WO2018207131A1 - Procédé de fabrication de pastilles/briquettes auto-réductrices à partir de poussière de dépoussiéreurs à manches mélangée avec du carbone à utiliser dans des fours de fabrication d'acier - Google Patents

Procédé de fabrication de pastilles/briquettes auto-réductrices à partir de poussière de dépoussiéreurs à manches mélangée avec du carbone à utiliser dans des fours de fabrication d'acier Download PDF

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Publication number
WO2018207131A1
WO2018207131A1 PCT/IB2018/053262 IB2018053262W WO2018207131A1 WO 2018207131 A1 WO2018207131 A1 WO 2018207131A1 IB 2018053262 W IB2018053262 W IB 2018053262W WO 2018207131 A1 WO2018207131 A1 WO 2018207131A1
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WO
WIPO (PCT)
Prior art keywords
iron
oxide
zinc
briquette
weight
Prior art date
Application number
PCT/IB2018/053262
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English (en)
Inventor
Narottam BEHERA
Mohammed Abdulwahab TAYEB
Mohammed SAMMAN
Original Assignee
Sabic Global Technologies 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 Sabic Global Technologies B.V. filed Critical Sabic Global Technologies B.V.
Priority to EP18728966.5A priority Critical patent/EP3635142A1/fr
Priority to US16/611,579 priority patent/US20200399723A1/en
Priority to CN201880038094.8A priority patent/CN110741101A/zh
Publication of WO2018207131A1 publication Critical patent/WO2018207131A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/008—Use of special additives or fluxing agents
    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24—Binding; Briquetting ; Granulating
    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24—Binding; Briquetting ; Granulating
    • C22B1/242—Binding; Briquetting ; Granulating with binders
    • C22B1/244—Binding; Briquetting ; Granulating with binders organic
    • C22B1/245—Binding; Briquetting ; Granulating with binders organic with carbonaceous material for the production of coked agglomerates
    • 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
    • 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

  • This invention relates to the fields of steel-making and bag house dust remediation.
  • EAF dust is formed during steelmaking operations from metal oxidation and volatilization at high processing temperatures, and collected as dust in bag houses. Because EAFs typically rely on scrap metal for their charge, the composition of the dust correlates with the chemistry of the metallic charge used, and can vary from one melt to the next. Iron is the primary component of steel, and bag house dust from steel mills consequently includes high concentrations of iron oxide (40-60%). Zinc oxide and metals including manganese, calcium, magnesium, silicon, lead, copper, chromium, aluminum, mercury, and their compounds are also present in bag house dust.
  • the present disclosure provides a method for recycling materials present in EAF bag house dust.
  • Inventors have found that combining bag house dust with a carbon source in briquettes or pellets provides a composition that may be used as a feedstock in steel making furnaces, including electric arc and basic oxygen furnaces.
  • a solid composition in the form of a briquette or pellet is provided, the solid composition is adapted for use as a feed stock in steel making furnaces and comprises a carbon source and a bag house dust comprising iron oxide and at least 1% zinc by weight.
  • the solid composition does not include a non-carbonaceous iron reducing agent.
  • non-carbonaceous iron reducing agents include ferrous chloride and ferrous sulfate.
  • the solid composition carbon source comprises greater than 90% carbon by weight, preferably greater than 80% carbon.
  • the solid composition carbon source is selected from the group consisting of anthracite, graphite, coal, coke, petcoke, coal tar pitch, tar, molasses, decanter sludge, petrochemical waste coke, aluminum smelter spent pot lining or combinations thereof.
  • the bag house dust iron oxide is iron (II) oxide (FeO), iron (III) oxide (Fe 2 0 3 ), iron ( ⁇ , ⁇ ) oxide (Fe 3 0 4 , FesCvs, FesCb), or mixtures thereof, preferably Fe 2 0 3 .
  • the bag house dust zinc is zinc oxide (ZnO), or any other zinc-containing oxide, zinc ferrite, or mixtures thereof.
  • the solid composition comprises 0 to 15% of an additive.
  • die additive is selected from the group consisting of lime, calcium chloride, silica, limestone, clay, iron and/or steel grindings, iron and/or steel borings, iron and/or steel turnings, or combinations thereof.
  • the bag house dust comprises greater than 30% by weight iron oxide. In further embodiments, the bag house dust comprises from greater than 0 to 70% by weight iron oxide.
  • a briquette or pellet adapted for use as a recycled feed stock in electric arc and/or basic oxygen furnaces comprising 60 to 90% by weight of a bag house dust comprising iron oxide and zinc, 3 to 20% by weight of a carbon source, and 0 to 15% by weight additive.
  • the briquette or pellet does not include a non-carbonaceous iron reducing agent.
  • non-carbonaceous iron reducing agents include ferrous chloride and ferrous sulfate.
  • the briquette or pellet carbon source comprises greater than 90% carbon by weight, preferably greater than 80% carbon.
  • the briquette or pellet carbon source is selected from the group consisting of anthracite, graphite, coal, coke, petcoke, coal tar pitch, tar, molasses, decanter stodge, or combinations thereof.
  • the briquette or pellet bag house dust iron oxide is iron (II) oxide (FeO), iron (III) oxide (Fe 2 0 3 ), iron ( ⁇ , ⁇ ) oxide (Fe 3 0 4 , Fes06, FesCb), or mixtures thereof, preferably Fe 2 0 3 .
  • the briquette or pellet bag house dust zinc is zinc oxide (ZnO), or any other zinc-containing oxide, zinc ferrite, or mixtures thereof
  • the briquette or pellet additive is selected from the group consisting of lime, calcium chloride, silica, limestone, clay, iron and/or steel grindings, iron and/or steel borings, iron and/or steel turnings, or combinations thereof.
  • the bag house dust comprises greater than 30% by weight iron oxide. In further embodiments, the bag house dust comprises 30 to 70% by weight iron oxide.
  • a steel product selected front the group of flat products and long products comprising ⁇ 99% by weight unrecycled iron, >1% by weight iron derived from recycled bag house dust in the form of a briquette or pellet; the recycled bag house dust comprising ⁇ 99% by weight iron oxide, >1% by weight zinc, a carbon source.
  • the recycled bag house dust comprises 0-15%) of an additive.
  • the recycled bag house dust does not include a non- carbonaceous iron reducing agent.
  • Non-limiting examples of non-carbonaceous iron reducing agents include ferrous chloride and ferrous sulfate.
  • the recycled bag house dust carbon source is selected from the group consisting of anthracite, graphite, coal, coke, petcoke, coal tar pitch, tar, molasses, decanter sludge, or combinations thereof.
  • the recycled bag house dust iron oxide is iron (II) oxide (FeO), iron (III) oxide (Fe 2 0 3 , iron ( ⁇ , ⁇ ) oxide (Fe 3 0 4 , Fes06, FesCb), or mixtures thereof preferably Fe 2 0 3 .
  • the recycled bag house dust zinc is zinc oxide (ZnO), or any other zinc- containing oxide, zinc ferrite, or mixtures thereof.
  • Some aspects of the disclosure are directed towards a method of making a steel product comprising die steps of obtaining a solid composition in the form of a briquette or pellet, introducing the solid composition into an electric arc furnace or basic oxygen furnace, operating said electric arc furnace or basic oxygen furnace to produce molten steel, and processing the molten steel from the electric arc furnace or basic oxygen furnace into a steel product.
  • the solid composition comprises a carbon source and a baghouse dust comprising iron oxide and at least 1% zinc by weight.
  • the solid composition comprises 60 to 90 % by weight of a bag house dust comprising iron oxide and zinc, 3 to 20 % by weight of a carbon source, and from 0 or greater than 0 to 15% by weight additive.
  • the iron oxide comprises 30 to 70 % by weight of the bag house dust.
  • Additives include lime, calcium chloride, silica, limestone, clay, iron and/or steel grindings, iron and/or steel borings, iron and/or steel turnings, and the like.
  • the briquette or pellet does not include a non-carbonaceous iron reducing agent.
  • Non-limiting examples of non-carbonaceous iron reducing agents include ferrous chloride and ferrous sulfate.
  • the carbon source is selected from the group consisting of anthracite, graphite, coal, coke, petcoke, coal tar pitch, tar, molasses, decanter sludge, or combinations thereof.
  • the iron oxide is iron (II) oxide (FeO), iron (III) oxide (Fe 2 0 3 ).
  • iron ( ⁇ , ⁇ ) oxide Fe 3 04, FesCvs, FesCb or mixtures thereof preferably Fe 2 0 3 .
  • the zinc is zinc oxide (ZnO), or any other zinc-containing oxide, zinc ferrite, or mixtures thereof.
  • Coupled is defined as connected, although not necessarily directly, and not necessarily mechanically.
  • Embodiment 1 is a solid composition adapted for use as a feed stock in steel making furnaces.
  • the solid composition contains a baghouse dust containing iron oxide and at least 1% zinc by weight; and a carbon source, wherein said solid composition is in the form of a briquette or pellet.
  • Embodiment 2 is the solid composition of embodiment 1, wherein the product does not contain either or both of ferrous chloride and ferrous sulfate amount that alters the properties of the composition as a feed stock in steel making furnaces.
  • Embodiment 3 is the solid composition of embodiments 1 or 2, wherein the carbon source contains greater than 50% carbon by weight.
  • Embodiment 4 is the solid composition of either of embodiments 1 to 3, wherein the carbon source is selected front the group consisting of anthracite, graphite, coal, coke, petcoke, coal tar pitch, tar, tar, molasses, decanter sludge, and combinations thereof.
  • Embodiment 5 is the solid composition of either of embodiments 1 to 4, wherein the iron oxide is iron (II) oxide (FeO), iron (III) oxide (Fe 2 0 3 ), iron (0,01) oxide (Fe 3 C"4, Fes06, FesCb), or mixtures thereof preferably Fe 2 0 3 .
  • Embodiment 6 is the solid composition of either of embodiments 1 to 5, wherein the zinc is zinc oxide (ZnO), or any other zinc containing oxide, zinc ferrite, or mixtures thereof.
  • Embodiment 7 is the solid composition of either of embodiments 1 to 6, further containing from greater than 0% up to 15% by weight of an additive.
  • Embodiment 8 is the solid composition of embodiment 6, wherein the additive is selected from the group consisting of lime, calcium chloride, silica, limestone, clay, iron and/or steel grindings, iron and/or steel borings, iron and/or steel turnings, and combinations thereof.
  • Embodiment 9 is the solid composition of either of embodiment 1 to 8, wherein the baghouse dust contains greater than 30% iron oxide by weight.
  • Embodiment 10 is the solid composition of either of embodiment 1 to 9, wherein the baghouse dost contains 30% to 70% iron oxide by weight.
  • Embodiment 11 is a briquette or pellet adapted for use as a recycled feed stock in electric arc and/or basic oxygen furnaces, the briquette or pellet containing: 60 to 90 % by weight of a bag house dust containing iron oxide and zinc, wherein the iron oxide contains 30 to 70 % by weight of the bag house dust; 3 to 20 % by weight of a carbon source; and 0 to 15% by weight additive.
  • Embodiment 12 is the briquette or pellet of embodiment 11, wherein the product does not contain either or both of ferrous chloride and ferrous sulfate.
  • Embodiment 13 is the briquette or pellet of embodiment 11 or 12, wherein the carbon source contains greater than 50% carbon by weight.
  • Embodiment 14 is the briquette or pellet of either of embodiment 11 to 13 wherein the carbon source is selected from the group consisting of anthracite, graphite, coal, coke, petcoke, coal tar pitch, tar, tar, molasses, decanter sludge, and combinations thereof.
  • Embodiment 15 is the briquette or pellet of either of embodiment 11 to 14, wherein the additive is selected from 'the group consisting of lime, calcium chloride, silica, limestone, clay , iron and/or steel grindings, iron and/or steel borings, iron and/or steel turnings, and combinations thereof.
  • Embodiment 16 is the briquette or pellet of either of embodiment 11 to 15, wherein the iron oxide is iron (II) ox ide (FeO), iron (III) oxide (Fe203), iron ( ⁇ , ⁇ ) oxide (Fe304, Fe506, Fe507), or mixtures thereof preferably Fe203.
  • Embodiment 17 is the briquette or pellet of either, of embodiment 11 to 16, wherein the zinc is zinc oxide (ZnO), or any other zinc-containing oxide, zinc ferrite, or mixtures thereof.
  • FIG. 1 is a graph of exhaust gas composition and furnace temperature during reduction as per Example 1.
  • FIG. 2 shows the XRD pattern of an unreduced briquette according to Example 1.
  • FIG. 3 shows the XRD pattern of a reduced briquette according to Example 1.
  • the present disclosure provides methods and compositions that make use of the steel-making waste by-product, bag house dust.
  • the bag house dust contains valuable materials such as iron and zinc, primarily in the form of oxides. High oxide content in the bag house dust oxide precludes direct use of bag house dust in industrial steel furnaces.
  • the bag house dust is combined with a carbon source and optionally an additive, and molded into briquettes or pellets.
  • the carbon source is believed to act as an in situ reducing agent that assists in transformation of metal oxides to useful metals.
  • the briquettes or pellets may be employed as a source of iron, zinc, and/or carbon in iron, zinc, or steelmaking processes.
  • the bag house dust is mixed with, a carbon source and molded into briquettes or pellets.
  • the carbon source carbon source may be anthracite, graphite, coal, coke, petcoke, coal tar pitch, tar, molasses, decanter sludge, or combinations thereof.
  • the carbon source and bag house dust are combined in a weight ratio ranging from 0.03 : 1 to 0.18: 1, with carbon as the major weight constituent of the carbon source.
  • the briquettes or pellets comprise a 0.06: 1 weight ratio of carbon source to bag house dust.
  • One or more additives may optionally be included in the pellets or briquettes, including lime, calcium chloride, silica, limestone, day, iron and/or steel grindings, iron and/or steel borings, iron and/or steel turnings, and the like.
  • the pellets or briquettes may include an optional binder.
  • the pellets or briquettes may include one or more non-carbonaceous reducing agents. In preferred embodiments, non-carbonaceous reducing agents are excluded from the pellets or briquettes.
  • the pellets or briquettes may be employed in a steelmaking process wherein the bag house dust iron oxide is used as an iron source for the production of steel.
  • the pellets or briquettes may be combined with recycled iron or steel, unrecycled iron, or a metal ore.
  • bag house dust is combined with a carbon source and shaped into briquettes or pellets.
  • the bag house dust, carbon source, optional additive, and optional binder are combined in a mixing apparatus.
  • the carbon source acts as a binder.
  • the binder, if added, will be sufficient to bind together the carbon source and the BHD to be formed into briquettes via the chosen processing technique.
  • the binder will be present in an amount of from 1 to 20% by weight of the mixture of BHD, carbon source and the binder.
  • Preferred binders include hydrocarbon binders such as, e.g., corn starch, cellulose, and the like. Water may be optionally added to the mixture to create a slurry.
  • the relative amounts of bag house dust, carbon source, and optional components may be adjusted in order to improve the adherence of the mixture and/or the strength of the briquette or pellet product.
  • the mixture may he mixed at room temperature, or it may be subjected to heating conditions.
  • the mixture is formed into briquettes or pellets using any molding or shaping method known in the art. Exemplary methods include extrusion and pelletizing.
  • the shaped briquette or pellet may be further coated with additional bag house dust mixture and subsequently molded or shaped.
  • the shaped briquette or pellet may be heated in an oven.
  • the oven may be used to remove water, increase binding, and/or cause at least a portion of the metal oxide content to be reduced.
  • the oven may be provided with a stream of oxygen or an oxygen-containing gas or in inert atmosphere such as Ar and N.
  • the briquettes or pellets may be used immediately or may be aged prior to using. Aging of the briquettes or pellets may be accomplished at ambient temperature or under elevated temperature.
  • the briquettes or pellets may he used in iron or steel-making furnaces.
  • the briquettes or pellets may be used in other processes, for example, the briquettes or pellets may be used in a Midrex and HYL processes or any other reduction technology whereby the iron oxide is reduced in the absence of melting.
  • the briquettes or pellets may be used as an aggregate and added to concrete.
  • the briquettes or pellets may be used to enhance zinc content in zinc distillation or extraction methods.
  • the recycling of bag house dust may provide financially advantageous environmental protection credits for waste reduction and/or recycling of iron and zinc oxides.
  • Baghouse dust (BHD) briquettes containing carbon as a reductant in briquettes containing carbon as a reductant in a 1.6: 1 molar ratio of carbon to Fe 2 Cb The BHD briquettes were prepared by mixing 10 wt% carbon with 90 wt% BHD along with water. The wet mixture was then pressed into briquettes with a roller press cold briquetting machine. The BHD was provided by SABIC, and was obtained from an electric arc furnace.
  • the chemical composition of an exemplary, non-limiting BHD analyzed by X-ray fluorescence spectrometry (XRF) used in accordance with the present invention is provided below in Table 1 :
  • Example 1 The briquettes of Example 1 were subjected to reduction at 1100°C and analyzed. Analysis of the as-received and reduced briquettes was performed by x-ray diffraction (XRD) for phase identification, and x-ray fluorescence (XRF) spectrometry to determine approximate elemental composition.
  • XRD x-ray diffraction
  • XRF x-ray fluorescence
  • XRD patterns were analyzed by using the QualX software package (See A. Altomare, N. Corriero, C. Cuocci, A. Falcicchio, A. Moliterni, and R. Rizzi, "QUALX2.0: a qualitative phase analysis software using the freely available database POW COD," J. Appl. Crystallogr., vol. 48, no. 2, pp. 598-603, Apr. 2015).
  • the search-match database was restricted to elements listed in Table 1, in addition to carbon and oxygen in order to account for oxides and carbides that may have been present. The phases that best accounted for the peaks were selected manually. Results
  • Fig. 1 Data gathered from the infrared gas analyzer is plotted in Fig. 1. It shows a sudden increase in the CO generation rate, which peaks after approximately 10 minutes, then decays. Similar peaks are seen in the concentration of CO2 and H2. The presence of hydrogen gas indicates that the reductant is not pure carbon, but likely a pulverized coal. The long decay time is due to the residence time of the exhaust gasses in the furnace (caused by the low flow rate, 150 mL/minute); note that the rate of decay does not significantly change after the furnace begins to cool after the 1 hour dwell at 1100 °C. Reduction was likely completed shortly after the peak in CO concentration was reached.
  • the data suggests that the rate of reduction is quite fast.
  • the infrared (IR) spectrometer data is particularly useful for determining the total amount of CO, CO2, and H2 produced by integration of the curves.
  • the inside surface of the furnace tube was also coated with a gray powder, which was analyzed by scanning electron microscope (SEM) and Energy Dispersive X-ray Spectroscopy (EDS) and found to zinc-contain primarily zinc.
  • SEM scanning electron microscope
  • EDS Energy Dispersive X-ray Spectroscopy
  • XRD of an unreduced ground briquette shows in Fig. 2 that the main crystalline phases are magnetite (Fe 3 0 4 , phase P. l in Fig. 2), wustite (FeO, phase P.2), lime (CaO, phase P.3), zinc oxide (ZnO, phase P.4), and sodium and potassium oxides (Na 2 0 and K2O, phases P.6 and P.5, respectively).
  • the other constituents shown in the chemical analysis are not visible over the background, either because they are not present in significant enough concentrations or because they are not crystalline enough to generate a strong x-ray signal.
  • XRD on the reduced briquette as shown in Fig.
  • Example 1 having the composition shown in Table 1 above process was premixed with anthracite as a carbon source according to the procedure and ratios described in Example 1 above and shaped into pellets/briquettes using the method of Example 1.
  • Alumina crucible was used to conduct experiment.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Geochemistry & Mineralogy (AREA)
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Abstract

La poussière de dépoussiéreurs à manches est combinée à une source de carbone et façonnée en pastilles ou briquettes et utilisée pour recycler des métaux précieux présents dans la poussière de dépoussiéreurs à manches.
PCT/IB2018/053262 2017-05-10 2018-05-10 Procédé de fabrication de pastilles/briquettes auto-réductrices à partir de poussière de dépoussiéreurs à manches mélangée avec du carbone à utiliser dans des fours de fabrication d'acier WO2018207131A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP18728966.5A EP3635142A1 (fr) 2017-05-10 2018-05-10 Procédé de fabrication de pastilles/briquettes auto-réductrices à partir de poussière de dépoussiéreurs à manches mélangée avec du carbone à utiliser dans des fours de fabrication d'acier
US16/611,579 US20200399723A1 (en) 2017-05-10 2018-05-10 A process for manufacturing self-reducing pellets/briquettes from bag house dust mixed with carbon to be used in steelmaking furnaces
CN201880038094.8A CN110741101A (zh) 2017-05-10 2018-05-10 从用于炼钢炉的混合有碳的集尘灰来制造自还原团粒/块的方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201762504496P 2017-05-10 2017-05-10
US62/504,496 2017-05-10

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WO2018207131A1 true WO2018207131A1 (fr) 2018-11-15

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EP (1) EP3635142A1 (fr)
CN (1) CN110741101A (fr)
WO (1) WO2018207131A1 (fr)

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CN109847751A (zh) * 2019-03-04 2019-06-07 张家港江苏科技大学产业技术研究院 一种利用冶金粉尘定向制备多元磁性铁基复合材料、方法及应用
CN110512087A (zh) * 2019-09-27 2019-11-29 广东金宇环境科技有限公司 一种高温熔炼炉处理炼钢集尘灰的方法
TWI856888B (zh) 2023-11-27 2024-09-21 亞比斯循環科技股份有限公司 金屬粉屑用的架橋母粒及待還原的球狀物料

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