CN101031513A - A method for producing iron oxide nano particles - Google Patents
A method for producing iron oxide nano particles Download PDFInfo
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- CN101031513A CN101031513A CN 200580027372 CN200580027372A CN101031513A CN 101031513 A CN101031513 A CN 101031513A CN 200580027372 CN200580027372 CN 200580027372 CN 200580027372 A CN200580027372 A CN 200580027372A CN 101031513 A CN101031513 A CN 101031513A
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- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 229940031182 nanoparticles iron oxide Drugs 0.000 title 1
- 239000002245 particle Substances 0.000 claims abstract description 228
- 238000000034 method Methods 0.000 claims abstract description 196
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 191
- 239000000243 solution Substances 0.000 claims abstract description 171
- 229910052742 iron Inorganic materials 0.000 claims abstract description 76
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000007864 aqueous solution Substances 0.000 claims abstract description 41
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 230000007062 hydrolysis Effects 0.000 claims abstract description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims description 51
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 49
- 230000008569 process Effects 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 41
- 238000002156 mixing Methods 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000006185 dispersion Substances 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 230000018044 dehydration Effects 0.000 claims description 25
- 238000006297 dehydration reaction Methods 0.000 claims description 25
- -1 iron ion Chemical class 0.000 claims description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 238000012545 processing Methods 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 12
- 150000002505 iron Chemical class 0.000 claims description 12
- 239000012266 salt solution Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 229910002588 FeOOH Inorganic materials 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 230000000630 rising effect Effects 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 238000010790 dilution Methods 0.000 claims description 7
- 239000012895 dilution Substances 0.000 claims description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 7
- 235000014413 iron hydroxide Nutrition 0.000 claims description 7
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000011707 mineral Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003929 acidic solution Substances 0.000 claims description 6
- 238000005054 agglomeration Methods 0.000 claims description 6
- 230000002776 aggregation Effects 0.000 claims description 6
- 230000002829 reductive effect Effects 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000000049 pigment Substances 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000013543 active substance Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 229920000831 ionic polymer Polymers 0.000 claims description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 4
- 238000012423 maintenance Methods 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 150000003016 phosphoric acids Chemical class 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 238000007669 thermal treatment Methods 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 229920006318 anionic polymer Polymers 0.000 claims description 3
- 229920006317 cationic polymer Polymers 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000009776 industrial production Methods 0.000 claims description 2
- 150000002506 iron compounds Chemical class 0.000 claims description 2
- 235000013980 iron oxide Nutrition 0.000 claims description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000007865 diluting Methods 0.000 abstract description 9
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract description 5
- 230000007423 decrease Effects 0.000 abstract description 3
- 230000003028 elevating effect Effects 0.000 abstract 1
- 229910001447 ferric ion Inorganic materials 0.000 abstract 1
- 230000014759 maintenance of location Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 230000004048 modification Effects 0.000 description 13
- 238000012986 modification Methods 0.000 description 13
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 11
- 238000009826 distribution Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 235000010755 mineral Nutrition 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 5
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052951 chalcopyrite Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 2
- 229910052683 pyrite Inorganic materials 0.000 description 2
- 239000011028 pyrite Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 230000010512 thermal transition Effects 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 230000001131 transforming effect Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical group C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910001608 iron mineral Inorganic materials 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920003228 poly(4-vinyl pyridine) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Compounds Of Iron (AREA)
Abstract
The invention provides a method for the formation of small-size iron oxide particles comprising the steps of preparing a starting aqueous solution comprising at least one of ferric ions and complexes thereof, at a concentration of at least 0.1% w/w iron and a pH greater than about 1.5; maintaining said solution at a temperature lower than 55 DEG C for a retention time in which hydrolysis takes place, the extent of said hydrolysis being sufficient to decrease the pH by at least 0.2 units, wherein said time does not exceed 14 days, to form a system containing a modified solution; and adjusting the conditions in said system by at least one of the steps of heating the modified solution to elevate the temperature thereof by at least 10 DEG C; elevating the pH of the modified solution by at least 0.3 units; and diluting the modified solution by at least 20%; whereby there are formed particles, wherein the majority of the particles formed are between about 2nm and about 500nm in size.
Description
The present invention relates to a kind of method of producing ferric oxide nanometer particle, relate more specifically to a kind of produce in available mode on the industrial and economics have desired particle size, the method for the ferric oxide particles of size-grade distribution and crystalline form (habit).Among the present invention, chemical formula Fe is represented and comprised to the term ferric oxide
xO
yThe ferriferous oxide (Fe in rhombohedral iron ore and the magnetite for example
2O
3), chemical formula Fe
p(OH)
qO
rIron hydrogen-oxygen oxide compound (for example FeOOH in pyrrhosiderite and the akaganeite), those compounds various hydrated forms and wherein those compounds be the composition of principal constituent, x, y, p, q, the r integer of respectively doing for oneself wherein.
The ferriferous oxide powder is used for various application widely in industry at present: magnetic data storage medium, catalyzer, mineral dye and wustite synthesize precursor.Have the improvement performance in order the to produce material of (for example the goods of nanocrystal degree, narrow size-grade distribution, metastable phasing etc.) adopts chemical technology widely, comprises that hydro-thermal (hydrothermallurgic) is synthetic.Under the situation of hydro-thermal synthesizing superfine croci, the ironic hydroxide that forms in neutrality or basic solution is mainly as precursor.At high temperature by even acid formulations prepared from solutions iron (III) oxide compound.
Ferriferous oxide brings the variation of granularity, color, density, porosity, surface-area and shape.These parameters have great effect to its purposes and performance.The finished product performance depends on that being used to of being researched and developed precipitate the step with the ageing product.
Ferric oxide nanometer particle demonstrates the color that (limonite and pyrrhosiderite), light red change to scarlet (rhombohedral iron ore), orange (lepidocrotite) and brown (akaganeite) from the yellow to the yellowish brown.The color of every kind of ferric oxide depends on granularity, size-grade distribution and crystalline form.For example, the rhombohedral iron ore particle has the different colours that changes from the light red to the scarlet.The rhombohedral iron ore particle that has than volume particle size tends to show darker tone.For example, median size is 200nm (nanometer) at the most, and for example the particulate state rhombohedral iron ore particle of 50-200nm shows light red, and median size to be those particles of 400-600 nanometer show scarlets.
A lot of patents relate to the problem of producing the ferric oxide particles with certain particle size, size-grade distribution and crystalline form.For example, a kind of production fusiformis pyrrhosiderite particle and fusiformis rhombohedral iron ore particulate method have been put down in writing in the United States Patent (USP) 6391450 (2002), described particle contains a selected amount of cobalt and aluminium, have uniform particle size, big minor axis diameter and suitable aspect ratio, and anti-sintering character is very excellent, and the document has also been put down in writing the fusiformis magnetic iron base alloy particle that is obtained by described fusiformis rhombohedral iron ore particle.
In the United States Patent (USP) 5652192 of relevant catalystic material and preparation method thereof; record and claimed a kind of preparation nano particle size particulate method and apparatus; described particle is ferric oxide, titanium oxide, nickel oxide, zirconium white, aluminum oxide and silicon oxide for example; by making continuous flow solution through hot vessel; in this hot vessel by pressurization with heat described fluent solution initiating chamical reaction; make the fluent solution quenching of described heating form particle subsequently, and the growth that stops described solid particulate.Described patent expection productivity for tens gram particles per hour to several kilograms of particles approximately per hour, still do not instruct or provide and can per hour produce at least tens kilograms of particulate commercial runs.
Big quantity research relates to the thermal transition of the ferric oxide particles of hyperhydrated degree to the ferric oxide particles of low hydration levels.The result of this conversion produces the crystalline form highly porous particle close with granularity with the precursor granule crystalline form with granularity.The present invention relates to produce and can use by existing sample, but the ferric oxide particles that also has the advantageous characteristic relevant with the performance in its conversion reaction.
An object of the present invention is to provide a kind of industry and economically feasible production has the method for the ferric oxide particles of desired particle size, size-grade distribution and crystalline form.The particle of Sheng Chaning is other ferric oxide type particle with low hydration levels by thermal conversion easily by this way, obtains having the particle of highly porous and required type, form, crystal size, crystal size distribution and crystalline form thus.
In order to realize this purpose, a kind of method of producing ferric oxide particles in the aqueous solution is provided, this method comprises and perferrite solution is remained below that next section of temperature of 55 ℃ is enough to because hydrolysis descends time of 0.2 pH unit pH value of solution at least.The solution that obtains is carrying out modification aspect temperature and/or Fe (III) concentration (dilution) then, and/or adds reagent, improves pH value of solution thus.The preferred modification of described parameter is in two-forty.
Aspect second of the present invention, be provided for raw material by other ferric oxide particles of thermal transition gained particle manufacture.
According to the present invention, more specifically, provide a kind of method that forms the small grain size ferric oxide particles now, this method may further comprise the steps:
A) preparation comprises the initial aqueous solution of iron ion or its complex compound, and concentration is 0.1%w/w iron at least, and pH is greater than about 1.5,
B) described solution being remained below next section of temperature residence time of 55 ℃ contains the system of modified solution with formation, in this residence time hydrolysis takes place, and the degree of described hydrolysis is enough to make pH at least 0.2 unit that descends, the wherein said time be no more than 14 days and
C) regulate condition in the described system by at least one of following steps:
I) heat described modified solution, so that its temperature raises 10 ℃ at least,
Ii) make at least 0.3 unit of pH rising of modified solution; With
Iii) with described modified solution dilution at least 20%;
Form particle thus, wherein most of particulate granularity that forms arrives about 500nm for about 2nm.
In a preferred embodiment of the invention, described solution remained under the described modified condition 0.5 minute at least.
Preferably, the modification of described condition proceeds to many 1 hour time.
In a preferred embodiment of the invention, described method is per hour produced at least 50 kilograms of particles.
Preferably, the modification of described condition is being carried out under 100 normal atmosphere at the most.
In a preferred embodiment of the invention, described method is further characterized in that most of particle that forms has the degree of crystallinity less than 50%.
Preferably, described method is further characterized in that 50% particulate smallest particles that forms and the size ratio between the largest particle are lower than about 10.
In particularly preferred embodiment, described method is further characterized in that 50% particulate smallest particles that forms and the size ratio between the largest particle are lower than about 5.
Preferably, described method is further characterized in that most of particle that forms has the structure that is different from long strip shape.
In a preferred embodiment of the invention, described method is further characterized in that most of particle that forms has a kind of structure, and the ratio between one of them dimension and any other dimension is lower than about 3.
In other preferred embodiment of the present invention, most of particle that forms has elongate formation.
Preferably, most of particle that forms has 30m at least
2The surface-area of/g.
Preferably, most of particle that forms has 100m at least
2The surface-area of/g.
In particularly preferred embodiment of the present invention, described method further may further comprise the steps:
(iv) under about 800 ℃ dehydration temperaturre, make the particle dehydration of described formation to form the particle of dehydration at about 60 ℃.
In described preferred embodiment, described method preferably further is included in described promotion (facilitating) afterwards, and before described dehydration, simultaneously or remove the step of portion water in the described particle suspension liquid afterwards.
In described preferred embodiment, described dehydration is preferably carried out under superatmospheric pressure.
In described preferred embodiment, the temperature of described particle suspension liquid is preferably through being elevated to described dehydration temperaturre at the most in 2 hours.
In described particularly preferred embodiment, the particle of most of dehydration preferably has the structure that is different from long strip shape.
In described particularly preferred embodiment, the particle of most of dehydration preferably has 30m at least
2The surface-area of/g.
Preferably, described particle is selected from pyrrhosiderite, rhombohedral iron ore and magnetite.
Particularly preferably be particle with chemical formula FeOOH.
Equally preferably has chemical formula Fe
2O
33H
2The particle of O.
In a preferred embodiment of the invention, the preparation of the described aqueous solution comprises oxidation.
Preferably, the pH of the described aqueous solution is about 1.0 to about 5 at the length at least of described promotion step.
Particularly preferably be a kind of method, the pH of the wherein said aqueous solution is about 1.5 to about 4 at the length at least of described promotion step.
Most preferably a kind of method, the pH of the wherein said aqueous solution is about 1.7 to about 2.5 at the length at least of described promotion step.
In a preferred embodiment of the invention, the preparation of the described aqueous solution comprises the oxidation of ferrous ion.
Preferably, the oxygenant that is selected from oxygen, hydrogen peroxide, nitric acid and nitrate is used in described oxidation.
Preferably, described oxidation is carried out in the solution that comprises sulfuric acid and nitric acid.
In preferred embodiments, described oxidation is carried out in being lower than about 5 pH.
Preferably, described oxidation is that chemistry or biology are catalytic.
In a preferred embodiment of the invention, the preparation of the described aqueous solution comprises the dissolving of iron cpd.
In described preferred embodiment, described iron cpd is preferably selected from molysite, ferriferous oxide, iron hydroxide, iron mineral and combination thereof.
Preferably, described iron cpd chosen from Fe oxide compound, iron hydroxide, contain mineral of ferriferous oxide or iron hydroxide and composition thereof, described compound is dissolved in the acidic solution that comprises acid, and described acid is selected from sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, its acid salt and combination thereof.
In a preferred embodiment of the invention, the aqueous solution of described preparation comprises the negatively charged ion that is selected from vitriol, muriate, nitrate, phosphoric acid salt and composition thereof.
In a preferred embodiment of the invention, described modification comprises at least two heating stepses.
In described preferred modification procedure, preferably carry out at least one heating steps by contacting with hot-fluid, described hot-fluid is selected from hydrothermal solution, hot gas and steam.
In preferred embodiments, described method preferably further comprises the particle that grinds formation.
In preferred embodiments, described method preferably further comprises the particle that screening forms.
In preferred embodiments, described method preferably further comprises the particle that hydrogenation forms.
The invention still further relates to according to the ferric oxide particles of aforesaid method formation and the product of their conversions.
The invention further relates to and comprise described particulate goods.
In the preferred embodiment of described goods, described particle preferably is dispersed in the liquid, be carried on the solid chemical compound or agglomerate into larger particles.
In another aspect of the present invention, a kind of method of producing the goods of above definition is provided, this method comprises the step that is selected from the described particle of dispersion, interpolation carrier, thermal treatment, mixing, water evaporation and combination thereof.
In particularly preferred embodiment of the present invention, described particle and goods are used for making paint.
In other preferred embodiment of the present invention, described particle and goods are used to make catalyzer.
In another preferred embodiment of the present invention, a kind of method that forms the small grain size ferric oxide particles is provided now, this method may further comprise the steps:
A) preparation comprises at least a initial aqueous solution in iron ion and the complex compound thereof, and concentration is 0.1%w/w iron at least, and this solution has at least 1.2 pH;
B) preparation temperature is greater than 80 ℃ modified aqueous solution;
C) starting soln is contacted with modified solution, form modified system;
D) with plug flow (plug-flow) mode from mixing section shift out modified solution and
This method feature is:
(i) residence time in the mixing section is lower than about 1 minute,
(ii) form particle or its aggregate, wherein most of particulate granularity that forms arrives about 500nm for about 2nm; With
(iii) the particle of Xing Chenging comprises FeOOH, Fe
2O
3, Fe (OH)
3, Fe
3O
4Or its combination.
In particularly preferred embodiment of the present invention, modified solution rests on and is less than 5 seconds in the mixing section, and in more preferred, modified solution rests on and is less than 1 second in the mixing section.
In a preferred embodiment of the invention, utilization enters the flow of solution or mixes in mixing section by use mechanically mixing mode or other hybrid mode.
In a preferred embodiment of the invention, modified solution leaves mixing section in the plug flow mode.In more preferred, plug flow continues to surpass 0.1 second, and in most preferred embodiment, plug flow continued above 5 seconds.
In a preferred embodiment of the invention, the solution that leaves plug flow enters container.In more preferred of the present invention, the solution in the container mixes.
Detailed Description Of The Invention
The present invention now will be in the following detailed description of doing.
At first, description is according to the method for production ferric oxide particles of the present invention.
Be used for initial molysite aqueous solution of the present invention and be preferably a kind of molysite aqueous solution that comprises iron ion or its complex compound, concentration is 0.1%w/w iron at least, and pH is greater than about 1.5.
According to preferred embodiment, the iron w/w concentration in the starting soln is at least 1%, more preferably at least 5%, most preferably at least 10%.Concentration for starting soln does not have the upper limit.But according to preferred embodiment, this concentration is lower than saturation concentration.According to another preferred embodiment, do not wish the viscosity height.According to preferred embodiment, the pH of starting soln is at least 1.7, preferably at least 1.9.According to particularly preferred embodiment, the pH of the starting soln of preparation is acid or neutral, is for example measured by the OH/Fe ratio in the solution.According to preferred embodiment, this ratio is more preferably less than 2.5 less than 3.According to preferred embodiment, the temperature of the starting soln of preparation is lower than 55 ℃.
Any source of iron all is suitable for preparing starting soln of the present invention, comprises various scrap iron, Qie Ge scrap iron etc. for example, and iron-stone, the chip of this ore, its converted products, molysite or iron-containing liquor for example leave the aqueous solution of iron-stone.
According to preferred embodiment, after reaching desired concn and pH, and then carry out step (b).According to another preferred embodiment, the solution that is used for step (b) prepares at short notice, and is not combined in iron ion or its complex compound that the different time preparation mixes then.Because similar reason does not wish that preparation time prolongs.According to preferred embodiment, preparation time is shorter than 20 hours, preferably is shorter than 10 hours, most preferably is shorter than 2 hours.Have early solution (for example circulate soln) therein and wish to mix under the situation that forms starting soln with fresh solution, be somebody's turn to do than morning solution at first by acidifying, as described below.
Freshly prepd iron salt solutions can contain any negatively charged ion, comprises muriate, vitriol, nitrate, phosphoric acid salt, carbonyl hydrochlorate, organic anion and various its mixtures etc.According to preferred embodiment, freshly prepd solution comprises ferric sulfate.According to another preferred embodiment, this salt belongs to organic acid salt.
Be used for the solution (, for example leaving the solution in mine) that the freshly prepd salts solution of the inventive method can be produced with iron-stone in natural condition, or the solution of the manual method preparation that comprises chemistry or bio-oxidation of serving as reasons.This solution can be by the whole bag of tricks or its combined preparation, be included in and dissolve molysite, dissolving ferrous salt, dissolving double salt, dissolving in the acidic solution and contain ferric oxide ore, for example dissolving scrap iron in the oxidizing solution such as molysite, salpeter solution, lixiviate is the iron-bearing mineral etc. of pyrite and chalcopyrite etc. for example.
According to preferred embodiment, the preparation aqueous solution carried out in a step.According to optional embodiment, preparation comprises two or more steps.According to an embodiment, for example prepare the strong solution of molysite by dissolved salt in the water or the aqueous solution.Though be temporary transient and/or partial, in dissolution process, reached the required pH and the concentration of starting soln, be usually less than the required pH of starting soln at the pH of the strong solution that forms to the small part homogenizing.According to preferred embodiment, this moment reaches required condition and is not considered to prepare starting soln.The pH of strong solution reaches desired level by any suitable mode then, and described mode is for example to remove the concentration of disacidify, interpolation and/or rising basic cpd or the combination of those modes.According to preferred embodiment, form starting soln in this case and be considered to pH regulator is arrived selected scope, and according to another preferred embodiment, the pH of starting soln is obtaining to the small part homogenizing.According to another preferred embodiment, the preparation strong solution and with pH regulator to being lower than required level slightly.Prepare starting soln by diluting soln then, make pH be elevated to desired level like this.Equally, according to preferred embodiment, the pH of starting soln is obtaining to the small part homogenizing.Other method for the rapid preparation of the multistep of starting soln is like this equally, is for example forming ferrous salt solution and its oxidation is being formed the situation of iron salt solutions.
Under certain situation of the present invention, the source of iron of solution can be scrap iron etc. and/or iron (II), and must carry out oxidation step, so that obtain ferrous solution.This oxidation can be used any known oxygenant, for example air, oxygen, hydrogen peroxide, nitric acid and nitrate and combination thereof.Oxidation can be finished under any temperature and pressure.Usually, high temperature and high pressure promote the oxidation reaction.Can use biological catalyst, chemical catalyst or its combination.Do not need complete oxidation, particle of the present invention can be formed by the solution that contains iron and ferrous ion.
According to preferred embodiment, the prepared fresh starting soln.According to another preferred embodiment, solution is not included in the ion and/or the complex compound of different time preparation, as under with circulate soln and freshly prepd solution blended situation.According to preferred embodiment, be lower than 1.5 at pH, under high density (for example being higher than 10% iron) and the low temperature (for example being lower than 40 ℃), solution keeps its freshness for a long time, and can be used as liquid storage.According to another preferred embodiment, under other condition, after several hours or several days, do not think that solution is fresh.According to preferred embodiment, recover the freshness of solution by acid treatment.This more stale solution is acidified to pH is lower than 2.0, preferred pH is lower than 1.5, and before getting back to the pH liter above 1.7, preferably mixes, stirs or shook at least 5 minutes, to form fresh solution again.According to preferred embodiment, this fresh solution that forms is again mixed with other fresh solution.
In next step of this method, ferrous solution preferably keeps being no more than 10 days the residence time being lower than under 55 ℃ the temperature.Hydrolysis took place during the residence time.Preferably, this residence time is enough to make pH because at least 0.2 unit of described hydrolysis decline.According to another preferred embodiment, the residence time is to produce at least 1 required time of mmole H+ (proton) in solution.According to another preferred embodiment, the residence time is to form 0.0001 mole of proton ion of every mole of Fe (III) solution, more preferably 0.001 mole of required time of proton ion of every mole of Fe (III) solution in solution.Adding under the situation of alkali or basic cpd to solution during the residence time therein, the residence time is for forming the required time of proton of those amounts on the basis of not adding alkali.
According to preferred embodiment, the residence time reduces along with the rising of the pH of prepared solution.Therefore, for example be lower than under 2.5 the pH, the residence time is preferably 1 hour to several days.Under 2.5 to 5.0 pH, the residence time preferably is less than 1 day.Changing under the situation of pH the influence of the maximum pH that the residence time is reached during the residence time.Usually, the residence time reduces along with the rising of solution temperature.
Realize rising pH and/or temperature for realizing that the 3rd required step of above-mentioned coprecipitation mode is modified to solution condition, and/or at least a in the diluting soln.
The modification of condition is preferably finished at short notice, and keeps the modified condition of short period of time.The time length of modified condition is less than 24 hours, according to exemplary, preferably is less than 4 hours, more preferably less than 1 hour, most preferably is less than 10 minutes.In other preferred embodiment of the present invention, in 1 hour, preferably in 10 minutes, more preferably modified condition in 1 minute.
Improving pH in step (c) can realize by any currently known methods, for example removes disacidify or interpolation basic cpd or improves basic cpd concentration.Remove disacidify and can pass through currently known methods, for example extraction or distillation are carried out.Can add any basic cpd.According to preferred embodiment, basic cpd is a kind of than the ferric sulfate compound of alkalescence more, as by relatively they wait molar solution pH measured.Therefore, this basic cpd is preferably inorganic or organic bases, or at least a in the alkali precursor, for example oxide compound, oxyhydroxide, carbonate, supercarbonate, ammonia, urea etc.According to another preferred embodiment, basic cpd is ferrous salt, for example ferrous sulfate.According to preferred embodiment, ferrous sulfate forms by introducing the metallic iron original position.The method of this raising pH also is suitable for preparing in the step (a) of starting soln.According to preferred embodiment, run through present method major part, alkaline pH is avoided, so as in step (c) rising pH, make that most of duration in this step, pH are acid or subacidity slightly.
According to another preferred embodiment, solution is diluted in step (c).According to preferred embodiment, dilute and be at least 20%, more preferably at least 100%, most preferably at least 200%.
According to another preferred embodiment, the temperature of rising solution.According to preferred embodiment, temperature raises 10 ℃ at least, and more preferably at least 30 ℃, most preferably at least 50 ℃.Temperature raises and influenced by any currently known methods, for example contacts the combination of ir radiation, microwave or those methods with hot surface, hot liquid, hot steam.
According to another preferred embodiment, order or carry out two kinds or all three kinds of modifications simultaneously.Therefore,, add basic cpd in the iron salt solutions after the residence time in the aqueous solution, so also make the molysite dilution according to preferred embodiment.According to another preferred embodiment, the solution of molysite contacts with the diluting soln that comprises the water and/or the aqueous solution, and the temperature of described diluting soln according to first preferred embodiment, is preferably up to few 100 ℃ than at least 50 ℃ of iron salt solutions height.According to optional embodiment, the temperature of described diluting soln be about 100 ℃ to 250 ℃, according to preferred embodiment, be 100 ℃ to 180 ℃, and, be 150 ℃ to 250 ℃ according to another preferred embodiment.According to another preferred embodiment, diluting soln comprise with iron ion, its complex compound and/or with the synergistic reagent of the particle that contains iron ion and complex compound thereof.
According to another preferred embodiment, after the residence time, iron salt solutions in step (c) with comprise that this second solution temperature is than iron salt solutions height than molysite second aqueous solution of solute of alkalescence more.According to preferred embodiment, iron salt solutions and described second solution for example mechanically mix in the equipment that is fit to, and described equipment provides intense mixing to reach the homogeneity system rapidly.At least a temperature in those solution surpasses under the situation of boiling point therein, preferably selects mixing equipment, so that it can stand superatmospheric pressure.According to preferred embodiment, implement to mix by for example the iron salt solutions that flows being contacted with mobile second aqueous solution in the plug flow mode.Preferably, the blended logistics remains on formation temperature or remains on by cooling or heat under another temperature that one period short period of time obtains and is less than 1 day, according to an exemplary, and preferred 1 to 60 minute, more preferably 3 to 15 minutes.
When carrying out with single modified method or with array configuration, heating, pH rise and the degree of dilution influences the particulate chemical property that forms.For example, usually, temperature is high more, and the hydration levels of grain fraction is low more.Crystalline form and shape also are affected.Therefore, produce spheroidal particle for embodiment 1 selected condition.
According to preferred embodiment, the finished product oxide compound forms in the step (c) of present method.According to another preferred embodiment, required the finished product are further processed and be converted into to the product of step (c).Therefore according to preferred embodiment, the ironic hydroxide in the particle is converted into pyrrhosiderite or rhombohedral iron ore.
According to preferred embodiment, this further processing comprises heating.Preferably be heated to about 60 ℃ to 800 ℃ temperature.According to preferred embodiment, heating is that the particulate solution that comprises in the step (c) or for example part is removed the formation that obtains after some processing of anhydrating is carried out.According to another preferred embodiment, the particle of formation at first with solution separating.Isolating particle can be handled like this, or is for example being handled after other processing of washing and/or exsiccant.Preferably under superatmospheric pressure and be applicable to finish in solution in the equipment of this pressure and heat.According to preferred embodiment, apply external pressure.The character of heating also is a controlling factor, makes that the effect of heating is different from rapid heating sometimes gradually.According to preferred embodiment, preferably order is carried out step (c) and further heating in same containers.
According to preferred embodiment, the particulate crystalline form of conversion belongs to the common crystalline form of initial particulate, and the particle of described conversion is by described initial particle manufacture.For example bar-shaped pyrrhosiderite particle can be converted into long strip shape rhombohedral iron ore particle, or in another embodiment of the invention, the amorphous granular with low particle dimension ratio can be converted into the pyrrhosiderite with low particle dimension ratio.In another embodiment of the invention, the agglomerate that the agglomerate that has the agglomerate of bar-shaped crystalline form or have a spherical crystalline form can be separately converted to pyrrhosiderite with bar-shaped crystalline form or rhombohedral iron ore particle or have spherical crystalline form.
As will be recognized, the invention provides and produce the sedimentary condition that transforms easily, and the conversion product with high-performance is provided.
According to preferred embodiment, at least one step of method, there is at least a dispersion agent.As used herein, dispersion agent, tensio-active agent, polymkeric substance and rheological reagent are represented and comprised to the term dispersion agent.Therefore, according to preferred embodiment, dispersion agent is introduced wherein dissolving maybe will dissolve the solution of molysite, or join the precursor of solution, for example in the mineral ore.According to another preferred embodiment, during the residence time or after it, dispersion agent is joined in the solution.According to optional embodiment, before or after regulating step, dispersion agent is joined in the solution.According to another preferred embodiment, before step of converting, in the process or add dispersion agent afterwards.According to another preferred embodiment, present method further is included in the concentration and/or the character of modification dispersion agent in the course of processing, and/or the step of adding another kind of dispersion agent.According to preferred embodiment, suitable dispersion agent is for being adsorbed onto the compound on nano particle and/or the nucleating surface.The dispersion agent that is fit to comprises cationic polymers, anionic polymer, non-ionic polymers, tensio-active agent polyion and composition thereof.In this manual, term " dispersion agent " expression can be stablized the particle dispersion of formation, and/or modification forms the mechanism of nano particle, and/or the molecule of structure, performance and the size of any material of forming in forming the nano particle technological process of modification.
According to preferred embodiment, described dispersion agent is selected from diallyl dimethyl ammoniumchloride, sodium cellulose glycolate, polyacrylate, polyoxyethylene glycol, and commercial dispersants, for example Solsperse level, Efka level, Disperbyk or Byk level, Daxad level and Tamol level (trade mark).
According to preferred embodiment, present method further is included at least one method steps process or the step of supersound process solution afterwards.
According to preferred embodiment, present method further is included at least one method steps process or the step of microwave treatment solution afterwards.
According to another preferred embodiment, further processing comprises that ferric oxide in the particle that will form is reduced to Fe (II) by Fe (III) or to metallic iron.According to preferred embodiment, reduction is a part, and according to another preferred embodiment, reduction is near complete.Can use any reductive agent, for example hydrogen.According to preferred embodiment, reduce with independent process, according to optional embodiment, so that particle is converted into the finished product, for example the part of the method for catalyzer is reduced.
According to preferred embodiment, further processing comprises particulate fraction fused into to have the more particle of volume particle size.According to another preferred embodiment, the agglomeration of particles body is carried out mechanical treatment pulverized.
As forming in step (c) or after further transforming, product of the present invention is preferably the small size particle of ferric oxide.According to preferred embodiment, granularity is that 2nm is to 500nm.According to another preferred embodiment, product particulate narrow particle size distribution makes 50% particulate smallest particles that forms and the size ratio between the largest particle less than about 10, is more preferably less than 5, most preferably less than 3.
Form isolating particle according to preferred embodiment.According to another embodiment, partial coalescence at least takes place in the particle of formation.
According to preferred embodiment, most of particle that forms has by what X-ray analysis was measured and is lower than 50% degree of crystallinity.
According to preferred embodiment, in the step (c) or the coating of particles of formation after further transforming be long strip shape, for example aciculiform, clavate or raft shape.
According to another preferred embodiment, particle is sphere or subglobular, makes to have wherein by most of particle that forms the ratio of one dimension and other dimension is less than about 3 structure.
According to preferred embodiment, most of particle that forms has 30m at least
2/ g, more preferably 100m at least
2The surface-area of/g.High surface area grain of the present invention is suitable for Preparation of Catalyst.
Method of the present invention can form high purity ferric oxide by the relative low-purity precursor of the iron ore of for example pyrite or chalcopyrite.According to preferred embodiment, be at least 95% with respect to the purity of other metal, more preferably at least 99%.
According to another preferred embodiment, ferric oxide particles is doped with the ion or the atom of other transition metal.
According to preferred embodiment, obtain particle with the form of the particulate particle that is selected from the particle that is dispersed in the liquid, is carried on particle on the solid compounds, agglomeration is larger particles, partially fused particle, coatedparticles or its combination.
Particle, its goods and/or its converted product are suitable for many industrial application, for example produce pigment, catalyzer, coating, hot coating etc.According to preferred embodiment, in those and other are used, in statu quo use this particle,, this particle is further processed according to another preferred embodiment, according to another preferred embodiment, this particle is formed the part of the preparation material of this type of application.
Ji Zai many methods belong to laboratory character and scale in the literature, for example begin, utilize high dilution solution by high-purity precursor and/or with low capacity and/or low rate work.Method of the present invention is very suitable for attractive economically industrial-scale production.According to preferred embodiment, present method is with 50Kg/ hour at least, and more preferably at least 500Kg/ hour, most preferably at least 5 tons/hours output running.
According to preferred embodiment, because iron salt hydrolysis and form acid thus, sulfuric acid for example, the pH of solution descends in the course of processing.According to preferred embodiment, this acid is reused, and for example for example is used for forming iron salt solutions in the dissolving of iron-bearing mineral.According to another preferred embodiment, the acid of formation is partially or completely neutralized in the course of processing, forms hydrochlorate thus.According to preferred embodiment, this salt has industrial use, for example finishes under the situation of neutralization formation ammonium salt with ammonia therein, is suitable for as fertilizer.
According to optional method, be formed up to the small grain size ferric oxide particles of small part dehydration.This method may further comprise the steps: preparation concentration is the initial aqueous solution that comprises iron ion or its complex compound of 0.1%w/w iron at least, and this solution has at least 1.2 pH; Preparation temperature is greater than 80 ℃ modified aqueous solution; Starting soln is contacted with modified solution, form modified system, and this modified system is remained on greater than under 80 ℃ the temperature 0.5 minute at least.Most of particle that forms has the granularity of about 2nm to about 500nm, and comprises FeOOH, Fe
2O
3, Fe
3O
4Or its combination.
Can use with above-mentioned those similar methods and prepare starting soln.According to preferred embodiment, the concentration of iron in the described starting soln is greater than 2%.According to preferred embodiment, the pH of starting soln is at least 1.5, more preferably at least 1.7.According to optional embodiment, the OH/Fe mol ratio in the starting soln is at least 0.05.According to preferred embodiment, the temperature of modified solution is 100 ℃ to 300 ℃.
According to preferred embodiment, at least one of starting soln and modified solution comprises and can or comprise iron ion or the synergistic reagent of the particle of its complex compound with iron ion, its complex compound.According to preferred embodiment, described reagent is dispersion agent or basic cpd.Use therein basic cpd is preferably ammonia, volatile salt, bicarbonate of ammonia or urea.According to preferred embodiment, in modified solution, should avoid alkaline pH.Preferably, the OH/Fe mol ratio in the solution of described modified system is less than 3, and more preferably 0.5 to 2.
The temperature of modified solution is determined by the temperature of the temperature of starting soln and heat modification solution, their thermal capacitance and their relative quantity.According to preferred embodiment, the temperature of modified solution keeps minimum variation, for example changes being not more than 20 ℃.According to preferred embodiment, modified system kept under its temperature 1 to 30 minute, more preferably 3 to 15 minutes.
According to another preferred embodiment, starting soln with keep one period preliminary residence time before modified solution carries out described the contact.Preferably, during the preliminary residence time, solution be lower than 55 ℃ temperature and greater than 1.5 pH under leave standstill.The time length of the preliminary residence time is enough to make pH to be reduced by at least 0.2 unit, but according to preferred embodiment, is no more than 14 days.
According to preferred embodiment, the particle that forms in the processing is selected from each step of disperseing described particle, adding carrier, thermal treatment, mixing, vaporize water, spraying drying, thermospray and combination thereof.
According to the preferred embodiments of the invention, preparation concentration is at least a initial aqueous solution in iron ion and the complex compound thereof of comprising of 0.1%w/w iron at least, and this solution has at least 1.2 pH.
Temperature contacts in mixing section with starting soln in a continuous manner greater than 80 ℃ modified aqueous solution, forms modified system.Mixing section guarantees that with a kind of the also effective fast blended mode of solution makes up.Modified solution is discharged in the plug flow mode from mixing section.Finish precipitation in the plug flow process, or in a further preferred embodiment, during plug flow, do not discharge solution, and in another container, continue precipitation.
Preferred utilization enters the flow velocity of solution or mixes in mixing section by use mechanically mixing mode or other hybrid mode.
In a preferred embodiment, the temperature in temperature in the mixing section and the plug flow process is close.In a further preferred embodiment, the temperature of solution is higher than the temperature in the mixing section in the plug flow process, and in another preferred embodiment, the temperature of solution is lower than the temperature in the mixing section in the plug flow process.
In a preferred embodiment of the invention, the residence time in the mixing section is lower than about 5 minutes, and more preferably the residence time is lower than 1 minute.In being more preferably embodiment, the residence time in the mixing section is lower than about 5 seconds, and in particularly preferred embodiment, the residence time is lower than 1 second.
In a preferred embodiment of the invention, the solution that leaves plug flow enters container.In more preferred of the present invention, the solution in the container mixes.
Though some preferred embodiment in inciting somebody to action is with the following Examples now described the present invention, so that can more fully understand and understand its each side, does not wish to limit the invention to these particular.On the contrary, it is used for containing all possibilities, improvement project and the equivalent that can be included in the scope of the invention that is defined by the following claims.Therefore, the following examples that comprise preferred embodiment are used for illustrating actually operating of the present invention, details shown in should understanding only is to be used for for example and to discuss for the illustrative of the preferred embodiment of the invention, and in order to provide anything to be considered to the most useful and provide, and understand the explanation of preparation steps and the explanation of the principle of the invention and notion aspect easily.
Embodiment 1
By in water, dissolving Fe
2(SO
4)
3Crystal is also regulated pH to 2.3 preparation 0.25MFe with ammonia
2(SO
4)
3100g fresh solution (about 2.8% iron).Solution was placed 1 hour down at 25 ℃.The pH that reaches is 1.9.
By in the violent churned mechanically while of 600rpm, solution joined in 80 ℃ the 900g water, described water diluting soln, heated solution also improves its pH, thus the condition in the regulator solution.After 10 minutes, stop to mix.Observe particle.After the sedimentation 1 hour, remove the clarification liquid phase.Wash throw out with water 3 times, then centrifugal treating.
The material that obtains is the Fe (OH) of ultra-fine single dispersed powders form
3The SEM photo shows epigranular and is about 45nm that average dimension ratio is about 1.5.This particle has sphere.
Embodiment 2
As embodiment 1, preparation 0.25M Fe
2(SO
4)
3The 100g fresh solution, and under 25 ℃, leave standstill.In the violent churned mechanically while of 600rpm, solution joined to form pressure be in 122 ℃ the 900g water in the about 2 atmospheric pressurized vessels.After 30 minutes, stop to mix and observing particle.Make the particle suspension liquid cool to room temperature and observe throw out.Sediment separate out also washes with water 3 times, then centrifugal treating.
The material that obtains is the form D eOOH of ultra-fine single dispersed powders.Particle is that spherical and average dimension ratio is about 1.5.
Embodiment 3
Repeat the step among the embodiment 1, have a difference.900g hot water contain 0.1% dispersion agent a part amount be 200000 to 300000 poly-(diallyldimethylammonium chloride) (PDAC).After 10 minutes, stop to mix.Observe particle suspension liquid.Not sedimentation of particle during leaving standstill 1 hour.As embodiment 1, also washed by the centrifugal treating separating particles.Particle that forms and among the embodiment 1 those are similar.
Embodiment 4
By in water, dissolving Fe
2(SO
4)
3Crystal prepares 0.25M Fe
2(SO
4)
31000g fresh solution (about 2.8% iron).In the 100g liquor sample, add ammonia, reach NH
3/ Fe mol ratio is 1.Solution is placed the different residence time (T down at 25 ℃
Ret).
After the residence time, the ach of the solution of formation mixes with the 900g water that contains 0.25% dispersion agent (PDAC) in some cases under differing temps, and follows the violent mechanical stirring of 600rpm to remain in the Parr equipment (high pressure vessel).After 5 minutes, stop to stir.Observe particle and by centrifugal treating and solution separating.Wash throw out with water 3 times, then centrifugal treating.
Analyze the water-content of gained material by thermogravimetry (TGA), and pass through the SEM photo and analyze the gained material.The result provides in table 1.
Table 1
| The residence time | Temperature | Whether there is dispersion agent | The particle crystalline form | Mean particle size nm | Deviation (50%) * | Remarks |
| My god | (℃) | |||||
| 7 | 150 | Not | Even clavate | 13×53 | (47-60)× (11-16) | Sphere aggregates |
| 7 | 150 | Be | Clavate | 15.5×60 | (57-63)× (13-18) | |
| 14 | 150 | Not | Sphere with the clavate arrangement | 13 | 11-15 | The sphere aggregates of 300-600nm |
| 14 | 150 | Be | Spherical | 13 | 11-15 | The sphere aggregates of 100-500nm |
The particulate size range that is about mean particle size (nm) of deviation (50%) *=50%.
* the particle in the non-dispersant sample condenses with aggregate form, and those are attached to each other with having loose particles in the sample of dispersion agent
Embodiment 5
By in water, dissolving Fe
2(SO
4)
3The Fe of crystal preparation 25%
2(SO
4)
3The 1000g fresh solution.In the 100g liquor sample, add ammonia, reach different N H
3/ Fe mol ratio.Solution is placed the different residence time (T down at 25 ℃
Ret).
After the residence time, the ach of solution is joined in 85 ℃ the 900g water that contains 0.1% dispersion agent (PDAC), simultaneously vigorous stirring.After 10 minutes, stop to stir.Observe particle.Remove solution and centrifugal treating.Wash throw out with water 3 times, then centrifugal treating.
The material that obtains by the analysis of SEM photo.The result provides in table 2.
Table 2
| Initial Fe solution | Crystalline form | Granularity | Size-grade distribution | |||
| NH 3/Fe | Fe 2(SO 4) 3 | T ret | PDAC | |||
| wt％ | min | |||||
| 1.75 | 25 | 13 | + | Spherical | 20 | Narrow |
| 1.50 | 25 | 13 | + | Spherical | 80-100 | Narrow |
The comparative example A
By mixing some different N H
325% Fe of/Fe ratio and different incubation times
2(SO
4)
325% the Fe that three kinds of formulations prepared from solutions are different
2(SO
4)
3Solution.
Every kind of 15g of three kinds of solution joined in 90 ℃ the 135g water, simultaneously vigorous stirring.After 5 minutes, stop to mix.Under all three kinds of situations, all observe particle.Remove solution by centrifugal treating.Wash throw out 3 times and centrifugal treating with water.
The material that obtains by the analysis of SEM photo.In all cases, particle is the distortion clavate that volume particle size distributes.
Embodiment 6
By in water, dissolving Fe
2(SO
4)
3Crystal prepares 0.21M Fe
2(SO
4)
3The 1000g fresh solution.Described in table 3, the ammonia of difference amount is joined in the 25g liquor sample.Solution is placed the different residence time (T down at 25 ℃
Ret).
Pumping 225g water section enters the 0.25ml mixing section through the heat exchanger that is arranged in 150 ℃ or 190 ℃ oil baths.Every kind of Fe of 25g after stopping
2(SO
4)
3Simultaneous pumping is gone in this identical mixing section, and it mixes the formation modified solution with preheating water therein.Every kind of modified solution flows through 50ml heat pipe (being arranged in identical oil bath) then and enters Parr equipment (high pressure vessel), and wherein temperature remains on the temperature identical with oil bath and mixing section.After other 5 minutes, stop to mix, from Parr, discharge solution and cooling.Solution is carried out from handling and remove the clarification liquid phase.Wash throw out 3 times and centrifugal treating with water.
Water-content of the material that analysis obtains (TG) and the material that obtains by sem analysis.The result provides in table 3.
Table 3
| T ret | NH 3/Fe | T | Mean particle size | Deviation (50%) * | Crystalline form | Remarks | Product |
| mol/mol | (℃) | nm | nm | ||||
| 1h | 0.3 | 95 | 69×25 | (60-81) ×(15-26) | Stub shape | Raft shape aggregate | Fe(OH) 3 |
| 1h | 0.59 | 95 | 62×14 | (59-65) ×(13-16) | Spherical | The aggregate of 80-200nm | Fe(OH) 3 |
| 1h | 1.02 | 95 | 10 | 9-11.0 | Spherical | Net formula bunch | Fe(OH) 3 |
| 1h | 0.3 | 150 | 60×18 | (53-68) ×(12-20) | Clavate | The uniform aggregate of granularity and shape | |
| 1h | 0.59 | 150 | 52×19 | (48-64) ×(15-22) | Clavate | ||
| 1h | 1.02 | 150 | 22 | 18-27 | Spherical | FeOOH | |
| 5 days | 0.3 | 95 | 79×12 | (70-79) ×(9-14) | Spicule | Spicule bunch | Fe(OH) 3 |
| 5 days | 0.59 | 95 | 37×12 | (33-44) ×(11-13) | Clavate | Extremely uniform small rod | Fe(OH) 3 |
| 5 days | 0.3 | 150 | 35 | 31-38 | Spherical | The sphere aggregates of about 100nm | |
| 5 days | 1.01 | 150 | Spherical | Fe 2O 3 | |||
| 1.02 | 190 | 29 | 22-41 | Spherical | The sphere aggregates of about 100nm | Fe 2O 3 | |
| 5 days | 0 | 190 | 11 | 10-14 | Spherical | Fe 2O 3 |
Deviation (50%)
*=50% the particulate size range that is about mean particle size (nm).
Embodiment 7
By in water, dissolving Fe
2(SO
4)
3Crystal prepares 0.25M Fe
2(SO
4)
3100g fresh solution (about 2.8% iron).(Reillex 425 to add weak anion exchanger
Tm), make pH rise to 2.5.Solution was placed 1 hour down at 25 ℃.The pH that reaches is 2.0.
By in the 600rpm vigorous stirring, solution joined in 80 ℃ the 900g water, described water diluting soln, heated solution also improves its pH, thus the condition in the regulator solution.After 10 minutes, stop to mix.Observe particle.After the sedimentation 1 hour, remove the clarification liquid phase.Wash throw out with water 3 times, then centrifugal treating.
The material that obtains is the Fe (OH) of ultra-fine single dispersed powders form
3The SEM photo shows that particle is spherical, has the uniform particle size of about 40nm.
It will be apparent to one skilled in the art that, the present invention is not limited to the details of above-mentioned illustrative embodiment, the present invention can be embodied in other particular form that does not break away from its essential characteristic, and therefore wish that non-limiting form takes in illustrative in every respect for the present embodiment and embodiment, with reference to claims rather than above-mentioned specification sheets, therefore wish and to be included in wherein in the equivalent scope of claim and all changes in the implication.
(according to the modification of the 19th of treaty)
[international office was received on July 5th, 2006 (05.07.2006)]
1. method that forms the small grain size ferric oxide particles may further comprise the steps:
A) preparation concentration for 0.1w/w iron at least and pH greater than about 1.5 the fresh initial aqueous solution at least a in iron ion and the complex compound thereof that comprises, and the solution of described prepared fresh is remained below next section of temperature residence time of 55 ℃ contain the system of modified solution with formation, hydrolysis takes place in this residence time, the degree of described hydrolysis is enough to make at least 0.2 unit of pH decline, and the wherein said time is no more than 14 days; With
B) regulate condition in the described system by at least one of following steps:
I) heat described modified solution, its temperature is raise 10 ℃ at least;
Ii) make at least 0.3 unit of pH rising of described modified solution; With
Iii) with described modified solution dilution at least 20%;
Form particle thus, wherein most of particulate granularity that forms is that 2nm is to 500nm.
2. according to the process of claim 1 wherein that solution kept 0.5 minute at least under the condition of described adjusting.
3. carry out according to the process of claim 1 wherein that being adjusted in of described condition is lower than in 1 hour the process.
4. according to the method for claim 1, be further characterized in that most of particle that forms has and be lower than 50% degree of crystallinity.
5. according to the method for claim 1, be further characterized in that the particulate of at least 50% formation is characterised in that the size ratio between smallest particles and the largest particle is lower than 10: 1.
6. according to the method for claim 1, be further characterized in that the particulate of at least 50% formation is characterised in that the size ratio between smallest particles and the largest particle is lower than 5: 1.
7. according to the method for claim 1, be further characterized in that most of particle that forms has the structure that is different from long strip shape.
8. according to the method for claim 1, be further characterized in that most of particle that forms has 30m at least
2The surface-area of/g.
9. according to the method for claim 1, further may further comprise the steps:
C) under 60 ℃ to 800 ℃ dehydration temperaturre, make the particle dehydration of described formation to form the particle of dehydration.
10. according to the method for claim 9, wherein said dehydration is carried out under superatmospheric pressure.
11. according to the method for claim 9, wherein said dehydrating step and described regulating step carry out simultaneously.
12., wherein regulate and comprise and be heated to dehydration temperaturre according to the method for claim 11.
13., be further characterized in that the particle of most of dehydration has the structure that is different from long strip shape according to the method for claim 9.
14., be further characterized in that the particle of most of dehydration has 30m at least according to the method for claim 9
2The surface-area of/g.
15. according to the method for claim 12, wherein said particle is selected from pyrrhosiderite, rhombohedral iron ore and magnetite.
16. according to the process of claim 1 wherein that described oxide compound has the chemical formula of FeOOH.
17. according to the process of claim 1 wherein that described oxide compound has Fe (OH)
3Chemical formula.
18. according to the process of claim 1 wherein that the preparation of the described aqueous solution comprises at least a in oxidized metal iron, iron protoxide ion, sulfur oxide ion, dissolved iron compound and the acidifying iron salt solutions.
19. according to the method for claim 18, the oxygenant that is selected from oxygen, hydrogen peroxide, nitric acid, nitrate and combination thereof is used in wherein said oxidation.
20. according to the method for claim 18, wherein said oxidation is by chemistry or biology catalysis.
21. method according to claim 18, mineral of wherein said iron cpd chosen from Fe oxide compound, iron hydroxide, oxides-containing iron or iron hydroxide and composition thereof, and wherein said compound is dissolved in acidic solution, and described acidic solution comprises the acid that is selected from sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, organic acid, its acid salt and combination thereof.
22. according to the process of claim 1 wherein that the aqueous solution of described preparation comprises the negatively charged ion that is selected from vitriol, muriate, nitrate, phosphoric acid salt, organic acid and composition thereof.
23. according to the process of claim 1 wherein that the most of negatively charged ion in the initial aqueous solution of described preparation is a sulfate anion.
24. according to the process of claim 1 wherein the preparation solution in concentration of iron greater than 5%.
25. according to the process of claim 1 wherein that at least 80% the course of processing, the pH of solution is less than 6.
26. according to the process of claim 1 wherein that the pH of the middle solution of step (a) remains on 2 to 3 during at least a portion residence time of step (a).
27. according to the process of claim 1 wherein that the pH of the described aqueous solution is 1.5 to 4 according to the time durations of step (b) regulation system condition wherein at least a portion.
28. according to the method for claim 1, further be included in described regulating step (b) afterwards, remove in the described particle suspension liquid step of portion water at least.
29., comprise at least two heating stepses according to the method for claim 1.
30. according to the method for claim 1, further comprise the particle that grinds described formation and sieve described formation particulate at least one.
31., further comprise the iron ion in the particle of the described formation of partial reduction at least according to the method for claim 1.
32. according to the process of claim 1 wherein that at least a dispersion agent is present at least one step of preparation, maintenance, promotion, dehydration and grinding.
33. according to the method for claim 32, wherein said at least a dispersion agent is selected from cationic polymers, anionic polymer, non-ionic polymers, tensio-active agent and composition thereof.
34., further comprise the step of the amount of regulating described at least a dispersion agent according to the method for claim 32.
35. according to the process of claim 1 wherein that solution is with at least a processing the in the ultrasonic and microwave.
36. the product that the ferric oxide particles that forms according to the method for claim 1 and their transform.
37. the ferric oxide particles of claim 36 is characterised in that the purity with respect to other metal is at least 95%.
38. the ferric oxide particles of claim 36, be characterised in that have the sphere of being selected from, the shape of clavate and raft shape.
39. the ferric oxide particles of claim 36 is characterised in that the atom that is doped with other compound.
40. goods comprise the described ferric oxide particles according to the method preparation of claim 1.
41. according to the goods of claim 39, wherein said particles dispersed in liquid, be carried on the solid compounds, particle that agglomeration is larger particles, partially fused, coated or its combination.
42. the method for the goods of production claim 40 comprises being selected from the step of disperseing described particle, adding carrier, thermal treatment, mixing, water evaporation, spraying drying, thermospray and combination thereof.
43. a method comprises at least a as pigment in the described goods of the described particle that uses claim 36 and claim 40.
44. a method is included in the catalyzer at least a in the described goods of the described particle that uses claim 36 and claim 40.
45. a method is included in the coating at least a in the described goods of the described particle that uses claim 36 and claim 40.
46. according to the particulate industrial production of claim 36, wherein particle forms with 50Kg/ hour at least output.
47. a method that forms pigment comprises the step of claim 1.
48. a method that forms catalyzer comprises the step of claim 1.
49. a method that forms the small grain size ferric oxide particles may further comprise the steps:
A) preparation comprises the fresh initial aqueous solution at least a in iron ion and the complex compound thereof, and concentration is 0.1%w/w iron at least, and this solution has at least 1.2 pH;
B) preparation temperature is greater than 80 ℃ modified aqueous solution;
C) starting soln is contacted with modified solution, form modified system;
D) with the plug flow mode from mixing section shift out modified solution and
This method feature is:
I. the residence time in the mixing section is lower than about 1 minute,
Ii. form particle or its aggregate, wherein most of particulate granularity that forms is that 2nm is to 500nm; With
Iii. the particle of Xing Chenging comprises FeOOH, Fe
2O
3, Fe (OH)
3, Fe
3O
4Or its combination.
50. according to the method for claim 49, the concentration of iron in the wherein said starting soln is greater than 2%.
51. according to the method for claim 49, at least a reagent that is selected from dispersion agent and basic cpd that comprises in wherein said fresh starting soln and the described modified solution.
52. according to the method for claim 51, wherein basic cpd is selected from ammonia, volatile salt, bicarbonate of ammonia and urea.
53. according to the method for claim 51, the OH/Fe mol ratio in the solution of wherein said modified system is less than 3.
54. according to the method for claim 51, the OH/Fe mol ratio in the solution of wherein said modified system is 0.5 to 2.
55. according to the method for claim 49, wherein the temperature of modified solution is 100 ℃ to 300 ℃.
56. according to the method for claim 49, wherein said modified system maintains and is lower than under the 100 atmospheric pressure.
57. according to the method for claim 56, the time length of wherein keeping this modified system is 1 to 30 minute.
58. according to the method for claim 56, in the wherein said maintenance process, temperature remains on from the temperature of modified system and starts at, within 20 ℃ the scope.
59. method according to claim 49, further be included in before the described contact, the initial aqueous solution of prepared fresh is maintained the temperature that is lower than 55 ℃ and is enough to make pH to be reduced by at least the preliminary residence time of 0.2 unit greater than next section of pH of 1.5, and the wherein said preliminary residence time is no more than 14 days.
60. according to the method for claim 49, wherein the residence time in mixing section is lower than 5 seconds.
61. according to the method for claim 49, wherein the residence time in mixing section is lower than 0.5 second.
62., wherein the modified system that shifts out was kept 0.5 minute at least according to the method for claim 49.
63. the product that the ferric oxide particles that forms according to the method for claim 49 and their transform.
64. the ferric oxide particles of claim 63 is characterised in that the purity with respect to other metal is at least 95%.
65. the ferric oxide particles of claim 63, be characterised in that have the sphere of being selected from, the shape of clavate and raft shape.
66. the ferric oxide particles of claim 63 is characterised in that the atom that is doped with other compound.
67. goods comprise the described ferric oxide particles according to the method preparation of claim 49.
68. according to the goods of claim 67, wherein said particles dispersed in liquid, be carried on the solid compounds, particle that agglomeration is larger particles, partially fused, coated or its combination.
69., be further characterized in that the particulate of at least 50% formation is characterised in that the size ratio between smallest particles and the largest particle is lower than 10: 1 according to the method for claim 49.
70., be further characterized in that the particulate of at least 50% formation is characterised in that the size ratio between smallest particles and the largest particle is lower than 5: 1 according to the method for claim 49.
71., be further characterized in that most of particle that forms has 30m at least according to the method for claim 49
2The surface-area of/g.
Claims (68)
1. method that forms the small grain size ferric oxide particles may further comprise the steps:
A) preparation concentration for 0.1w/w iron at least and pH greater than about 1.5 at least a initial aqueous solution in iron ion and the complex compound thereof of comprising;
B) described solution being remained below next section of temperature residence time of 55 ℃ contains the system of modified solution with formation, in this residence time hydrolysis takes place, and the degree of described hydrolysis is enough to make pH at least 0.2 unit that descends, and the wherein said time is no more than 14 days; With
C) regulate condition in the described system by at least one of following steps:
I) heat described modified solution, its temperature is raise 10 ℃ at least;
Ii) make at least 0.3 unit of pH rising of described modified solution; With
Iii) with described modified solution dilution at least 20%;
Form particle thus, wherein most of particulate granularity that forms arrives about 500nm for about 2nm.
2. according to the process of claim 1 wherein that solution kept 0.5 minute at least under the condition of described adjusting.
3. carry out according to the process of claim 1 wherein that being adjusted in of described condition is lower than in 1 hour the process.
4. according to the method for claim 1, be further characterized in that most of particle that forms has and be lower than 50% degree of crystallinity.
5. according to the method for claim 1, be further characterized in that the particulate smallest particles of 50% formation and the size ratio between the largest particle are lower than about 10.
6. according to the method for claim 1, be further characterized in that the particulate smallest particles of 50% formation and the size ratio between the largest particle are lower than about 5.
7. according to the method for claim 1, be further characterized in that most of particle that forms has the structure that is different from long strip shape.
8. according to the method for claim 1, be further characterized in that most of particle that forms has 30m at least
2The surface-area of/g.
9. according to the method for claim 1, further may further comprise the steps:
Iv) under about 800 ℃ dehydration temperaturre, make the particle dehydration of described formation to form the particle of dehydration at about 60 ℃.
10. according to the method for claim 9, wherein said dehydration is carried out under superatmospheric pressure.
11. according to the method for claim 9, wherein said dehydrating step and described regulating step carry out simultaneously.
12., wherein regulate and comprise and be heated to dehydration temperaturre according to the method for claim 11.
13., be further characterized in that the particle of most of dehydration has the structure that is different from long strip shape according to the method for claim 9.
14., be further characterized in that the particle of most of dehydration has 30m at least according to the method for claim 9
2The surface-area of/g.
15. according to the method for claim 12, wherein said particle is selected from pyrrhosiderite, rhombohedral iron ore and magnetite.
16. according to the process of claim 1 wherein that described oxide compound has the chemical formula of FeOOH.
17. according to the process of claim 1 wherein that described oxide compound has the chemical formula of Fe (OH) 3.
18. according to the process of claim 1 wherein that the preparation of the described aqueous solution comprises at least a in oxidized metal iron, iron protoxide ion, sulfur oxide ion, dissolved iron compound and the acidifying iron salt solutions.
19. according to the method for claim 18, the oxygenant that is selected from oxygen, hydrogen peroxide, nitric acid, nitrate and combination thereof is used in wherein said oxidation.
20. according to the method for claim 18, wherein said oxidation is by chemistry or biology catalysis.
21. method according to claim 18, mineral of wherein said iron cpd chosen from Fe oxide compound, iron hydroxide, oxides-containing iron or iron hydroxide and composition thereof, and wherein said compound is dissolved in acidic solution, and described acidic solution comprises the acid that is selected from sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, organic acid, its acid salt and combination thereof.
22. according to the process of claim 1 wherein that the aqueous solution of described preparation comprises the negatively charged ion that is selected from vitriol, muriate, nitrate, phosphoric acid salt, organic acid and composition thereof.
23. according to the process of claim 1 wherein that the most of negatively charged ion in the initial aqueous solution of described preparation is a sulfate anion.
24. according to the process of claim 1 wherein the preparation solution in concentration of iron greater than about 5%.
25. according to the process of claim 1 wherein that at least 80% the course of processing, the pH of solution is less than 6.
26. according to the process of claim 1 wherein that the pH of the middle solution of step (b) is maintained at about 2 to about 3 at least a portion step (b) process.
27. according to the process of claim 1 wherein that the pH of the described aqueous solution is about 1.5 to about 4 in the described regulating step of at least a portion.
28. according to the method for claim 9, further be included in after the described promotion, remove in the described particle suspension liquid step of portion water at least.
29., comprise at least two heating stepses according to the method for claim 1.
30. according to the method for claim 1, further comprise the particle that grinds described formation and sieve described formation particulate at least one.
31., further comprise the iron ion in the particle of the described formation of partial reduction at least according to the method for claim 1.
32. according to the process of claim 1 wherein that at least a dispersion agent is present at least one step of preparation, maintenance, promotion, dehydration and grinding.
33. according to the method for claim 32, wherein said at least a dispersion agent is selected from cationic polymers, anionic polymer, non-ionic polymers, tensio-active agent and composition thereof.
34., further comprise the step of the amount of regulating described at least a dispersion agent according to the method for claim 32.
35. according to the process of claim 1 wherein that solution is with at least a processing the in the ultrasonic and microwave.
36. the product that the ferric oxide particles that forms according to the method for claim 1 and their transform.
37. the ferric oxide particles of claim 36 is characterised in that the purity with respect to other metal is at least 95%.
38. the ferric oxide particles of claim 36, be characterised in that have the sphere of being selected from, the shape of clavate and raft shape.
39. the ferric oxide particles of claim 36 is characterised in that the atom that is doped with other compound.
40. goods comprise the described ferric oxide particles according to the method preparation of claim 1.
41. according to the goods of claim 39, wherein said particles dispersed in liquid, be carried on the solid compounds, particle that agglomeration is larger particles, partially fused, coated or its combination.
42. the method for the goods of production claim 40 comprises being selected from the step of disperseing described particle, adding carrier, thermal treatment, mixing, water evaporation, spraying drying, thermospray and combination thereof.
43. a method comprises and uses at least a as pigment in described particle and the described goods.
44. a method is included in the catalyzer and uses at least a in described particle and the described goods.
45. a method is included in the coating and uses at least a in described particle and the described goods.
46. the particulate industrial production of each that requires according to aforesaid right, wherein particle forms with 50Kg/ hour at least output.
47. a method that forms pigment comprises the step of claim 1.
48. a method that forms catalyzer comprises the step of claim 1.
49. a method that forms the small grain size ferric oxide particles may further comprise the steps:
A) preparation comprises at least a initial aqueous solution in iron ion and the complex compound thereof, and concentration is 0.1%w/w iron at least, and this solution has at least 1.2 pH;
B) preparation temperature is greater than 80 ℃ modified aqueous solution;
C) starting soln is contacted with modified solution, form modified system;
D) with the plug flow mode from mixing section shift out modified solution and
This method feature is:
I. the residence time in the mixing section is lower than about 1 minute,
Ii. form particle or its aggregate, wherein most of particulate granularity that forms arrives about 500nm for about 2nm; With
Iii. the particle of Xing Chenging comprises FeOOH, Fe
2O
3, Fe (OH)
3, Fe
3O
4Or its combination.
50. according to the method for claim 49, the concentration of iron in the wherein said starting soln is greater than 2%.
51. according to the method for claim 49, at least a reagent that is selected from dispersion agent and basic cpd that comprises in wherein said starting soln and the described modified solution.
52. according to the method for claim 51, wherein basic cpd is selected from ammonia, volatile salt, bicarbonate of ammonia and urea.
53. according to the method for claim 51, the OH/Fe mol ratio in the solution of wherein said modified system is less than 3.
54. according to the method for claim 51, the OH/Fe mol ratio in the solution of wherein said modified system is 0.5 to 2.
55. according to the method for claim 49, wherein the temperature of modified solution is 100 ℃ to 300 ℃.
56. according to the method for claim 49, wherein said modified system maintains and is lower than under the 100 atmospheric pressure.
57. according to the method for claim 49, the time length of wherein keeping this modified system is 1 to 30 minute.
58. according to the method for claim 49, in the wherein said maintenance process, temperature remains on from the temperature of modified system and starts at, within 20 ℃ the scope.
59. method according to claim 49, further be included in before the described contact, the initial aqueous solution of preparation is maintained the temperature that is lower than 55 ℃ and is enough to make pH to be reduced by at least the preliminary residence time of 0.2 unit greater than next section of pH of 1.5, and the wherein said preliminary residence time is no more than 14 days.
60. according to the method for claim 49, wherein the residence time in mixing section is lower than about 5 seconds.
61. according to the method for claim 49, wherein the residence time in mixing section is lower than about 0.5 second.
62., wherein the modified system that shifts out was kept 0.5 minute at least according to the method for claim 49.
63. the product that the ferric oxide particles that forms according to the method for claim 49 and their transform.
64. the ferric oxide particles of claim 63 is characterised in that the purity with respect to other metal is at least 95%.
65. the ferric oxide particles of claim 63, be characterised in that have the sphere of being selected from, the shape of clavate and raft shape.
66. the ferric oxide particles of claim 63 is characterised in that the atom that is doped with other compound.
67. goods comprise the described ferric oxide particles according to the method preparation of claim 49.
68. according to the goods of claim 67, wherein said particles dispersed in liquid, be carried on the solid compounds, particle that agglomeration is larger particles, partially fused, coated or its combination.
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| IL169384 | 2005-06-23 |
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| IL162742A (en) | 2008-12-29 |
| IL162742A0 (en) | 2005-11-20 |
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