WO2022164990A1 - Composition for briquetting and/or pelletization of iron ore fines and residues, iron-ore composite and method of preparing the iron-ore composite - Google Patents
Composition for briquetting and/or pelletization of iron ore fines and residues, iron-ore composite and method of preparing the iron-ore composite Download PDFInfo
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- WO2022164990A1 WO2022164990A1 PCT/US2022/014039 US2022014039W WO2022164990A1 WO 2022164990 A1 WO2022164990 A1 WO 2022164990A1 US 2022014039 W US2022014039 W US 2022014039W WO 2022164990 A1 WO2022164990 A1 WO 2022164990A1
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- Prior art keywords
- composite
- polymer
- iron
- monomer
- iron ore
- Prior art date
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000002131 composite material Substances 0.000 title claims abstract description 76
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 32
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000000203 mixture Substances 0.000 title description 11
- 238000005453 pelletization Methods 0.000 title description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 48
- 239000000178 monomer Substances 0.000 claims abstract description 37
- 239000002245 particle Substances 0.000 claims abstract description 24
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 238000005054 agglomeration Methods 0.000 claims abstract description 11
- 230000002776 aggregation Effects 0.000 claims abstract description 11
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000003926 acrylamides Chemical class 0.000 claims abstract description 7
- 125000000129 anionic group Chemical group 0.000 claims abstract description 6
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- -1 ethoxyl units Chemical group 0.000 claims description 36
- 239000008188 pellet Substances 0.000 claims description 36
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 235000013379 molasses Nutrition 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 229920002472 Starch Polymers 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 235000019698 starch Nutrition 0.000 claims description 8
- 239000008107 starch Substances 0.000 claims description 8
- 239000004484 Briquette Substances 0.000 claims description 7
- 229920000881 Modified starch Polymers 0.000 claims description 7
- 235000019426 modified starch Nutrition 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 235000012216 bentonite Nutrition 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000005367 electrostatic precipitation Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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
- C22B1/2406—Binding; Briquetting ; Granulating pelletizing
-
- 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
Definitions
- the disclosed technology generally provides for an iron-ore composite and method of preparing said iron-ore composite with a water-soluble polymer for agglomeration of iron ore fines and residues in the briquetting and/or pelletization process.
- the disclosed technology generally provides for an iron-ore composite and method of preparing an iron-ore based composite.
- an iron-ore based composite is provided.
- the composite according to the invention may further include one or more of the following features taken in isolation or according to any possible technical combinations.
- the composite comprises:
- iron ore particles comprising iron ore fines and/or iron ore residues
- R 1 and R 2 independently represent a hydrogen atom or a CH3 group; wherein m and n independently represent a number between 0 and 250, the sum of m and n is equal to or greater than 10 and n is greater than m; and wherein [(EO) n -(PO) m ] represents a poly- alkoxyl chain comprising ethoxyl units EO, propoxyl units PO or combinations thereof that are distributed in blocks, alternately or randomly. In all the embodiments, it must be understood that the term “between” includes the limits of the range (for numbers n and m).
- the composite comprises a moisture content of less than about 15% wt. relative to the total weight of the composite.
- the composite is in the form of a pellet or in the form of a briquette.
- the composite does not comprise molasses, starch, and/or starch derivatives.
- the polymer has a M w molecular weight from about 10,000 to 1,000,000 g/mol, preferably from about 15,000 to 500,000 g/mol, or from about 20,000 to 200,000 g/mol.
- the polymer is not neutralized. In an alternative embodiment, the polymer is totally or partially neutralized.
- the totally or partially neutralized polymer is neutralized by NaOH, KOH, ammonium derivatives, ammonia, amino-alkali substances, and/or combinations thereof.
- the amino-alkali substances comprise triethanolamine or 2-amino-2-methyl-propanol (AMP).
- the monomer (b) is selected from:
- R 1 represents a hydrogen atom
- R 2 represents a hy- drogen atom
- m and n independently represent a number between 1 and 250, and the sum of m and n is equal to or greater than 10 and n is greater than m
- represents a polyalkoxyl chain comprising ethoxyl units EO, propoxyl units PO or combinations thereof that are distributed in blocks, alternately or randomly; or
- R 1 represents a CEE group
- R 2 represents a hydrogen atom
- m and n independently represent a number between 1 and 250, and the sum of m and n is equal to or greater than 10 and n is greater than m
- [(EO) n - (PO)TM] represents a polyalkoxyl chain comprising ethoxyl units EO, propoxyl units PO or combinations thereof that are distributed in blocks, alternately or randomly.
- the method according to the invention may further include one or more of the following features taken in isolation or according to any possible technical combinations.
- the method comprises:
- said iron ore particles comprising iron ore fines and/or iron ore residues; said polymer being prepared in the absence of acrylamide and of acrylamide derivative; said polymer being prepared by polymerizing at least one anionic monomer (a) selected from acrylic acid, a salt of acrylic acid, methacrylic acid, a salt of methacrylic acid, and/or combinations thereof; and at least one monomer (b) of formula I:
- R 1 and R 2 independently represent a hydrogen atom or a CEE group; wherein m and n independently represent a number between 0 and 250, the sum of m and n is equal to or greater than 10 and n is greater than m; and wherein [(EO) n -(PO)TM] represents a polyalkoxyl chain comprising ethoxyl units EO, propoxyl units PO or combinations thereof that are distributed in blocks, alternately or randomly.
- contacting the plurality of iron ore particles with the polymer does not increase the amount of phosphorus present in the composite. In some embodiments, contacting the plurality of iron ore particles with the polymer does not increase the amount of silicon present in the composite. [0023] In some embodiments, forming a composite comprises feeding the agglomeration into a mixer and press to form a plurality of briquettes and/or pellets.
- forming a composite is carried out in the absence of molasses, starch, and/or starch derivatives.
- the composite comprises a moisture content of less than about 15% wt. relative to the total weight of the composite.
- the polymer has a M w molecular weight from about 10,000 to 1,000,000 g/mol, preferably from about 15,000 to 500,000 g/mol, or from about 20,000 to 200,000 g/mol.
- the polymer is not neutralized. In an alternative embodiment, the polymer is totally or partially neutralized.
- the totally or partially neutralized polymer is neutralized by NaOH, KOH, ammonium derivatives, ammonia, amino-alkali substances, and/or combinations thereof.
- the amino-alkali substances comprise triethanolamine or 2-amino-2-methyl-propanol (AMP).
- the monomer (b) is selected from:
- R 1 represents a hydrogen atom
- R 2 represents a hydrogen atom
- m and n independently represent a number between 1 and 250, and the sum of m and n is equal to or greater than 10 and n is greater than m
- represents a polyalkoxyl chain comprising ethoxyl units EO, propoxyl units PO or combinations thereof that are distributed in blocks, alternately or randomly; or
- R 1 represents a CH3 group
- R 2 represents a hydrogen atom
- m and n independently represent a number between 1 and 250, and the sum of m and n is equal to or greater than 10 and n is greater than m
- represents a polyalkoxyl chain comprising ethoxyl units EO, propoxyl units PO or combinations thereof that are distributed in blocks, alternately or randomly.
- Fig.1 is a general schematic process diagram of a typical briquetting process in which the disclosed polymer composition may be utilized.
- the disclosed technology generally provides for an iron-ore composite and method of preparing a composite, and more specifically, an iron-ore composite and method of preparing a composite with a water-soluble polymer for agglomeration of iron ore fines and residues in the briquetting and/or pelletization process, where the resulting briquettes and/or pellets can be used as feed to the blast furnace.
- an iron-ore based composite comprises a plurality of iron ore particles and at least one water-soluble polymer.
- the polymer composition and method as disclosed herein less moisture is present in the composite briquettes and/or pellets that are produced, resulting in less moisture being present in the blast furnace during production, and thus less energy is required. Since the energy requirement is reduced, the amount of carbon dioxide emissions is ultimately reduced as well. Further, by replacing the conventional binding materials with the disclosed water-soluble polymer composition, the quality of the briquettes/pellets are significantly improved.
- the iron ore particles comprise iron ore fines and/or iron ore residues. It should be understood that the iron ore fines and/or residues as described herein can be obtained from a variety of different sources.
- the iron ore particles can be recovered from, for example, but not limited to, mini-mills (e.g. steel dust with electrostatic precipitation in electric arc furnace), integrated plants from raw material management (storage/transfer/grinding/sizing), from blast furnace (hydrocyclones) and from converters (coarse, dust).
- the water-soluble polymer is prepared in the absence of acrylamide and of acrylamide derivative, said polymer being therefore free of acrylamide and of acrylamide derivative.
- the water-soluble polymer as disclosed herein is obtained by polymerizing:
- anionic monomer (a) selected from acrylic acid, a salt of acrylic acid, methacrylic acid, a salt of methacrylic acid, and/or combinations thereof, and
- R 1 and R 2 independently represent a hydrogen atom or a CH3 group; wherein m and n independently represent a number between 0 and 250, the sum of m and n is equal to or greater than 10 and n is greater than m; and wherein [(EO) n -(PO) m ] represents a poly- alkoxyl chain comprising ethoxyl units EO, propoxyl units PO or combinations thereof that are distributed in blocks, alternately or randomly.
- the polymer has a M w molecular weight from about 10,000 to 1,000,000 g/mol. In other embodiments, the polymer has a M w molecular weight from about 15,000 to 500,000 g/mol, and in other embodiments, from about 20,000 to 200,000 g/mol.
- the polymer is not neutralized. In an alternative embodiment, the polymer is totally or partially neutralized.
- the polymer is neutralized by NaOH, KOH, ammonium derivatives, ammonia, amino-alkali substances, and/or combinations thereof.
- the amino-alkali substances comprise triethanolamine or 2-amino-2-methyl-propanol (AMP).
- the monomer (b) of the disclosed polymer is:
- the monomer (b) of the disclosed polymer is:
- the monomer (b) of the disclosed polymer is:
- R 1 represents a hydrogen atom
- R 2 represents a hydrogen atom
- m and n independently represent a number between 1 and 250, and the sum of m and n is equal to or greater than 10 and n is greater than m
- represents a polyalkoxyl chain comprising ethoxyl units EO, propoxyl units PO or combinations thereof that are distributed in blocks, alternately or randomly.
- the monomer (b) of the disclosed polymer is:
- R 1 represents a CH3 group
- R 2 represents a hydrogen atom
- m and n independently represent a number between 1 and 250, and the sum of m and n is equal to or greater than 10 and n is greater than m
- [(EO) n - (PO) m ] represents a polyalkoxyl chain comprising ethoxyl units EO, propoxyl units PO or combinations thereof that are distributed in blocks, alternately or randomly.
- the iron-ore based composite is in the form of a pellet or in the form of a briquette.
- the composite does not comprise molasses, starch, and/or starch derivatives. Because the iron-ore composite of the disclosed technology does not include molasses, starch, and/or starch derivatives, undesired elements, such as, for example, phosphorus and silicon, are not introduced into the briquette or pellet, thus improving the quality of the briquettes and/or pellets obtained.
- the iron-ore based composite comprises a moisture content of less than about 15% wt. relative to the total weight of the composite. In some embodiments, the moisture content is less than about 12% wt. relative to the total weight of the composite, and in other embodiments, the moisture content is less than about 10% wt. relative to the total weight of the composite.
- a method of preparing an iron-ore based composite comprises:
- the iron ore particles comprise iron ore fines and/or iron ore residues.
- the polymer is prepared in the absence of acrylamide and of acrylamide derivative.
- the polymer is prepared by polymerizing at least one anionic monomer (a) selected from acrylic acid, a salt of acrylic acid, methacrylic acid, a salt of methacrylic acid, and/or combinations thereof; and at least one monomer (b) of formula I:
- R 1 and R 2 independently represent a hydrogen atom or a CEE group; wherein m and n independently represent a number between 0 and 250, the sum of m and n is equal to or greater than 10 and n is greater than m; and wherein [(EO) n -(PO) m ] represents a polyalkoxyl chain comprising ethoxyl units EO, propoxyl units PO or combinations thereof that are distributed in blocks, alternately or randomly.
- the method first provides for contacting a plurality of iron ore particles with at least one water-soluble polymer to form an agglomeration.
- the polymer may be applied to the iron ore particles by intimate mixing. Upon contact of the polymer and the iron particles, an agglomeration of these particles is facilitated.
- forming a composite is carried out in the absence of molasses, starch, and/or starch derivatives. Since formation of the composite does not include these substances, undesired elements, such as, for example, phosphorus and silicon, are not introduced into the briquette or pellet. It should be understood that any recovered iron ore composites may include trace amounts of phosphorus and/or silicon based on the source of the iron ore residues or recovered fines. However, the disclosed method does not increase the amount of phosphorus and/or silicon that is ultimately present in the final composite.
- contacting the plurality of iron ore particles with the polymer does not increase the amount of phosphorus present in the composite that is formed. In some embodiments, contacting the plurality of iron ore particles with the polymer does not increase the amount of silicon present in the composite that is formed.
- forming a composite comprises feeding the agglomeration into a mixer and press to form a plurality of briquettes and/or pellets.
- the composite as described herein comprises a moisture content of less than about 15% wt. relative to the total weight of the composite. In other embodiments, the composite comprises a moisture content of less than about 12% wt. relative to the total weight of the composite, and in other embodiments, the moisture content is less than about 10% wt. relative to the total weight of the composite.
- the disclosed polymer Pl was prepared according to the invention .
- monomer b compound of formula I wherein R 1 represents a CH3 group, R 2 represents a hydrogen atom, m represents 16, n represents 48 and [(EO) n - (PO) rule,
- compositions of reagents in two different beakers were prepared: in the first beaker, 1.69g of ammonium persulfate solubilized in 7.5g of water; and in the second beaker, 2.033g of DMDO (l,8-dimercapto-3,6-di oxaoctane).
- the reactor was heated to 64°C, and under stirring the reagents, firstly DMDO and secondly ammonium persulfate solution were introduced.
- the reactor was maintained under stirring for lh30min in a temperature range from 65°C to 69°C.
- Polymer Pl had a molecular weight of 130,000 g/mol (measured by SEC) and a polymolecularity (Ip) of 1.8.
- Iron ore pellets according to the disclosed technology were then prepared while using polymer Pl.
- Comparative iron ore pellets were also prepared with comparative binders.
- the various materials were thoroughly mixed with a planetary blender starting by introduction of the iron ore followed by water (added to obtain a constant humidity value of 12 wt% to 14 wt%) and the other ingredients. The components were blended for approximately 30 minutes.
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Abstract
An iron-ore based composite and method of preparing the composite by: - contacting a plurality of iron ore particles with at least one water-soluble polymer to form an agglomeration; and - forming a composite said iron ore particles comprising iron ore fines and/or iron ore residues; said polymer being prepared in the absence of acrylamide and of acrylamide derivative; said polymer being prepared by polymerizing at least one anionic monomer (a) selected from acrylic acid, a salt of acrylic acid, methacrylic acid, a salt of methacrylic acid, and/or combinations thereof; and at least one monomer (b) of formula I being: H2C=C(–R1)–C(=O)–O–[(EO) n –(PO) m ]–R2.
Description
Composition for Briquetting and/or Pelletization of Iron Ore Fines and Residues, Iron-ore Composite and Method of Preparing the Iron-ore Composite
[0001] Field of the invention
[0002] The disclosed technology generally provides for an iron-ore composite and method of preparing said iron-ore composite with a water-soluble polymer for agglomeration of iron ore fines and residues in the briquetting and/or pelletization process.
[0003] Background of the invention
[0004] Common briquetting and/or pelletizing processes require the use of mixed binders, such as lime, molasses, or bentonite. In turn, undesired elements, such as phosphorus, silicon, acid gangue, and/or additional slag are introduced into the briquette or pellet. Due to the current binding materials available in the pelletization and briquetting processes, these undesired elements that are introduced reduce the quality and the market value of the briquettes and pellets that are ultimately produced.
[0005] Thus, what is needed in the art is a composition and method for the briquetting and/or pelletization process which avoids the introduction of these undesired elements to improve briquette and/or pellet quality.
[0006] Summary of the invention
[0007] The disclosed technology generally provides for an iron-ore composite and method of preparing an iron-ore based composite.
[0008] In one aspect of the disclosed technology, an iron-ore based composite is provided.
[0009] The composite according to the invention may further include one or more of the following features taken in isolation or according to any possible technical combinations.
[0010] In some embodiments, the composite comprises:
- a plurality of iron ore particles, the iron ore particles comprising iron ore fines and/or iron ore residues; and
- at least one water-soluble polymer, said polymer being free of acrylamide and of acrylamide derivative, wherein said polymer is obtained by polymerizing:
- at least one anionic monomer (a) selected from acrylic acid, a salt of acrylic acid, methacrylic acid, a salt of methacrylic acid, and/or combinations thereof; and
- at least one monomer (b) of formula I:
I
wherein R1 and R2 independently represent a hydrogen atom or a CH3 group; wherein m and n independently represent a number between 0 and 250, the sum of m and n is equal to or greater than 10 and n is greater than m; and wherein [(EO)n-(PO)m] represents a poly- alkoxyl chain comprising ethoxyl units EO, propoxyl units PO or combinations thereof that are distributed in blocks, alternately or randomly. In all the embodiments, it must be understood that the term “between” includes the limits of the range (for numbers n and m).
[0011] In some embodiments, the composite comprises a moisture content of less than about 15% wt. relative to the total weight of the composite.
[0012] In some embodiments, the composite is in the form of a pellet or in the form of a briquette.
[0013] In some embodiments, the composite does not comprise molasses, starch, and/or starch derivatives.
[0014] In some embodiments, the polymer has a Mw molecular weight from about 10,000 to 1,000,000 g/mol, preferably from about 15,000 to 500,000 g/mol, or from about 20,000 to 200,000 g/mol.
[0015] In some embodiments, the polymer is not neutralized. In an alternative embodiment, the polymer is totally or partially neutralized.
[0016] In some embodiments, the totally or partially neutralized polymer is neutralized by NaOH, KOH, ammonium derivatives, ammonia, amino-alkali substances, and/or combinations thereof. In particular embodiments, the amino-alkali substances comprise triethanolamine or 2-amino-2-methyl-propanol (AMP).
[0017] In some embodiments, the monomer (b) is selected from:
- monomer (bl) of formula I, wherein R1 represents a hydrogen atom, R2 represents a CH3 group, m represents 0, n represents a number between 10 and 250, and [(EO)n] represents a polyalkoxyl chain comprising ethoxyl units EO;
- monomer (b2) of formula I, wherein R1 represents a CH3 group, R2 represents a CH3 group, m represents 0, n represents a number between 10 and 250, and [(EO)n] represents a polyalkoxyl chain comprising ethoxyl units EO;
- monomer (b3) of formula I, wherein R1 represents a hydrogen atom, R2 represents a hy-
drogen atom, m and n independently represent a number between 1 and 250, and the sum of m and n is equal to or greater than 10 and n is greater than m, and [(EO)n - (PO)„,| represents a polyalkoxyl chain comprising ethoxyl units EO, propoxyl units PO or combinations thereof that are distributed in blocks, alternately or randomly; or
- monomer (b4) of formula I, wherein R1 represents a CEE group, R2 represents a hydrogen atom, m and n independently represent a number between 1 and 250, and the sum of m and n is equal to or greater than 10 and n is greater than m, and [(EO)n- (PO)™] represents a polyalkoxyl chain comprising ethoxyl units EO, propoxyl units PO or combinations thereof that are distributed in blocks, alternately or randomly.
[0018] In yet another aspect of the disclosed technology, a method of preparing an iron-ore based composite is provided.
[0019] The method according to the invention may further include one or more of the following features taken in isolation or according to any possible technical combinations.
[0020] In some embodiments, the method comprises:
- contacting a plurality of iron ore particles, with at least one water-soluble polymer to form an agglomeration, and
- forming a composite; said iron ore particles comprising iron ore fines and/or iron ore residues; said polymer being prepared in the absence of acrylamide and of acrylamide derivative; said polymer being prepared by polymerizing at least one anionic monomer (a) selected from acrylic acid, a salt of acrylic acid, methacrylic acid, a salt of methacrylic acid, and/or combinations thereof; and at least one monomer (b) of formula I:
I
[0021] wherein R1 and R2 independently represent a hydrogen atom or a CEE group; wherein m and n independently represent a number between 0 and 250, the sum of m and n is equal to or greater than 10 and n is greater than m; and wherein [(EO)n-(PO)™] represents a polyalkoxyl chain comprising ethoxyl units EO, propoxyl units PO or combinations thereof that are distributed in blocks, alternately or randomly.
[0022] In some embodiments, contacting the plurality of iron ore particles with the polymer does not increase the amount of phosphorus present in the composite. In some embodiments, contacting the plurality of iron ore particles with the polymer does not increase the amount of silicon present in the composite.
[0023] In some embodiments, forming a composite comprises feeding the agglomeration into a mixer and press to form a plurality of briquettes and/or pellets.
[0024] In some embodiments, forming a composite is carried out in the absence of molasses, starch, and/or starch derivatives.
[0025] In some embodiments, the composite comprises a moisture content of less than about 15% wt. relative to the total weight of the composite.
[0026] In some embodiments, the polymer has a Mw molecular weight from about 10,000 to 1,000,000 g/mol, preferably from about 15,000 to 500,000 g/mol, or from about 20,000 to 200,000 g/mol.
[0027] In some embodiments, the polymer is not neutralized. In an alternative embodiment, the polymer is totally or partially neutralized.
[0028] In some embodiments, the totally or partially neutralized polymer is neutralized by NaOH, KOH, ammonium derivatives, ammonia, amino-alkali substances, and/or combinations thereof. In particular embodiments, the amino-alkali substances comprise triethanolamine or 2-amino-2-methyl-propanol (AMP).
[0029] In some embodiments, the monomer (b) is selected from:
- monomer (bl) of formula I, wherein R1 represents a hydrogen atom, R2 represents a CH3 group, m represents 0, n represents a number between 10 and 250, and [(EO)n] represents a polyalkoxyl chain comprising ethoxyl units EO;
- monomer (b2) of formula I, wherein R1 represents a CH3 group, R2 represents a CH3 group, m represents 0, n represents a number between 10 and 250, and [(EO)n] represents a polyalkoxyl chain comprising ethoxyl units EO;
- monomer (b3) of formula I, wherein R1 represents a hydrogen atom, R2 represents a hydrogen atom, m and n independently represent a number between 1 and 250, and the sum of m and n is equal to or greater than 10 and n is greater than m, and [(EO)n - (PO),„| represents a polyalkoxyl chain comprising ethoxyl units EO, propoxyl units PO or combinations thereof that are distributed in blocks, alternately or randomly; or
- monomer (b4) of formula I, wherein R1 represents a CH3 group, R2 represents a hydrogen atom, m and n independently represent a number between 1 and 250, and the sum of m and n is equal to or greater than 10 and n is greater than m, and [(EO)n - (PO)„,| represents a polyalkoxyl chain comprising ethoxyl units EO, propoxyl units PO or combinations thereof that are distributed in blocks, alternately or randomly.
[0030] Brief description of the drawings
[0031] Other features, details and advantages of the invention will become apparent on reading the detailed description. The accompanying figure is given as a non-limiting example.
[0032] Fig.1 is a general schematic process diagram of a typical briquetting process in which the disclosed polymer composition may be utilized.
[0033] Detailed description of exemplary embodiments
[0034] The disclosed technology generally provides for an iron-ore composite and method of preparing a composite, and more specifically, an iron-ore composite and method of preparing a composite with a water-soluble polymer for agglomeration of iron ore fines and residues in the briquetting and/or pelletization process, where the resulting briquettes and/or pellets can be used as feed to the blast furnace.
[0035] In one aspect of the disclosed technology, an iron-ore based composite is provided. The composite comprises a plurality of iron ore particles and at least one water-soluble polymer. With the use of the polymer composition and method as disclosed herein, less moisture is present in the composite briquettes and/or pellets that are produced, resulting in less moisture being present in the blast furnace during production, and thus less energy is required. Since the energy requirement is reduced, the amount of carbon dioxide emissions is ultimately reduced as well. Further, by replacing the conventional binding materials with the disclosed water-soluble polymer composition, the quality of the briquettes/pellets are significantly improved.
[0036] The iron ore particles comprise iron ore fines and/or iron ore residues. It should be understood that the iron ore fines and/or residues as described herein can be obtained from a variety of different sources. The iron ore particles can be recovered from, for example, but not limited to, mini-mills (e.g. steel dust with electrostatic precipitation in electric arc furnace), integrated plants from raw material management (storage/transfer/grinding/sizing), from blast furnace (hydrocyclones) and from converters (coarse, dust).
[0037] The water-soluble polymer is prepared in the absence of acrylamide and of acrylamide derivative, said polymer being therefore free of acrylamide and of acrylamide derivative.
[0038] The water-soluble polymer as disclosed herein is obtained by polymerizing:
- at least one anionic monomer (a) selected from acrylic acid, a salt of acrylic acid, methacrylic acid, a salt of methacrylic acid, and/or combinations thereof, and
- at least one monomer (b) of formula I:
I
wherein R1 and R2 independently represent a hydrogen atom or a CH3 group; wherein m and n independently represent a number between 0 and 250, the sum of m and n is equal to or greater than 10 and n is greater than m; and wherein [(EO)n-(PO)m] represents a poly- alkoxyl chain comprising ethoxyl units EO, propoxyl units PO or combinations thereof that are distributed in blocks, alternately or randomly.
[0039] In some embodiments, the polymer has a Mw molecular weight from about 10,000 to 1,000,000 g/mol. In other embodiments, the polymer has a Mw molecular weight from about 15,000 to 500,000 g/mol, and in other embodiments, from about 20,000 to 200,000 g/mol.
[0040] In some embodiments, the polymer is not neutralized. In an alternative embodiment, the polymer is totally or partially neutralized.
[0041] In such embodiments, wherein the polymer is totally or partially neutralized, the polymer is neutralized by NaOH, KOH, ammonium derivatives, ammonia, amino-alkali substances, and/or combinations thereof. In some embodiments, the amino-alkali substances comprise triethanolamine or 2-amino-2-methyl-propanol (AMP).
[0042] In some embodiments, the monomer (b) of the disclosed polymer is:
- monomer (bl) of formula I, wherein R1 represents a hydrogen atom, R2 represents a CH3 group, m represents 0, n represents a number between 10 and 250, and [(EO)n] represents a polyalkoxyl chain comprising ethoxyl units EO.
[0043] In some embodiments, the monomer (b) of the disclosed polymer is:
- monomer (b2) of formula I, wherein R1 represents a CH3 group, R2 represents a CH3 group, m represents 0, n represents a number between 10 and 250, and [(EO)n] represents a polyalkoxyl chain comprising ethoxyl units EO.
[0044] In some embodiments, the monomer (b) of the disclosed polymer is:
- monomer (b3) of formula I, wherein R1 represents a hydrogen atom, R2 represents a hydrogen atom, m and n independently represent a number between 1 and 250, and the sum of m and n is equal to or greater than 10 and n is greater than m, and [(EO)n - (PO)„,| represents a polyalkoxyl chain comprising ethoxyl units EO, propoxyl units PO or combinations thereof that are distributed in blocks, alternately or randomly.
[0045] In some embodiments, the monomer (b) of the disclosed polymer is:
- monomer (b4) of formula I, wherein R1 represents a CH3 group, R2 represents a hydrogen
atom, m and n independently represent a number between 1 and 250, and the sum of m and n is equal to or greater than 10 and n is greater than m, and [(EO)n- (PO)m] represents a polyalkoxyl chain comprising ethoxyl units EO, propoxyl units PO or combinations thereof that are distributed in blocks, alternately or randomly.
[0046] In a preferred embodiment, the iron-ore based composite is in the form of a pellet or in the form of a briquette.
[0047] In some embodiments, the composite does not comprise molasses, starch, and/or starch derivatives. Because the iron-ore composite of the disclosed technology does not include molasses, starch, and/or starch derivatives, undesired elements, such as, for example, phosphorus and silicon, are not introduced into the briquette or pellet, thus improving the quality of the briquettes and/or pellets obtained.
[0048] In some embodiments, the iron-ore based composite comprises a moisture content of less than about 15% wt. relative to the total weight of the composite. In some embodiments, the moisture content is less than about 12% wt. relative to the total weight of the composite, and in other embodiments, the moisture content is less than about 10% wt. relative to the total weight of the composite.
[0049] In yet another aspect of the disclosed technology, a method of preparing an iron-ore based composite is provided. The method comprises:
- contacting a plurality of iron ore particles with at least one water-soluble polymer to form an agglomeration, and
- forming a composite.
[0050] The iron ore particles comprise iron ore fines and/or iron ore residues.
[0051] The polymer is prepared in the absence of acrylamide and of acrylamide derivative.
[0052] The polymer is prepared by polymerizing at least one anionic monomer (a) selected from acrylic acid, a salt of acrylic acid, methacrylic acid, a salt of methacrylic acid, and/or combinations thereof; and at least one monomer (b) of formula I:
I
wherein R1 and R2 independently represent a hydrogen atom or a CEE group; wherein m and n independently represent a number between 0 and 250, the sum of m and n is equal to or greater than 10 and n is greater than m; and wherein [(EO)n-(PO)m] represents a polyalkoxyl chain comprising ethoxyl units EO, propoxyl units PO or combinations thereof that
are distributed in blocks, alternately or randomly.
[0053] The method first provides for contacting a plurality of iron ore particles with at least one water-soluble polymer to form an agglomeration. The polymer may be applied to the iron ore particles by intimate mixing. Upon contact of the polymer and the iron particles, an agglomeration of these particles is facilitated.
[0054] In some embodiments, forming a composite is carried out in the absence of molasses, starch, and/or starch derivatives. Since formation of the composite does not include these substances, undesired elements, such as, for example, phosphorus and silicon, are not introduced into the briquette or pellet. It should be understood that any recovered iron ore composites may include trace amounts of phosphorus and/or silicon based on the source of the iron ore residues or recovered fines. However, the disclosed method does not increase the amount of phosphorus and/or silicon that is ultimately present in the final composite.
[0055] In some embodiments, contacting the plurality of iron ore particles with the polymer does not increase the amount of phosphorus present in the composite that is formed. In some embodiments, contacting the plurality of iron ore particles with the polymer does not increase the amount of silicon present in the composite that is formed.
[0056] In some embodiments, forming a composite comprises feeding the agglomeration into a mixer and press to form a plurality of briquettes and/or pellets.
[0057] The composite as described herein comprises a moisture content of less than about 15% wt. relative to the total weight of the composite. In other embodiments, the composite comprises a moisture content of less than about 12% wt. relative to the total weight of the composite, and in other embodiments, the moisture content is less than about 10% wt. relative to the total weight of the composite.
[0058] Examples
[0059] The present technology will be further described in the following examples, which should be viewed as being illustrative and should not be construed to narrow the scope of the disclosed technology or limit the scope to any particular embodiments.
[0060] The disclosed polymer Pl was prepared according to the invention . In a 1 -liter reactor under stirring, we loaded 382.5g of de-ionized water, 441.3g of monomer b (compound of formula I wherein R1 represents a CH3 group, R2 represents a hydrogen atom, m represents 16, n represents 48 and [(EO)n- (PO)„,| represents a polyalkoxyl chain comprising ethoxyl units EO, propoxyl units PO) and 35.4g of monomer a (methacrylic
acid). Then, two compositions of reagents in two different beakers were prepared: in the first beaker, 1.69g of ammonium persulfate solubilized in 7.5g of water; and in the second beaker, 2.033g of DMDO (l,8-dimercapto-3,6-di oxaoctane).
[0061] The reactor was heated to 64°C, and under stirring the reagents, firstly DMDO and secondly ammonium persulfate solution were introduced. The reactor was maintained under stirring for lh30min in a temperature range from 65°C to 69°C.
[0062] The polymer was neutralized with a water solution of sodium hydroxide to adjust pH at 5.0. Solid content was then adjusted by de-ionized water addition until reaching 50wt% solid content. Polymer Pl had a molecular weight of 130,000 g/mol (measured by SEC) and a polymolecularity (Ip) of 1.8.
[0063] Iron ore pellets according to the disclosed technology were then prepared while using polymer Pl. Comparative iron ore pellets were also prepared with comparative binders. For preparing the pellets, the various materials were thoroughly mixed with a planetary blender starting by introduction of the iron ore followed by water (added to obtain a constant humidity value of 12 wt% to 14 wt%) and the other ingredients. The components were blended for approximately 30 minutes.
[0064] The comparative binders that were used are: molasses with lime and starch; a sodium polyacrylate polymer having a molecular weight Mw of 5,000 g/mol (solids content = 55%); and a sodium polyacrylate polymer having a molecular weight Mw of 70,000 g/mol (solids content = 40%).
[0065] A small amount of the blended compositions was set aside to control humidity. With the remaining compositions, two sets of 3 pellets were produced with a hydraulic press in a cylindrical mold (inside diameter 41 mm) fitted with a piston. The pellets were prepared using a pressing device resulting in pellets having controlled cylindrical shape and size (41 mm diameter x 12 mm height). The weight of each pellet was 35 g. Components and amounts are presented in Table 1.
[0066] The pellets according to the disclosed technology and the comparative pellets were then subjected to evaluations of their mechanical properties.
[0067] Mechanical strength of the pellets was evaluated by a drop test whereby integrity of the pellets was controlled after 3 drops from a height of 1.5 meter. Elasticity of the pellets was evaluated by means of a 3-point bending apparatus allowing controlling the deformation of the pellets. The second test being the measure of the deformation of the pellets on a three
points bending apparatus, a higher deformation giving a better resistance on impact.
[0068] For the drop testing, the pellets were pressed during one minute with a pressure of 4 tons, while for the deformation test a pressure of 2 tons was applied during 1 minute. Immediately after the pellets production the test was ran.
[0069] For the drop test, up to 4 drops were made and the appearance of the pellets was noted each time. For the deformation test, pellets were placed on two supporting rollers with a 30 mm span and pressure was applied in the center of the pellet with a third roller descending at a speed of 0. 1 mm per second. The resistance to pressure was then recorded and the displacement where resistance increases sharply was noted. The longer this displacement, the more deformable the pellet is and the less prone to breaking. Pellet composition and test results are presented in Table 1.
[0070] [Table 1]
[0071] The results confirmed the elimination of lime in order to further simplify the process and reduce the dose of the disclosed water-soluble polymer composition.
[0072] In the foregoing specification, the technology has been described with reference to specific embodiments thereof. While embodiments of the disclosed technology have been described, it should be understood that the present disclosure is not so limited and modifications may be made without departing from the disclosed technology. The scope of the disclosed technology is defined by the appended claims, and all devices, processes, and methods that come within the meaning of the claims, either literally or by equivalence, are intended to be embraced therein.
Claims
Claims ron-ore based composite, the composite comprising:
- a plurality of iron ore particles, said iron ore particles comprising iron ore fines and/or iron ore residues; and
- at least one water-soluble polymer, said polymer being free of acrylamide and of acrylamide derivative, wherein said polymer is obtained by polymerizing:
- at least one anionic monomer (a) selected from acrylic acid, a salt of acrylic acid, methacrylic acid, a salt of methacrylic acid, and/or combinations thereof; and
- at least one monomer (b) of formula I:
H2C=C(-R1)-C(=O)-O-[(EO)„-(PO)m]-R2 wherein R1 and R2 independently represent a hydrogen atom or a CH3 group; wherein m and n independently represent a number between 0 and 250, the sum of m and n is equal to or greater than 10 and n is greater than m; and wherein [(EO)n-(PO)m] represents a polyalkoxyl chain comprising ethoxyl units EO, propoxyl units PO or combinations thereof that are distributed in blocks, alternately or randomly. The composite according to the preceding claim, wherein said composite comprises a moisture content of less than about 15% wt. relative to the total weight of the composite. The composite according to any of the preceding claims, wherein said composite is in the form of a pellet or in the form of a briquette. The composite according to any of the preceding claims, wherein said composite does not comprise molasses, starch, and/or starch derivatives. The composite according to any of the preceding claims, wherein said polymer has a Mw molecular weight from about 10,000 to 1,000,000 g/mol, preferably from about 15,000 to 500,000 g/mol, or from about 20,000 to 200,000 g/mol. The composite according to any of the preceding claims, wherein said polymer is not neutralized, or is totally or partially neutralized. The composite according to Claim 6, wherein said totally or partially neutralized polymer is neutralized by NaOH, KOH, ammonium derivatives, ammonia, amino-alkali substances, and/or combinations thereof. The composite according to Claim 7, wherein said amino-alkali substances comprise triethanolamine or 2-amino-2-methyl-propanol (AMP).
The composite according to any of Claims 1 to 8, wherein said monomer (b) is selected from:
- monomer (bl) of formula I, wherein R1 represents a hydrogen atom, R2 represents a CH3 group, m represents 0, n represents a number between 10 and 250, and [(EO)n] represents a polyalkoxyl chain comprising ethoxyl units EO;
- monomer (b2) of formula I, wherein R1 represents a CH3 group, R2 represents a CH3 group, m represents 0, n represents a number between 10 and 250, and [(EO)n] represents a polyalkoxyl chain comprising ethoxyl units EO;
- monomer (b3) of formula I, wherein R1 represents a hydrogen atom, R2 represents a hydrogen atom, m and n independently represent a number between 1 and 250, and the sum of m and n is equal to or greater than 10 and n is greater than m, and [(EO)n - (PO),„| represents a polyalkoxyl chain comprising ethoxyl units EO, propoxyl units PO or combinations thereof that are distributed in blocks, alternately or randomly; or
- monomer (b4) of formula I, wherein R1 represents a CH3 group, R2 represents a hydrogen atom, m and n independently represent a number between 1 and 250, and the sum of m and n is equal to or greater than 10 and n is greater than m, and [(EO)n- (PO)m ] represents a polyalkoxyl chain comprising ethoxyl units EO, propoxyl units PO or combinations thereof that are distributed in blocks, alternately or randomly. ethod of preparing an iron-ore based composite according to one of claims 1 to 9, said method comprising:
- contacting a plurality of iron ore particles with at least one water-soluble polymer according to one of claims 1 to 9, to form an agglomeration; and
- forming a composite. method according to Claim 10, wherein contacting said plurality of iron ore particles with said polymer does not increase the amount of phosphorus present in said composite. method according to any of Claims 10 to 11, wherein contacting said plurality of iron ore particles with said polymer does not increase the amount of silicon present in said composite. method according to any of Claims 10 to 12, wherein said forming a composite comprises feeding the agglomeration into a mixer and press to form a plurality of briquettes and/or pellets. method according to any of Claims 10 to 13, wherein said forming a composite is carried out in the absence of molasses, starch, and/or starch derivatives.
15. The method according to any of Claims 10 to 14, wherein said composite comprises a moisture content of less than about 15% wt. relative to the total weight of the composite.
14
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR763A FR1345636A (en) | 1962-10-13 | 1962-10-13 | Device allowing the instant destruction of concrete runways |
| FRFR2100763 | 2021-01-27 |
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| Publication Number | Publication Date |
|---|---|
| WO2022164990A1 true WO2022164990A1 (en) | 2022-08-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2022/014039 WO2022164990A1 (en) | 2021-01-27 | 2022-01-27 | Composition for briquetting and/or pelletization of iron ore fines and residues, iron-ore composite and method of preparing the iron-ore composite |
Country Status (2)
| Country | Link |
|---|---|
| FR (1) | FR1345636A (en) |
| WO (1) | WO2022164990A1 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005089861A (en) * | 2003-08-12 | 2005-04-07 | Kobe Steel Ltd | Additive in granulating ironmaking raw material, and granular material for ironmaking raw material |
| EP3271306A1 (en) * | 2015-03-16 | 2018-01-24 | Coatex | Novel copolymer as a water-reducing agent in a hydraulic composition |
| WO2018153995A1 (en) * | 2017-02-22 | 2018-08-30 | Basf Se | Use of copolymers as binders for pelletizing metal containing ores |
-
1962
- 1962-10-13 FR FR763A patent/FR1345636A/en not_active Expired
-
2022
- 2022-01-27 WO PCT/US2022/014039 patent/WO2022164990A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005089861A (en) * | 2003-08-12 | 2005-04-07 | Kobe Steel Ltd | Additive in granulating ironmaking raw material, and granular material for ironmaking raw material |
| EP3271306A1 (en) * | 2015-03-16 | 2018-01-24 | Coatex | Novel copolymer as a water-reducing agent in a hydraulic composition |
| WO2018153995A1 (en) * | 2017-02-22 | 2018-08-30 | Basf Se | Use of copolymers as binders for pelletizing metal containing ores |
Also Published As
| Publication number | Publication date |
|---|---|
| FR1345636A (en) | 1963-12-13 |
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