EP0044669B1 - Self-reducing iron oxide agglomerates - Google Patents
Self-reducing iron oxide agglomerates Download PDFInfo
- Publication number
- EP0044669B1 EP0044669B1 EP81303130A EP81303130A EP0044669B1 EP 0044669 B1 EP0044669 B1 EP 0044669B1 EP 81303130 A EP81303130 A EP 81303130A EP 81303130 A EP81303130 A EP 81303130A EP 0044669 B1 EP0044669 B1 EP 0044669B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- mixture
- agglomerates
- finely
- process according
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired
Links
Classifications
-
- 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
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/10—Making spongy iron or liquid steel, by direct processes in hearth-type furnaces
- C21B13/105—Rotary hearth-type furnaces
-
- 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
Definitions
- This invention relates to a process for producing self-reducing agglomerates from finely-divided, iron ore concentrates.
- United States Specification 3,938,987 teaches that, when non-agglomerating coals, such as lignite, sub-bituminous coals, anthracite coal and coke breeze, are used at the carbonaceous material, the amount must be about 40-80% of that required to reduce iron oxide to metallic iron in order to produce pellets having adequate strength for use in a steel making furnace.
- United States Patent Specification 3,386,816 teaches that pellets containing as little as 8% coke have a compressive strength of 26 kg which is generally considered unacceptably low for use in most steel making processes.
- the problem to be solved by the invention is to provide a low cost process for forming finely-divided, iron ore concentrates into hardened agglomerates containing an amount of carbonaceous material at least sufficient to reduce all the iron oxide to metallic iron and yet having high compressive strengths.
- the process of invention includes the steps of preparing a moistened mixture of finely divided iron ore concentrates, a finely-divided, natural or pyrolyzed carbonaceous material having a volatile matter (on dry basis) content of about 20% by weight or less in an amount at least sufficient to reduce all the iron oxide to metallic iron, about 1 to about 30 weight % of a bonding agent selected from a group consisting of oxides, hydroxides and carbonates of calcium and magnesium and mixtures thereof, and 0 to about 3 weight % of a siliceous material (as available Si0 2 ); forming the resulting mixture into discrete green agglomerates; and hydrothermally hardening the green agglomerates by contacting them with steam for a time period sufficient to form them into hardened, integral bonded masses.
- a bonding agent selected from a group consisting of oxides, hydroxides and carbonates of calcium and magnesium and mixtures thereof, and 0 to about 3 weight % of a siliceous material (as
- the process is particularly suitable for producing high strength agglomerates from iron ores, such as haematite and magnetite, preferably in the form of high purity ores or concentrates containing about 45-70% iron and the balance gangue and oxide.
- a starting mixture is first prepared by thoroughly blending together an iron ore concentrate, a carbonaceous material, a bonding agent, a siliceous material and a sufficient amount of water to form a moistened mixture capable of being formed into discrete agglomerated masses or pellets.
- the carbonaceous material can be either naturally occurring or pyrolyzed so long as it has a volatile matter (on dry basis) content of about 20% by weight or less, preferably about 10 weight % or less. Pyrolyzed carbonaceous materials generally are preferred because .of their lower volatile content.
- Representative suitable natural carbonaceous materials include low volatile anthracite coal, graphite and the like.
- pyrolyzed carbonaceous material as used herein means a solid product produced by heating a naturally occurring, high carbonaceous material to elevated temperatures in the absence of oxygen to drive off a substantial portion of the volatile matter, primarily organic matter.
- suitable pyrolyzed carbonaceous materials include chars produced from non-coking bituminous, sub-bituminous and anthracite coals, lignite char, wood char, coke produced from bituminous coal, coke breeze, petroleum and coal tar pitch, and mixtures thereof. Of these, bituminous coal char, lignite char and coke breeze are preferred because of their lower cost.
- Suitable bonding agents include the oxides, hydroxides, and carbonates of calcium and magnesium and mixtures thereof. Burned lime (CaO) and hydrated lime (Ca(OH) 2 ) are preferred because, in addition to functioning as a bonding agent, they can assist in slag formation and sulfur removal when the agglomerates are used in a steel making process.
- Burned lime (CaO) and hydrated lime (Ca(OH) 2 ) are preferred because, in addition to functioning as a bonding agent, they can assist in slag formation and sulfur removal when the agglomerates are used in a steel making process.
- the amount of bonding agents used is about 0.1 to about 30% by weight, based on the total weight of the dry solids in the starting mixture. When less than about 0.1 weight % is used, the hardened pellets do not have sufficient crush resistance or compressive strength to withstand the loads normally imposed thereon during handling, storage and transportation. On the other hand, amounts of the bonding agents in excess of about 30% by weight do not appreciably increase the compressive strengths, can dilute the concentration of iron oxide in the final agglomerates to an undesirable level and can cause formation of excessive amounts of slag during melting.
- the preferred amount of bonding agent is about 2 to about 10% by weight.
- the iron ore concentrate contains an appreciable amount (e.g., about 0.5% by weight or more) of available Si0 2 capable of reacting with the bonding agent to formed silicate or hydrosilicate bonds therewith during the conditions of hydrothermal hardening, hardened pellets having compressive strengths up to about 90 kg can be obtained without adding a siliceous material to the starting mixture.
- an amount of natural or artificial siliceous material containing up to 3% by weight available Si0 2 is added to the starting mixture.
- the total available Si0 2 in the mixture should be at least 0.5% by weight.
- siliceous materials include finely ground quartz, silica sand, bentonite, diatomaceous earth, fuller's earth, sodium, calcium magnesium, and aluminum silicates, pyrogenic silica, various hydrated silicas and mixtures thereof. Of these, finely ground quartz and silica sand are preferred.
- strengthening additives can be included in a starting mixture to further increase the strength of the hardened agglomerates.
- oxides, hydroxides, carbonates, bicarbonates, sulfates, bisulfate, and borates of alkali metals (e.g. potassium and sodium) and mixtures thereof can be added in amounts ranging to about 3% by weight.
- alkali metals e.g. potassium and sodium
- sodium hydroxide, sodium carbonate, and sodium bicarbonate are preferred.
- quaternary ammonium hydroxides, quaternary ammonium chlorides or quaternary amines or mixtures thereof may be used as strengthening additives.
- the presence of some of these strengthening additives might be considered undesirable when the hardened agglomerates are used as a charge for blast furnaces. In those cases, such additives can be omitted without significantly reducing the strength of the agglomerates.
- the preferred amount of the strengthening additives is about 0.15 to about 1% by weight.
- the amount of water included in the starting mixture varies, depending on the physical properties of the materials and the particular agglomeration technique employed. For example, when a pelletizing process employing a balling drum or disc is used to form spherical pellets, the total amount of water in the moistened starting mixture generally should be about 5 to about 20% by weight, preferably about 10 to about 15% by weight. On the other hand, when a briquetting press is used, the amount of water in the moistened starting moisture generally should be about 3 to about 15% by weight, preferably from about 5 to about 10% by weight.
- the average particle size of the various solid materials included in the starting mixture generally can range from about 10 to about 325 mesh with all preferably being less than about 200 mesh. Particle sizes coarser than about 100 mesh make it difficult to obtain a homogeneous mixture of the constituents and, in some cases, produce insufficient surface area to obtain the requisite high strength bond in the hardened agglomerates. Also, it is difficult to form pellets from mixtures containing coarser particles. Preferably, at least half of all solid materials in the starting mixture have an average particle size less than about 200 mesh for pelletizing. Briquettes can be produced with coarser particles.
- the time and conditions for this holding or standing step can vary considerably depending primarily on the particular type of carbonaceous material and bonding agent being used. Removal of excess internal moisture from the pores or cavities in the carbonaceous material can be accelerated by heating the moistened mixture to an elevated temperature. When burned lime and/or magnesium oxide is used as the bonding agent, they react with the moisture present to form hydrates. This exothermic hydration reaction tends to accelerate migration of the free internal moisture to the particle surface, resulting in a shortening of the standing time required without external heating.
- the moistened mixture prior to agglomeration, is allowed to stand for about 0.5 to about 48 hours, preferably about 2 to about 3 hours, at a temperature of about 60 to about 90°C. Higher temperatures and pressures can be used, but are less desirable because of the higher operational costs.
- burned lime or magnesium oxide is used as the bonding agent, the moistened mixture preferably is placed in a closed, thermally insulated container to take advantage of the exothermic hydration reaction.
- the moistened mixture is next formed into green agglomerates of the desired size and shape for the intended end use by a conventional agglomeration technique, such as molding, briquetting, pelletizing, extruding and the like.
- a conventional agglomeration technique such as molding, briquetting, pelletizing, extruding and the like.
- Pelletizing with a balling disc or drum is preferred because of the lower operating costs.
- the green agglomerates When in the form of spherical pellets, the green agglomerates generally have a diameter of about 5 to about 25 mm, preferably about 10 to about 20 mm. When briquetting is used, the agglomerates preferably are in a spherical-like or egg shape and have a major diameter ranging up to about 75 mm. Larger pellets and briquettes can be used if desired.
- the crush resistance or compressive strength of the hardened agglomerates can be increased by drying the green agglomerates to a free moisture content of about 5% by weight or less, preferably about 3% by weight or less, prior to the hydrothermal hardening step.
- This drying can be accomplished by conventional means, such as by placing the green agglomerates in an oven or by blowing a heated gas thereover, using drying temperatures up to the decomposition temperature of the carbonaceous material.
- the time required to reduce the free moisture content to about 5% by weight or less depends upon the drying temperatures used, the moisture content of the green agglomerates, flow rate of the drying gas, the level to which the moisture content is reduced, size and shape of the green agglomerates, etc.
- the green agglomerates are introduced into a reaction chamber or pressure vessel, such as an autoclave, wherein they are heated to an elevated temperature in the presence of moisture to effect a hardening and bonding of the individual particle into an integral, high strength mass.
- a reaction chamber or pressure vessel such as an autoclave
- the compressive strength of the hardened agglomerates produced by this hydrothermal hardening step depends to some extent upon the temperature, time, and moisture content of the atmosphere use.
- the application of heat to the green agglomerates can be achieved by any one of a number of methods.
- the use of steam is preferred because it simultaneously provides a source of heat and moisture necessary for the hydrothermal reaction.
- Either saturated steam or substantially saturated steam can be used.
- Superheated steam tends to produce hardened agglomerates having reduced strengths. Therefore, steam at temperatures and pressures at or close to that of saturated steam is preferred.
- Temperatures generally ranging from about 100 to about 250°C, preferably 200 to about 225°C, can be satisfactorily employed to achieve the desired hardening of the green agglomerates within a reasonable time period.
- Autoclaving pressures substantially above atmospheric pressure are preferred in order to decrease the hardening time and to improve the strength of the hardened agglomerates.
- the retention time of the pellets in the reaction chamber or pressure vessel depends upon several process variables, such as pressure, temperature, and atmosphere of the chamber, size and composition of the pellets, etc. In any case, this time should be sufficient for the bonding agent to form silicate and/or hydrosilicate bonds in the available Si0 2 and bond the individual particles into a hardened, high strength condition.
- the time for the hydrothermal hardening generally is about 5 minutes to about 15 hours, preferably about 30 to about 60 minutes.
- the hardened agglomerates are removed from the reacting chamber and, upon cooling, are ready for use.
- the hot, hardened agglomerates usually contain up to about 1.5% free moisture and have compressive strength characteristics suitable for most uses.
- the compressive strength of the hardened agglomerates can be increased by rapidly drying them, preferably immediately after removal from the reaction chamber and before appreciable cooling has occurred, to remove substantially all of the free moisture therefrom. This drying can be accomplished in a convenient manner.
- the minimum compressive strength of hardened agglomerates produced by the process of the invention varies depending on the size of the agglomerate.
- spherical pellets with a diameter of 12-15 mm have a compressive strength of at least 45 kg and those with a diameter of about 30 mm have a compressive strength in the neighbourhood of about 90 kg or more.
- pellets containing a carbonaceous material having a low volatile matter content or which was pyrolyzed (bituminous coal char, lignite char and coke)
- bituminous coal char, lignite char and coke had compressive strengths in excess of 45 kg.
- those containing a carbonaceous material having a high volatile matter content had substantially lower compressive strengths.
- the use of chars from non-coking bituminous coal, lignite and other low grade carbonaceous materials is particularly advantageous because of the low cost of these materials and the volatiles driven off during the pyrolyzing process can be burned and used as a heat source.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Mechanical Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Manufacture Of Iron (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US17064380A | 1980-07-21 | 1980-07-21 | |
US170643 | 1980-07-21 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0044669A1 EP0044669A1 (en) | 1982-01-27 |
EP0044669B1 true EP0044669B1 (en) | 1988-04-06 |
Family
ID=22620722
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP81303130A Expired EP0044669B1 (en) | 1980-07-21 | 1981-07-09 | Self-reducing iron oxide agglomerates |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP0044669B1 (ru) |
JP (1) | JPS5773136A (ru) |
AU (1) | AU543924B2 (ru) |
BR (1) | BR8104694A (ru) |
CA (1) | CA1158442A (ru) |
DE (1) | DE3176704D1 (ru) |
ES (1) | ES504099A0 (ru) |
IN (1) | IN157793B (ru) |
MX (1) | MX156802A (ru) |
ZA (1) | ZA814465B (ru) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6047330B2 (ja) * | 1982-02-02 | 1985-10-21 | 日本鋼管株式会社 | 非焼成塊成鉱の製造方法および装置 |
US5045112A (en) * | 1988-02-08 | 1991-09-03 | Northern States Power Company | Cogeneration process for production of energy and iron materials, including steel |
US5066325A (en) * | 1987-08-31 | 1991-11-19 | Northern States Power Company | Cogeneration process for production of energy and iron materials, including steel |
US5055131A (en) * | 1987-08-31 | 1991-10-08 | Northern States Power Company | Cogeneration process for production of energy and iron materials |
US5064174A (en) * | 1989-10-16 | 1991-11-12 | Northern States Power Company | Apparatus for production of energy and iron materials, including steel |
WO1997016573A1 (en) * | 1995-11-01 | 1997-05-09 | Westralian Sands Limited | Agglomeration of iron oxide waste materials |
IT1304374B1 (it) * | 1998-05-27 | 2001-03-15 | Gloster Nv | Metodo per il riciclaggio delle polveri derivanti dai processi dilavorazione dell'acciaio o simili mediante la fabbricazione di |
TW562860B (en) * | 2000-04-10 | 2003-11-21 | Kobe Steel Ltd | Method for producing reduced iron |
CN101151380B (zh) | 2004-12-07 | 2012-12-05 | 纽-铁科技有限责任公司 | 用于生产金属铁矿块的方法和系统 |
JP5825180B2 (ja) * | 2012-04-03 | 2015-12-02 | 新日鐵住金株式会社 | 石炭チャーを使用した高炉用非焼成含炭塊成鉱の製造方法 |
CN105907954A (zh) * | 2016-06-06 | 2016-08-31 | 江苏省冶金设计院有限公司 | 复合粘结剂及其在矿粉成型中的应用 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2806779A (en) * | 1953-09-29 | 1957-09-17 | Mcwane Cast Iron Pipe Co | Method of producing iron |
US2793109A (en) * | 1954-04-09 | 1957-05-21 | Surface Combustion Corp | Induration process for powdered iron oxide containing material |
DE1243880B (de) * | 1958-07-18 | 1967-07-06 | Blocked Iron Corp | Verfahren zur Herstellung eines Stueckerzproduktes |
US3264092A (en) * | 1963-06-20 | 1966-08-02 | Mcdowell Wellman Eng Co | System for producing carbonized and metallized iron ore pellets |
DE1583942C3 (de) * | 1968-01-31 | 1975-02-06 | Blocked Iron Corp., Albany, N.Y. (V.St.A.) | Verfahren zur Herstellung eines stückigen Erzes |
US3895088A (en) * | 1971-01-14 | 1975-07-15 | Control Michigan Technological | Method for agglomerating steel plant waste dusts |
US3770416A (en) * | 1972-04-17 | 1973-11-06 | Univ Michigan Tech | Treatment of zinc rich steel mill dusts for reuse in steel making processes |
DE2517543C2 (de) * | 1975-04-21 | 1985-12-12 | Board Of Control Of Michigan Technological University, Houghton, Mich. | Verfahren zum Herstellen von gehärteten Agglomeraten aus Hüttenstäuben |
-
1981
- 1981-06-29 CA CA000380807A patent/CA1158442A/en not_active Expired
- 1981-07-01 ZA ZA814465A patent/ZA814465B/xx unknown
- 1981-07-09 DE DE8181303130T patent/DE3176704D1/de not_active Expired
- 1981-07-09 AU AU72726/81A patent/AU543924B2/en not_active Ceased
- 1981-07-09 EP EP81303130A patent/EP0044669B1/en not_active Expired
- 1981-07-20 MX MX188374A patent/MX156802A/es unknown
- 1981-07-20 JP JP56113442A patent/JPS5773136A/ja active Granted
- 1981-07-20 ES ES504099A patent/ES504099A0/es active Granted
- 1981-07-21 BR BR8104694A patent/BR8104694A/pt unknown
-
1982
- 1982-05-06 IN IN517/CAL/82A patent/IN157793B/en unknown
Also Published As
Publication number | Publication date |
---|---|
JPS5773136A (en) | 1982-05-07 |
BR8104694A (pt) | 1982-04-06 |
JPH0123531B2 (ru) | 1989-05-02 |
ES8205434A1 (es) | 1982-06-01 |
MX156802A (es) | 1988-10-05 |
DE3176704D1 (en) | 1988-05-11 |
AU7272681A (en) | 1982-01-28 |
EP0044669A1 (en) | 1982-01-27 |
IN157793B (ru) | 1986-06-21 |
ES504099A0 (es) | 1982-06-01 |
AU543924B2 (en) | 1985-05-09 |
CA1158442A (en) | 1983-12-13 |
ZA814465B (en) | 1982-07-28 |
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