ ,. j~.. .
~ o ~ o 0 0 Ir ' :' '' o A A A
:: ~ o o o 3 , . . V~ ~ I o ~ _ ~, - .
/\ A o~ o Iz -. -?~ N ~ ¦ _ ^, 1297S(;~Z
Water is added for consistency to insure flowability of the mixture. One skilled in the art could readily determine that quantity of water to be added to the mixture. Since mixing may be automatic, or even manual, one can easily determine the amount of water needed to achieve a thorough but flowable mixture for the manner and total quantity to be mixed. From TABLE V, the percentage of water varied between about 17.5% (Sample P') to about 28.9% (Sample T').
While Samples Q', R', T', V', W', and X' represent samples from practices within the scope of this invention, particular attention is drawn to the comparison of Samples U', V' and W'. In U', without the addition of ferrous ions, the constituent levels for Pb and Cr were well above the levels to be achieved by the chemical stabilization process of this invention even though these levels may be less than the required (6XDWS) for delisting. In V', with the addition of less than 1% by weight ferrous ions, the levels of Pb and Cr were significantly reduced. In W', by doubling the amount of ferrous ions, Pb and Cr levels were furthered reduced.
While the presence of ferrous ions has a clear demonstrated impact on the successful practice of this invention, there is an obvious leveling off as the quantity increases. For example, in X', the weight % of ferrous ions was about 3Ø However, the constituent levels for Pb, Cd and Cr varied very little from W'. Accordingly, the upper limit for the ferrous ions is dictated more by economics and effects on pH, rather than results.
All of the above test samples listed in TABLE V
were prepared on the basis of first combining the dry materials, i.e. EAF dust, lime kiln dust, fly ash, hydrated \~
izg750~
lime and ferrous sulfate hepta hydrate followed by mixing with water for consistency. However, based on experience and knowledge in selecting the various constituents, it is possible to mix all desired constituents in a single batch mixing operation.
Finally, the efficiency of the process from the dual standpoint of controlling toxicity and cost of operations, dictates that as much EAF dust be treated as practical. It has been shown that the EAF dust may comprise approximately 65% by weight.
Claims (18)
PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method of chemically stabilizing material, such as dusts and sludges, where such material containing heavy metals may be classified as hazardous waste, comprising the steps of (1) mixing said material with chemicals containing anhydrous alumino-silicates, lime, ferrous ions and water to yield a flowable blend, (2) drying said blend to produce a relatively impermeable concrete-llke solid waste in which said heavy metals are physi-cally entrapped or adsorbed therein.
2. The method of chemically stabilizing hazardous waste in the form of dust and/or sludge according to claim 1, wherein the quantity of ferrous ions present in said blend is at least 0.2%, by weight.
3. The method of chemically stabilizing hazardous waste accord-ing to claim 2, wherein the quantity of ferrous ions present in said blend is at least about 1.0%, by weight.
4. The method of chemically stabilizing hazardous waste accord-ing to claim 1, wherein the waste to be treated is the dust by-product of the emissions from an electric arc furnace and said heavy metals are selected from the group consisting of lead, cadmium, and chromium.
5. The method of chemically stabilizing hazardous waste accord-ing to claim 4, wherein said lead, cadmium and chromium exhibit a reduced hazardous constituent level not to exceed 6XDWS.
6. The method of chemically stabilizing hazardous waste accord-ing to claim l, wherein the quantity of the material does not exceed about 65% by weight of said blend.
7. The method of chemically stabilizing hazardous waste accord-ing to claim l, wherein said anhydrous alumino-silicates are derived from fly ash, blast furnace slag, and/or other pozzolanic type materials, and said lime is derived from lime waste and/or other lime products.
8. A method of chemically stabilizing material, such as dusts and sludges, where such material containing heavy metals may be classified as hazardous waste, comprising the steps of (1) mixing said material with chemicals containing anhydrous alumino-silicates and lime to yield a mixture having an available alkalinity of between about 6.9 and 11.5, (2) adding thereto a solution containing ferrous ions in an amount sufficient for immobilizing said heavy metals, (3) adjusting the consistency of said blend by the addition of water to yield a flowable mass, and (4) drying said mass to produce a relatively impermeable concrete-like solid waste in which said heavy metals are encapsu-lated or adsorbed therein.
9. The method of chemically stabilizing hazardous waste accord-ing to claim 8, wherein the quantity of ferrous ions present in said solution is sufficient to comprise at least 0.2% by weight of said flowable mass.
10. The method of chemically stabilizing hazardous waste accord-ing to claim 9, wherein the quantity of ferrous ions is at least about 1.0%
by weight.
by weight.
11. The method of chemically stabilizing hazardous waste accord-ing to claim 10, wherein said material is the dust by-product of the emissions from an electric arc furnace and said heavy metals are selected from the group consisting of lead, cadmium, and chromium.
12. The method of chemically stabilizing hazardous waste accord-ing to claim 11, wherein said lead, cadmium and chromium exhibit a reduced hazardous constituent level not to exceed 6XDWS.
13. The method of chemically stabilizing hazardous waste accord-ing to claim 10, wherein said anhydrous alumino-silicates are derived from fly ash, blast furnace slag, and/or other pozzolanic type materials, and said lime is derived from lime waste and/or other lime products.
14. The method of chemically stabilizing hazardous waste accord-ing to claim 8, wherein the pH of said ferrous ion containing solution is between about 6.2 to 11.4.
15. The method of chemically stabilizing hazardous waste accord-ing to claim 8, wherein the quantity of the material does not exceed about 65% by weight of the flowable mass.
16. A method of chemically stabilizing material, such as dusts and sludges, where such material containing heavy metals may be classified as hazardous waste, comprising the steps of (1) preparing a ferrous ion containing solution having a pH
between about 6.2 to 11.4, (2) adding to said solution a quantity of said material, fly ash and lime, (3) thoroughly blending the ingredients to form a flowable mass, and (4) drying said mass to produce a relatively impermeable concrete-like solid waste in which said heavy metals are physi-cally entrapped or adsorbed therein.
between about 6.2 to 11.4, (2) adding to said solution a quantity of said material, fly ash and lime, (3) thoroughly blending the ingredients to form a flowable mass, and (4) drying said mass to produce a relatively impermeable concrete-like solid waste in which said heavy metals are physi-cally entrapped or adsorbed therein.
17. The method of chemically stabilizing hazardous waste accord-ing to claim 16, wherein said lead, cadmium and chromium exhibit a reduced hazardous constituent level not to exceed 6XDWS.
18. The method of chemically stabilizing hazardous waste accord-ing to claim 16, wherein said lead, cadmium and chromium exhibit a reduced hazardous constituent level not to exceed 6XDWS.
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US6360587A | 1987-06-18 | 1987-06-18 | |
US063,605 | 1987-06-18 |
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CA 569828 Expired - Lifetime CA1297502C (en) | 1987-06-18 | 1988-06-17 | Process for chemical stabilization of heavy metal bearing dusts and sludges, such as eaf dust |
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US (1) | US4911757A (en) |
EP (1) | EP0363429B1 (en) |
JP (1) | JPH03500502A (en) |
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DE (1) | DE3878691T2 (en) |
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RU (1) | RU2046112C1 (en) |
WO (1) | WO1988010243A1 (en) |
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- 1988-05-26 ZA ZA883753A patent/ZA883753B/en unknown
- 1988-06-03 IN IN459/CAL/88A patent/IN169600B/en unknown
- 1988-06-09 RU SU884742838A patent/RU2046112C1/en not_active IP Right Cessation
- 1988-06-09 EP EP19880906314 patent/EP0363429B1/en not_active Expired - Lifetime
- 1988-06-09 JP JP63505771A patent/JPH03500502A/en active Pending
- 1988-06-09 RO RO143356A patent/RO105948B1/en unknown
- 1988-06-09 AT AT88906314T patent/ATE85907T1/en not_active IP Right Cessation
- 1988-06-09 AU AU19929/88A patent/AU615458B2/en not_active Ceased
- 1988-06-09 HU HU884174A patent/HU206300B/en not_active IP Right Cessation
- 1988-06-09 WO PCT/US1988/001879 patent/WO1988010243A1/en active IP Right Grant
- 1988-06-09 DE DE19883878691 patent/DE3878691T2/en not_active Expired - Fee Related
- 1988-06-15 MX MX1190488A patent/MX168796B/en unknown
- 1988-06-17 ES ES8801902A patent/ES2006985A6/en not_active Expired
- 1988-06-17 GR GR880100386A patent/GR1001977B/en unknown
- 1988-06-17 CA CA 569828 patent/CA1297502C/en not_active Expired - Lifetime
-
1989
- 1989-05-09 US US07/349,006 patent/US4911757A/en not_active Expired - Lifetime
- 1989-12-14 NO NO895024A patent/NO300095B1/en not_active IP Right Cessation
- 1989-12-15 DK DK637989A patent/DK172051B1/en not_active IP Right Cessation
- 1989-12-15 FI FI896036A patent/FI100093B/en not_active IP Right Cessation
- 1989-12-15 BG BG9066089A patent/BG60266B2/en unknown
Also Published As
Publication number | Publication date |
---|---|
DE3878691D1 (en) | 1993-04-01 |
WO1988010243A1 (en) | 1988-12-29 |
RU2046112C1 (en) | 1995-10-20 |
NO895024L (en) | 1989-12-14 |
GR880100386A (en) | 1989-03-08 |
RO105948B1 (en) | 1993-01-30 |
DE3878691T2 (en) | 1993-06-09 |
ES2006985A6 (en) | 1989-05-16 |
DK637989A (en) | 1989-12-15 |
FI100093B (en) | 1997-09-30 |
EP0363429A4 (en) | 1990-11-29 |
DK637989D0 (en) | 1989-12-15 |
AU615458B2 (en) | 1991-10-03 |
MX168796B (en) | 1993-06-08 |
FI896036A0 (en) | 1989-12-15 |
NO300095B1 (en) | 1997-04-07 |
BG60266B1 (en) | 1994-03-31 |
JPH03500502A (en) | 1991-02-07 |
US4911757A (en) | 1990-03-27 |
AU1992988A (en) | 1989-01-19 |
HU206300B (en) | 1992-10-28 |
DK172051B1 (en) | 1997-09-29 |
NO895024D0 (en) | 1989-12-14 |
IN169600B (en) | 1991-11-16 |
ZA883753B (en) | 1989-03-29 |
ATE85907T1 (en) | 1993-03-15 |
EP0363429B1 (en) | 1993-02-24 |
GR1001977B (en) | 1995-10-09 |
EP0363429A1 (en) | 1990-04-18 |
HUT52743A (en) | 1990-08-28 |
BG60266B2 (en) | 1994-03-31 |
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