CN108726575A - The method for preparing nanometer di-iron trioxide iron oxide red as raw material using rutile mether liquor - Google Patents
The method for preparing nanometer di-iron trioxide iron oxide red as raw material using rutile mether liquor Download PDFInfo
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- CN108726575A CN108726575A CN201810489762.0A CN201810489762A CN108726575A CN 108726575 A CN108726575 A CN 108726575A CN 201810489762 A CN201810489762 A CN 201810489762A CN 108726575 A CN108726575 A CN 108726575A
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- China
- Prior art keywords
- iron oxide
- oxide red
- iron
- rutile mether
- mether liquor
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 65
- 239000002994 raw material Substances 0.000 title claims abstract description 30
- WGRVPNPDKUHAOL-UHFFFAOYSA-N [O-2].[O-2].[O-2].O.[Fe+2].[Fe+2].[Fe+2] Chemical compound [O-2].[O-2].[O-2].O.[Fe+2].[Fe+2].[Fe+2] WGRVPNPDKUHAOL-UHFFFAOYSA-N 0.000 title claims abstract description 22
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 266
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 26
- 230000001376 precipitating effect Effects 0.000 claims abstract description 26
- 239000013049 sediment Substances 0.000 claims abstract description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 239000002270 dispersing agent Substances 0.000 claims abstract description 17
- 239000012141 concentrate Substances 0.000 claims description 61
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 claims description 60
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 230000009467 reduction Effects 0.000 claims description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000002955 isolation Methods 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 72
- 238000005516 engineering process Methods 0.000 abstract description 19
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical compound [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 abstract description 16
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003889 chemical engineering Methods 0.000 abstract description 4
- 230000033228 biological regulation Effects 0.000 abstract description 2
- 238000004663 powder metallurgy Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 91
- 239000000243 solution Substances 0.000 description 66
- 229910052742 iron Inorganic materials 0.000 description 26
- 150000002505 iron Chemical class 0.000 description 21
- -1 Iron ion Chemical class 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 13
- 150000002431 hydrogen Chemical class 0.000 description 12
- 230000008859 change Effects 0.000 description 11
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 11
- 239000004094 surface-active agent Substances 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 230000033116 oxidation-reduction process Effects 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 238000010792 warming Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 235000011121 sodium hydroxide Nutrition 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000012452 mother liquor Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000001507 sample dispersion Methods 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229920000428 triblock copolymer Polymers 0.000 description 3
- 239000012491 analyte Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 206010068052 Mosaicism Diseases 0.000 description 1
- 241000736199 Paeonia Species 0.000 description 1
- 235000006484 Paeonia officinalis Nutrition 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- ONTQJDKFANPPKK-UHFFFAOYSA-L chembl3185981 Chemical compound [Na+].[Na+].CC1=CC(C)=C(S([O-])(=O)=O)C=C1N=NC1=CC(S([O-])(=O)=O)=C(C=CC=C2)C2=C1O ONTQJDKFANPPKK-UHFFFAOYSA-L 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004094 preconcentration Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- WPPDXAHGCGPUPK-UHFFFAOYSA-N red 2 Chemical compound C1=CC=CC=C1C(C1=CC=CC=C11)=C(C=2C=3C4=CC=C5C6=CC=C7C8=C(C=9C=CC=CC=9)C9=CC=CC=C9C(C=9C=CC=CC=9)=C8C8=CC=C(C6=C87)C(C=35)=CC=2)C4=C1C1=CC=CC=C1 WPPDXAHGCGPUPK-UHFFFAOYSA-N 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 210000003765 sex chromosome Anatomy 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/10—Halides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Compounds Of Iron (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to the methods for preparing nanometer di-iron trioxide iron oxide red as raw material using rutile mether liquor, include the following steps：(1)：Rutile mether liquor is taken, sequentially adds dispersant and precipitating reagent thereto to get to sediment iron oxide red presoma；(2)：Iron oxide red presoma in step (1) is transferred in hydrothermal reactor, hydro-thermal reaction, is filtered, washed, dries to get to nanometer di-iron trioxide iron oxide red product.Compared with prior art, the present invention prepares serial high added value nanometer Fe using technology of chemical engineering, nanotechnology and Jie's scale regulation and control method2O3Iron oxide red product, synthesis technology is simple, be easy it is extensive prepare, product colour is from pale red to deep brown red, choice is provided to the selection of new product to user.The technology of the present invention updates prior powder metallurgy enterprise technology, the high-end iron oxide red technology blockage of breaks through foreign and promotion china natural resources clean utilization are of great significance.
Description
Technical field
The invention belongs to nanometer di-iron trioxide iron oxide red preparing technical fields, are related to one kind using rutile mether liquor as raw material system
The method of standby nanometer di-iron trioxide iron oxide red.
Background technology
Synthetic rutile refers to being separated most of ferrous components in ilmenite concentrate using chemical method, obtains one kind and exists
Ingredient and structural behaviour rich titanium material identical with natural rutile, main group become TiO2, content wave between 91-96%
It is dynamic.Titanium and iron content are higher in usual ilmenite concentrate, and ratio is close to 1:1 or so, also contain the impurity such as a small amount of manganese, chromium, in people
It makes in rutile production process, a large amount of ferrous components enter solution with ferrous iron or ferric form in ilmenite concentrate, form a large amount of gold
Red stone mother liquor.
Present traditional technology method is by rutile mether liquor concentration, crystallization, purification, ammonium hydrogen carbonate double hydrolysis, coating, calcinings
Fe is prepared in equal technological processes2O3Iron oxide red pigment.Traditional technology method there are technology paths it is complicated, of high cost and prepare
Fe2O3The problems such as iron oxide red product color is poor, composition content is low.The Fe prepared using conventional method2O3Iron oxide red product is mostly low side
Fe2O3Iron oxide red product, for price at 3000-5000 yuan/ton, production cost can sometimes reach 5500-6000 yuan/ton or so.
Therefore, because a large amount of rutile mether liquors generated during Production of Artificial Rutile, according to national discharge of wastewater mark
Quasi- rutile mether liquor can not direct emission, if conventionally method prepares low side Fe2O3Iron oxide red product, enterprise face again
Lose awkward situation.Meanwhile high-end iron oxide red production technology mainly rest in external Ji Jia major companies on hand (for example, Bayer A.G,
Fei Ze companies of the U.S. and Reichard companies of the U.S. etc.), if introduction of foreign technology, expense is again very high.
China ZL201310111493.1 of the present invention discloses a kind of processing method of artificial rutile mether liquor, first will be artificial
Rutile mether liquor carries out heating pre-concentration, makes Fe in mother liquor3+Mixing source of iron is in logical HCl gases after concentration is increased to 150g/L or more
Fluidized-bed reactor in react, improve the concentration of iron of mother liquor, then filter acid hydrolysis solution, freezing and crystallizing obtains ferric trichloride crystalline substance
Body finally roasts crystal and obtains high-grade iron oxide red.The above-mentioned method for preparing iron oxide red using rutile mether liquor, which still remains, to be prepared
Journey is complicated, the not high problem of technology stability.
Invention content
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind with rutile mether liquor
For the method that raw material prepares nanometer di-iron trioxide iron oxide red, method is regulated and controled using technology of chemical engineering, nanotechnology and Jie's scale,
High-end nanometer Fe is prepared by raw material of industrial rutile mether liquor2O3Iron oxide red product breaches foreign technology block, makes full use of gold
Ferro element in red stone mother liquor, coincide sustainable development and environmentally protective plant networki, to conventional artificial's rutile manufacturing enterprise
Technology innovation, new-product development and meets the market demand and be of great significance.
The purpose of the present invention can be achieved through the following technical solutions：
It is a kind of using rutile mether liquor as raw material preparation nanometer di-iron trioxide iron oxide red it is an object of the invention to propose
Method comprising following steps in no particular order：
(1)：Rutile mether liquor is taken, sequentially adds dispersant and precipitating reagent thereto to get to sediment iron oxide red presoma；
(2)：Iron oxide red presoma in step (1) is transferred in hydrothermal reactor, hydro-thermal reaction is filtered, washed, dries, i.e.,
Obtain a nanometer di-iron trioxide iron oxide red product.
Further, in step (1), the rutile mether liquor is made by the following method：
(A)：It takes industrial ilmenite concentrate to calcine, after being cooled to room temperature, then places it under reducing gas atmosphere and restore, reaction knot
Shu Hou, isolation air cooling to room temperature obtain the ilmenite concentrate of oxidation/reduction modification；
(B)：The ilmenite concentrate that oxidation/reduction in step (A) is modified is added in dilute hydrochloric acid, heating, and control condensing reflux is simultaneously
It is stirred to react, is cooled to room temperature after reaction, to get to rutile mether liquor after acquired solution filtering.
Further, in step (A), the process conditions of calcining are：4-6h is calcined at 950-1050 DEG C；
The process conditions of reduction are：4h is restored at 850-950 DEG C.
Further, the reducing gas is hydrogen, and intake is 5.5g/ batch industry ilmenite concentrates, commercial titanium
Concentrate is 60g/ batches.
Further, in step (B), dilute hydrochloric acid be 20-25% dilute hydrochloric acid, oxidation/reduction be modified ilmenite concentrate with it is dilute
The mass ratio of hydrochloric acid is 1:5.
Further, it in step (B), heats up and the actual conditions being stirred to react is：It is 95-105 DEG C, stirs in temperature
Speed stirs 10-24h under the conditions of being 800-1000rpm.
Further, in step (1), the dispersant is cetyl trimethylammonium bromide, dodecyl benzene sulfonic acid
One or more of sodium, triblock copolymer F127 and polyethylene glycol；
The precipitating reagent is that ammonium hydroxide, sodium carbonate, sodium bicarbonate and sodium hydroxide are one or more of.
Further, in step (1), a concentration of 1-10M of precipitating reagent, additive amount meets：Rutile mether liquor and precipitation
Agent volume ratio is 1:3-8；
A concentration of 0.01-0.1M of dispersant (i.e. surfactant), additive amount meet：Rutile mether liquor and dispersant
Volume ratio is 100:1.
Further, in step (1), the pH value of solution controls between 3.0-8.5.
Further, the condition of hydro-thermal reaction is in step (2)：150-220 DEG C of temperature, time 1-3h.
The preparation of rutile mether liquor of the present invention is carried out according to current industrial production technology route, is simulation real industrial
What the methods and procedures of production rutile mether liquor was come, to enable the technology of the present invention method to be preferably connected with industry, it is convenient for
Commercial application.Gained rutile mether liquor main component is FeCl2And FeCl3, after adding surfactant, since surface is lived
Property agent molecule in contain lone pair electrons, can be complexed with the unoccupied orbital of ferro element, to realize from molecule, atomic level to golden red
Stone mother liquor is disperseed, and the iron oxide red presoma that can be disperseed after precipitating reagent is added, and the dosage and rutile of surfactant are female
Iron ion content is related in liquid, and the surfactant concentration that the present invention uses is 0.01-0.1M, the volume ratio with rutile mether liquor
It is 1:100, the use scope of surfactant can effectively disperse the iron ion in solution.If dosage of surfactant mistake
Low, surfactant molecule can not effectively disperse the iron ion of system, and the iron oxide red product agglomeration of preparation is than more serious；
If dosage of surfactant is higher, one side industrial production cost can increase, and on the other hand after having prepared iron oxide red product, wash
It washs iron oxide red product and needs a large amount of water, and a large amount of surfactant is also required to be further processed and could discharge in cleaning solution,
Also entreprise cost can be further increased.The precipitant concentration 1-10M that the present invention uses, rutile mether liquor are with precipitating reagent volume ratio
1:The pH value of 3-8, solution control between 3.0-8.5, and the nanometer iron oxide red product purity of preparation can reach 99.0% or more, such as
Fruit not the present invention claims in the range of, the purity of product is relatively low.Iron oxide red presoma is through hydro-thermal reaction (temperature 150-220
DEG C, time 1-3h) can decompose reaction, generate nanometer iron oxide red (Fe2O3) product.Iron oxide red presoma under hydrothermal conditions into
Row decomposition reaction, and the color and luster and Fe of iron oxide red product2O3Crystallinity and the factor of microcosmic micro-structure have relationship, by hydro-thermal
The regulation and control of reaction temperature (150-220 DEG C) and precipitating reagent additive amount so that the nanometer iron oxide red product crystallinity of preparation and microcosmic micro-
Structure difference so that iron oxide red color is had nothing in common with each other, to realize the variation of nanometer iron oxide red color from dark red to pale red.
High-quality iron oxide red material in the present invention is obtained in complicated solid-liquid/gas three-phase hydrothermal system, reactant
It is Jie's ruler there are many levels such as typical material surface and interface, presoma phase transformation, decomposition and fusion and complication system be integrated
Degree behavior.There is individual base in complicated hydrothermal system in the volume primitive such as ferriferous oxide presoma, organic molecule and anion
It is first mutually transmit, Jie's Scaling behavior of many levels such as reaction coupling and material surface and interface behavior, cause iron oxide red material size,
It is multifarious in terms of pattern, structure and color, to influence giving full play to for iron oxide red material macroscopic view superiority.The present invention passes through comprehensive
It closes and considers presoma phase change, hydrothermal growth habit, aquation and ion induction effect and iron-based hybrid surface and interface reaction-
Oriented control rule is spread, regulates and controls method using technology of chemical engineering, nanotechnology and Jie's scale, prepares serial high-quality iron oxide red
Product.
Compared with prior art, the invention has the characteristics that：
(1) using industrial rutile mether liquor as raw material, regulate and control method using technology of chemical engineering, nanotechnology and Jie's scale,
The serial iron oxide red product of high-quality is prepared, and is comparable with the color of 4130 iron oxide red product of Bayer and composition；
(2) the serial nano Fe prepared2O3Iron oxide red product colour maroon from pale red to deep, product purity is 99.0%
More than, the iron oxide red crystallinity height of preparation, aqueous dispersion are better than 4130 iron oxide red product of Bayer；
(3) it is the iron oxide red product that raw material prepares serial high added value that the method for the present invention, which is suitable for rutile mether liquor, is used
Technical method it is simple and effective, most of ferro element can be made to be utilized in rutile mether liquor, and it is low with manufacturing cost,
Low energy consumption, consersion unit is simple, stable processing technique, is easy to the advantages that large-scale production.
Description of the drawings
Fig. 1 is the preparation flow schematic diagram of the present invention；
Fig. 2 is nanometer Fe prepared by the present invention2O3Iron oxide red series of products photo compared with 4130 iron oxide red powder sample of Bayer；
Fig. 3 is nanometer Fe prepared by invention2O3Iron oxide red series of products are with 4130 iron oxide red powder sample dispersion of Bayer in aqueous solution
In after optical photograph；
Fig. 4 is nanometer Fe prepared by invention2O3Iron oxide red series of products are with 4130 iron oxide red powder sample dispersion of Bayer in aqueous solution
Optical photograph after middle 1h；
Fig. 5 is nanometer Fe prepared by invention2O3Iron oxide red series of products are with 4130 iron oxide red powder sample dispersion of Bayer in aqueous solution
Optical photograph after middle 18h；
Fig. 6 is nanometer Fe prepared by the present invention2O3Scanning electron microscope (SEM) photo of iron oxide red product 1；
Fig. 7 is nanometer Fe prepared by the present invention2O3The SEM photograph of iron oxide red product 2；
Fig. 8 is nanometer Fe prepared by the present invention2O3The SEM photograph of iron oxide red product 3；
Fig. 9 is nanometer Fe prepared by the present invention2O3The SEM photograph of iron oxide red product 4；
Figure 10 is nanometer Fe prepared by the present invention2O3Transmission electron microscope (TEM) photo of iron oxide red product 4；
Figure 11 is the SEM photograph of 4130 iron oxide red product of Bayer；
Figure 12 adds nanometer Fe prepared by relatively low amount dispersant2O3The SEM photograph of iron oxide red product.
Specific implementation mode
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.The present embodiment is with technical solution of the present invention
Premised on implemented, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to
Following embodiments.
The present invention proposes a kind of method preparing nanometer di-iron trioxide iron oxide red as raw material using rutile mether liquor comprising
Following steps in no particular order：
(1)：Rutile mether liquor is taken, sequentially adds dispersant and precipitating reagent thereto to get to sediment iron oxide red presoma；
(2)：Iron oxide red presoma in step (1) is transferred in hydrothermal reactor, hydro-thermal reaction is filtered, washed, dries, i.e.,
Obtain a nanometer di-iron trioxide iron oxide red product.
In a kind of preferred embodiment of the present invention, in step (1), the rutile mether liquor is by the following method
It is made：
(A)：It takes industrial ilmenite concentrate to calcine, after being cooled to room temperature, then places it under reducing gas atmosphere and restore, reaction knot
Shu Hou, isolation air cooling to room temperature obtain the ilmenite concentrate of oxidation/reduction modification；
(B)：The ilmenite concentrate that oxidation/reduction in step (A) is modified is added in dilute hydrochloric acid, heating, and control condensing reflux is simultaneously
It is stirred to react, is cooled to room temperature after reaction, to get to rutile mether liquor after acquired solution filtering.
In embodiment still more preferably, in step (A), the process conditions of calcining are：It is forged at 950-1050 DEG C
Burn 4-6h；
The process conditions of reduction are：4h is restored at 850-950 DEG C.
In embodiment still more preferably, the reducing gas is hydrogen, and intake is 5.5g/ batch industry
Ilmenite concentrate, industrial ilmenite concentrate are 60g/ batches.
In embodiment still more preferably, in step (B), dilute hydrochloric acid is 20-25% dilute hydrochloric acid, and oxidation/reduction changes
Property ilmenite concentrate and dilute hydrochloric acid mass ratio be 1:5.
In embodiment still more preferably, in step (B), heats up and the actual conditions being stirred to react are：In temperature
10-24h is stirred under the conditions of being 800-1000rpm for 95-105 DEG C, mixing speed.
In a kind of preferred embodiment of the present invention, in step (1), the dispersant is cetyl trimethyl
One or more of ammonium bromide, neopelex, triblock copolymer F127 and polyethylene glycol.
In a kind of preferred embodiment of the present invention, the precipitating reagent is ammonium hydroxide, sodium carbonate, sodium bicarbonate and hydrogen
Sodium oxide molybdena is one or more of.
In a kind of preferred embodiment of the present invention, in step (1), a concentration of 1-10M of precipitating reagent, additive amount
Meet：Rutile mether liquor is 1 with precipitating reagent volume ratio:3-8.
In a kind of preferred embodiment of the present invention, a concentration of 0.01- of dispersant (i.e. surfactant)
0.1M, additive amount meet：Rutile mether liquor is 100 with dispersant volume ratio:1.
In a kind of preferred embodiment of the present invention, in step (1), the control of the pH value of solution 3.0-8.5 it
Between.
In a kind of preferred embodiment of the present invention, the condition of hydro-thermal reaction is in step (2)：Temperature 150-220
DEG C, time 1-3h.
The present invention is further detailed with reference to specific embodiment.
Embodiment 1
As shown in Figure 1, a kind of preparing serial high added value nanometer Fe by raw material Jie's scale of industrial rutile mether liquor2O3Iron
Red method, detailed process are as follows：
200g industry ilmenite concentrates are calcined (980 DEG C, 5h) in Muffle furnace, cooled to room temperature after calcining, then by oxygen
Industrial ilmenite concentrate after change restores 4h under 900 DEG C of atmosphere of hydrogen, and then the modified ilmenite concentrate of oxidationreduction is added again
22% dilute hydrochloric acid, ilmenite concentrate are 1 with dilute hydrochloric acid mass ratio:5, solution after mixing is then warming up to 102 DEG C, condensing reflux, machine
Tool stirs 15h, and mixing speed is 900 revs/min, is cooled to room temperature after reaction, obtained solution is through filtering-standing-mistake
Filter is handled, and acquired solution is rutile mether liquor, and main component is divalent iron salt and trivalent iron salt.
500mL rutile mether liquors obtained above are measured, 5mL (0.05M) cetyl trimethylammonium bromide is sequentially added
With 2000mL sodium hydroxides (2M) precipitating reagent, solution ph controls between 3.0-8.5, until iron ion is largely heavy in solution
It forms sediment, gained sediment is iron oxide red presoma.Obtained iron oxide red presoma is transferred to hydrothermal reactor, through hydro-thermal reaction (210 DEG C,
2h), it is filtered, washed and dried to obtain 1 product of iron oxide red.
Embodiment 2
As shown in Figure 1, a kind of preparing serial high added value nanometer Fe by raw material Jie's scale of industrial rutile mether liquor2O3Iron
Red method, detailed process are as follows：
200g industry ilmenite concentrates are calcined (980 DEG C, 5h) in Muffle furnace, cooled to room temperature after calcining, then by oxygen
Industrial ilmenite concentrate after change restores 4h under 900 DEG C of atmosphere of hydrogen, and then the modified ilmenite concentrate of oxidationreduction is added again
22% dilute hydrochloric acid, ilmenite concentrate are 1 with dilute hydrochloric acid mass ratio:5, solution after mixing is then warming up to 102 DEG C, condensing reflux, machine
Tool stirs 15h, and mixing speed is 900 revs/min, is cooled to room temperature after reaction, obtained solution is through filtering-standing-mistake
Filter is handled, and acquired solution is rutile mether liquor, and main component is divalent iron salt and trivalent iron salt.
500mL rutile mether liquors obtained above are measured, 5mL (0.05M) cetyl trimethylammonium bromide is sequentially added
With 2000mL sodium hydroxides (4M) precipitating reagent, solution ph controls between 3.0-8.5, until iron ion is largely heavy in solution
It forms sediment, gained sediment is iron oxide red presoma.Obtained iron oxide red presoma is transferred to hydrothermal reactor, through hydro-thermal reaction (180 DEG C,
2h), it is filtered, washed and dried to obtain 2 product of iron oxide red.
Embodiment 3
As shown in Figure 1, a kind of preparing serial high added value nanometer Fe by raw material Jie's scale of industrial rutile mether liquor2O3Iron
Red method, detailed process are as follows：
200g industry ilmenite concentrates are calcined (980 DEG C, 5h) in Muffle furnace, cooled to room temperature after calcining, then by oxygen
Industrial ilmenite concentrate after change restores 4h under 900 DEG C of atmosphere of hydrogen, and then the modified ilmenite concentrate of oxidationreduction is added again
22% dilute hydrochloric acid, ilmenite concentrate are 1 with dilute hydrochloric acid mass ratio:5, solution after mixing is then warming up to 102 DEG C, condensing reflux, machine
Tool stirs 15h, and mixing speed is 900 revs/min, is cooled to room temperature after reaction, obtained solution is through filtering-standing-mistake
Filter is handled, and acquired solution is rutile mether liquor, and main component is divalent iron salt and trivalent iron salt.
500mL rutile mether liquors obtained above are measured, 5mL (0.05M) cetyl trimethylammonium bromide is sequentially added
With 2000mL sodium hydroxides (8M) precipitating reagent, solution ph controls between 3.0-8.5, until iron ion is largely heavy in solution
It forms sediment, gained sediment is iron oxide red presoma.Obtained iron oxide red presoma is transferred to hydrothermal reactor, through hydro-thermal reaction (180 DEG C,
2h), it is filtered, washed and dried to obtain 3 product of iron oxide red.
Embodiment 4
As shown in Figure 1, a kind of preparing serial high added value nanometer Fe by raw material Jie's scale of industrial rutile mether liquor2O3Iron
Red method, detailed process are as follows：
200g industry ilmenite concentrates are calcined (980 DEG C, 5h) in Muffle furnace, cooled to room temperature after calcining, then by oxygen
Industrial ilmenite concentrate after change restores 4h under 900 DEG C of atmosphere of hydrogen, and then the modified ilmenite concentrate of oxidationreduction is added again
22% dilute hydrochloric acid, ilmenite concentrate are 1 with dilute hydrochloric acid mass ratio:5, solution after mixing is then warming up to 102 DEG C, condensing reflux, machine
Tool stirs 15h, and mixing speed is 900 revs/min, is cooled to room temperature after reaction, obtained solution is through filtering-standing-mistake
Filter is handled, and acquired solution is rutile mether liquor, and main component is divalent iron salt and trivalent iron salt.
500mL rutile mether liquors obtained above are measured, 5mL (0.05M) cetyl trimethylammonium bromide is sequentially added
With 2000mL sodium hydroxides (10M) precipitating reagent, solution ph controls between 3.0-8.5, until iron ion is largely heavy in solution
It forms sediment, gained sediment is iron oxide red presoma.Obtained iron oxide red presoma is transferred to hydrothermal reactor, through hydro-thermal reaction (150 DEG C,
2h), it is filtered, washed and dried to obtain 4 product of iron oxide red.
It synthesizes shown in serial nano iron oxide red and 4130 iron oxide red product optical photograph such as Fig. 2 (a) of Bayer.It can be with from Fig. 2 (a)
Find out that the iron oxide red product 1 of synthesis is peony, from Fig. 2 (d) it can be seen that the iron oxide red 4 of synthesis is light red, from Fig. 2 (b) and 2
(c) non-with 4130 iron oxide red of Bayer (Fig. 2 (e)) color it can be seen that the iron oxide red 2 of synthesis and 3 colors are between dark red and pale red
Very close to.To verify ferrite red and 4130 iron oxide red product dispersibility difference of Bayer, by the iron series proof sheet product and Bayer of preparation
4130 iron oxide red sample copies do not disperse in aqueous solution, as shown in Figure 3.From figure 3, it can be seen that synthesis serial iron oxide red product with visit
4130 iron oxide red product of ear can well disperse in aqueous solution.After iron oxide red solution left standstill 1h (Fig. 4), it can be seen that prepare
Iron oxide red series of products do not have separation of solid and liquid phenomenon, and 4130 iron oxide red product of Bayer has occurred slightly being separated by solid-liquid separation sign, molten
Translucent is presented in liquid upper layer.After iron oxide red solution left standstill 18h (figure (5)), the serial iron oxide red product of preparation also upper solution
There is translucent, and 4130 iron oxide red product upper solution of Bayer has become to clarify very much.Iron oxide red solution left standstill experimental result
Show that dispersibility is better than 4130 iron oxide red product of Bayer in aqueous solution for the iron oxide red series of products of synthesis.The iron oxide red product of preparation
1 (Fig. 6), iron oxide red product 2 (Fig. 7), iron oxide red product 3 (Fig. 8) and iron oxide red product 4 (Fig. 9) SEM photograph can be seen that synthesis
For serial iron oxide red product cut size size in 200nm or so, pattern is spherical in shape, product favorable dispersibility.It is prepared by Figure 10 present invention
Nanometer Fe2O3The TEM photos of iron oxide red product 4.From fig. 10 it can be seen that the nanometer Fe of synthesis2O3Iron oxide red product lattice fringe is very
Clearly, there is higher crystallinity.It is well known that Fe2O3The crystallinity of nano material is promoted with the increase of hydrothermal temperature,
Reaction temperature of the present invention can ensure the serial nano Fe of synthesis between 150-220 DEG C2O3Iron oxide red product has higher knot
Brilliant degree, and on the one hand excessively high hydrothermal temperature can increase production cost, on the other hand can also require more consersion unit
Harshness also brings along potential production safety sex chromosome mosaicism.The SEM photograph of 4130 iron oxide red product of Bayer is as shown in figure 11.From Figure 11
As can be seen that 4130 iron oxide red product of Bayer is made of a large amount of 100-200nm or so particle, but agglomeration is very tight between particle
Weight, intergranular reunion cause the aggregate of large-size to generate, thus are easy sedimentation in aqueous solution.The SEM of iron oxide red product
Photo is consistent with iron oxide red standing experimental result, the serial iron oxide red product favorable dispersibility synthesized by the present invention, and 4130 iron of Bayer
Red product agglomeration causes 4130 iron oxide red product of Bayer to occur more apparent solid-liquid after standing 18h than more serious
Segregation phenomenon.
Table 1 is nanometer Fe prepared by the present invention2O3Iron oxide red series of products and the X rays of 4130 iron oxide red powder sample of Bayer are glimmering
Light spectrum analysis (XRF) result.
Table 1
As it can be seen from table 1 the iron oxide red product 1 of synthesis, iron oxide red product 2, iron oxide red product 3 and 4 purity of iron oxide red product difference
It is 99.1607%, 99.0629%, 99.1300% and 99.1215%, and 4130 iron oxide red product purity of Bayer is 99.2944%,
Its purity is slightly above the iron oxide red product synthesized.From ferrite red product color, aqueous dispersion experiment, SEM morphology observations and
XRF composition analysis experimental result is it can be proved that the serial iron oxide red product synthesized through the invention has with 4130 iron oxide red product of Bayer
There is comparativity, is of great significance to the comprehensive utilization of china natural resources.
When dispersant additive amount is 0.005M (inventive dispersant concentration is in 0.01-0.1M), the body with rutile mether liquor
Product is than being 1:When 100, the nanometer Fe of preparation2O3Iron oxide red product SEM photograph is as shown in figure 12.From Figure 12 as can be seen that relatively low use
The surfactant of amount can not effectively disperse nanometer Fe2O3Product, product agglomeration is very serious, mutually reunites between particle
Form the aggregate of large-size, and Fe2O3Particle size is also uneven.Therefore, inventive dispersant use scope it
Outside, the nanometer Fe of high dispersive can not be prepared2O3Iron oxide red product.150-220 DEG C of hydrothermal temperature temperature of the present invention, time 1-
3h can ensure that iron oxide red presoma is decomposed into Fe completely after hydro-thermal reaction2O3.When 140 DEG C (reactions 3h) to presoma into
Row processing finds that product and presoma appearance are very close after reaction, rather than Fe2O3The red feature that should have, I
May determine that under the conditions of compared with low reaction temperatures, iron oxide red presoma can not thoroughly be decomposed into Fe2O3.Rutile of the present invention is female
Liquid is controlled with precipitating reagent volume ratio 1:3-8, when the two volume ratio is less than 1:When 3, iron ion cannot big portion in rutile mether liquor
Fractional precipitation, and when the two volume ratio is more than 1:When 8, the significant decrease of iron oxide red product purity is prepared.For example, when rutile mether liquor with it is heavy
Shallow lake agent volume ratio is adjusted to 1:When 8.2, the nanometer Fe of preparation2O3The results are shown in Table 2 for iron oxide red product XRF analysis.It can be with from table 2
Find out, when precipitant concentration dosage is higher, not in the present invention claims range, gained iron oxide red product purity is relatively low, due to impurity
Content is more, and the iron oxide red product colour of preparation is also poor.If not being unable to get the present invention under above-mentioned crucial treatment conditions
High-crystallinity, high-purity and high aqueous dispersion high added value iron oxide red product.Therefore, the side such as the process step of the invention
Face has apparent innovative.
Table 2
| Analyte | Fe2O3 | Al2O3 | V2O5 | Co2O3 | Mn2O3 | ZnO |
| Content | 86.6824% | 4.0935% | 3.5865% | 1.5214% | 1.3172% | 1.1026% |
| Analyte | Cr2O3 | PbO | TiO2 | Cl | ||
| Content | 0.5675% | 0.5123% | 0.3587% | 0.2579% |
Embodiment 5
As shown in Figure 1, a kind of preparing serial high added value nanometer Fe by raw material Jie's scale of industrial rutile mether liquor2O3Iron
Red method, detailed process are as follows：
200g industry ilmenite concentrates are calcined (1050 DEG C, 4h) in Muffle furnace, cooled to room temperature after calcining, then by oxygen
Industrial ilmenite concentrate after change restores 4h under 850 DEG C of atmosphere of hydrogen, and then the modified ilmenite concentrate of oxidationreduction is added again
20% dilute hydrochloric acid, ilmenite concentrate are 1 with dilute hydrochloric acid mass ratio:5, solution after mixing is then warming up to 95 DEG C, condensing reflux is mechanical
For 24 hours, mixing speed is 800 revs/min, is cooled to room temperature after reaction, obtained solution is through filtering-standing-filtering for stirring
Processing, acquired solution are rutile mether liquor, and main component is divalent iron salt and trivalent iron salt.
500mL rutile mether liquors obtained above are measured, 5mL (0.01M) cetyl trimethylammonium bromide is sequentially added
With 1500mL ammonium hydroxide (6M) precipitating reagent, solution ph controls between 3.0-8.5, until iron ion largely precipitates in solution, institute
It is iron oxide red presoma to obtain sediment.Obtained iron oxide red presoma is transferred to hydrothermal reactor, through hydro-thermal reaction (180 DEG C, 2h), mistake
Filter, wash and be dried to obtain iron oxide red product.
Embodiment 6
As shown in Figure 1, a kind of preparing serial high added value nanometer Fe by raw material Jie's scale of industrial rutile mether liquor2O3Iron
Red method, detailed process are as follows：
200g industry ilmenite concentrates are calcined (980 DEG C, 5h) in Muffle furnace, cooled to room temperature after calcining, then by oxygen
Industrial ilmenite concentrate after change restores 4h under 900 DEG C of atmosphere of hydrogen, and then the modified ilmenite concentrate of oxidationreduction is added again
22% dilute hydrochloric acid, ilmenite concentrate are 1 with dilute hydrochloric acid mass ratio:5, solution after mixing is then warming up to 102 DEG C, condensing reflux, machine
Tool stirs 15h, and mixing speed is 900 revs/min, is cooled to room temperature after reaction, obtained solution is through filtering-standing-mistake
Filter is handled, and acquired solution is rutile mether liquor, and main component is divalent iron salt and trivalent iron salt.
500mL rutile mether liquors obtained above are measured, 5mL (0.05M) cetyl trimethylammonium bromide is sequentially added
With 2000mL sodium hydroxides (2M) precipitating reagent, solution ph controls between 3.0-8.5, until iron ion is largely heavy in solution
It forms sediment, gained sediment is iron oxide red presoma.Obtained iron oxide red presoma is transferred to hydrothermal reactor, through hydro-thermal reaction (150 DEG C,
3h), it is filtered, washed and dried to obtain iron oxide red product.
Embodiment 7
As shown in Figure 1, a kind of preparing serial high added value nanometer Fe by raw material Jie's scale of industrial rutile mether liquor2O3Iron
Red method, detailed process are as follows：
200g industry ilmenite concentrates are calcined (980 DEG C, 5h) in Muffle furnace, cooled to room temperature after calcining, then by oxygen
Industrial ilmenite concentrate after change restores 4h under 900 DEG C of atmosphere of hydrogen, and then the modified ilmenite concentrate of oxidationreduction is added again
22% dilute hydrochloric acid, ilmenite concentrate are 1 with dilute hydrochloric acid mass ratio:5, solution after mixing is then warming up to 102 DEG C, condensing reflux, machine
Tool stirs 15h, and mixing speed is 900 revs/min, is cooled to room temperature after reaction, obtained solution is through filtering-standing-mistake
Filter is handled, and acquired solution is rutile mether liquor, and main component is divalent iron salt and trivalent iron salt.
500mL rutile mether liquors obtained above are measured, 5mL (0.05M) cetyl trimethylammonium bromide is sequentially added
With 2000mL sodium hydroxides (2M) precipitating reagent, solution ph controls between 3.0-8.5, until iron ion is largely heavy in solution
It forms sediment, gained sediment is iron oxide red presoma.Obtained iron oxide red presoma is transferred to hydrothermal reactor, through hydro-thermal reaction (220 DEG C,
1h), it is filtered, washed and dried to obtain iron oxide red product.
Embodiment 8
It is shown in Figure 1, it is a kind of to prepare serial high added value nanometer Fe by raw material Jie's scale of industrial rutile mether liquor2O3
The method of iron oxide red, detailed process are as follows：
200g industry ilmenite concentrates are calcined (950 DEG C, 6h) in Muffle furnace, cooled to room temperature after calcining, then by oxygen
Industrial ilmenite concentrate after change restores 4h under 950 DEG C of atmosphere of hydrogen, and then the modified ilmenite concentrate of oxidationreduction is added again
25% dilute hydrochloric acid, ilmenite concentrate are 1 with dilute hydrochloric acid mass ratio:5, solution after mixing is then warming up to 105 DEG C, condensing reflux, machine
Tool stirs 10h, and mixing speed is 1000 revs/min, is cooled to room temperature after reaction, obtained solution is through filtering-standing-mistake
Filter is handled, and acquired solution is rutile mether liquor, and main component is divalent iron salt and trivalent iron salt.
Measure 500mL rutile mether liquors obtained above, sequentially add 5mL (0.1M) neopelexes and
4000mL sodium bicarbonates (1M) precipitating reagent, solution ph control between 3.0-8.5, until iron ion largely precipitates in solution,
Gained sediment is iron oxide red presoma.Obtained iron oxide red presoma is transferred to hydrothermal reactor, through hydro-thermal reaction (150 DEG C, 3h),
It is filtered, washed and dried to obtain iron oxide red product.
Embodiment 9
It is shown in Figure 1, it is a kind of to prepare serial high added value nanometer Fe by raw material Jie's scale of industrial rutile mether liquor2O3
The method of iron oxide red, detailed process are as follows：
200g industry ilmenite concentrates are calcined (1000 DEG C, 5h) in Muffle furnace, cooled to room temperature after calcining, then by oxygen
Industrial ilmenite concentrate after change restores 4h under 900 DEG C of atmosphere of hydrogen, and then the modified ilmenite concentrate of oxidationreduction is added again
22% dilute hydrochloric acid, ilmenite concentrate are 1 with dilute hydrochloric acid mass ratio:5, solution after mixing is then warming up to 100 DEG C, condensing reflux, machine
Tool stirs 18h, and mixing speed is 950 revs/min, is cooled to room temperature after reaction, obtained solution is through filtering-standing-mistake
Filter is handled, and acquired solution is rutile mether liquor, and main component is divalent iron salt and trivalent iron salt.
500mL rutile mether liquors obtained above are measured, 2mL (0.06M) neopelexes and 3mL are sequentially added
(0.06M) polyethylene glycol and 1000mL sodium carbonate (5M) and 1500mL sodium bicarbonates (5M) precipitating reagent, solution ph control
Between 3.0-8.5, until iron ion largely precipitates in solution, gained sediment is iron oxide red presoma.Before obtained iron oxide red
It drives body and is transferred to hydrothermal reactor, through hydro-thermal reaction (150 DEG C, 3h), be filtered, washed and dried to obtain iron oxide red product.
Embodiment 10
It is shown in Figure 1, it is a kind of to prepare serial high added value nanometer Fe by raw material Jie's scale of industrial rutile mether liquor2O3
The method of iron oxide red, detailed process are as follows：
200g industry ilmenite concentrates are calcined (1000 DEG C, 5h) in Muffle furnace, cooled to room temperature after calcining, then by oxygen
Industrial ilmenite concentrate after change restores 4h under 900 DEG C of atmosphere of hydrogen, and then the modified ilmenite concentrate of oxidationreduction is added again
22% dilute hydrochloric acid, ilmenite concentrate are 1 with dilute hydrochloric acid mass ratio:5, solution after mixing is then warming up to 100 DEG C, condensing reflux, machine
Tool stirs 18h, and mixing speed is 950 revs/min, is cooled to room temperature after reaction, obtained solution is through filtering-standing-mistake
Filter is handled, and acquired solution is rutile mether liquor, and main component is divalent iron salt and trivalent iron salt.
500mL rutile mether liquors obtained above are measured, 5mL (0.08M) triblock copolymer F127 is sequentially added, with
And 1000mL sodium hydroxides (5M) and 1000mL ammonium hydroxide (5M) precipitating reagent, solution ph controls between 3.0-8.5, until in solution
Iron ion largely precipitates, and gained sediment is iron oxide red presoma.Obtained iron oxide red presoma is transferred to hydrothermal reactor, through water
Thermal response (150 DEG C, 3h) is filtered, washed and dried to obtain iron oxide red product.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiment without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be the present invention's
Within protection domain.
Claims (10)
1. the method for preparing nanometer di-iron trioxide iron oxide red as raw material using rutile mether liquor, which is characterized in that include the following steps：
(1)：Rutile mether liquor is taken, sequentially adds dispersant and precipitating reagent thereto to get to sediment iron oxide red presoma；
(2)：Iron oxide red presoma in step (1) is transferred in hydrothermal reactor, hydro-thermal reaction, be filtered, washed, dry to get to
Nanometer di-iron trioxide iron oxide red product.
2. the method according to claim 1 for preparing nanometer di-iron trioxide iron oxide red as raw material using rutile mether liquor, special
Sign is that in step (1), the rutile mether liquor is made by the following method：
(A)：It takes industrial ilmenite concentrate to calcine, after being cooled to room temperature, then places it under reducing gas atmosphere and restore, reaction terminates
Afterwards, isolation air cooling obtains the ilmenite concentrate of oxidation/reduction modification to room temperature；
(B)：The ilmenite concentrate that oxidation/reduction in step (A) is modified is added in dilute hydrochloric acid, heating, controls condensing reflux and stirs
Reaction, is cooled to room temperature after reaction, to get to rutile mether liquor after acquired solution filtering.
3. the method according to claim 2 for preparing nanometer di-iron trioxide iron oxide red as raw material using rutile mether liquor, special
Sign is that in step (A), the process conditions of calcining are：4-6h is calcined at 950-1050 DEG C；
The process conditions of reduction are：4h is restored at 850-950 DEG C.
4. the method according to claim 2 or 3 that nanometer di-iron trioxide iron oxide red is prepared as raw material using rutile mether liquor,
It is characterized in that, the reducing gas is hydrogen, and intake is 5.5g/ batch industry ilmenite concentrates, and industrial ilmenite concentrate is 60g/
Batch.
5. the method according to claim 2 for preparing nanometer di-iron trioxide iron oxide red as raw material using rutile mether liquor, special
Sign is, in step (B), dilute hydrochloric acid is 20-25% dilute hydrochloric acid, the mass ratio for the ilmenite concentrate and dilute hydrochloric acid that oxidation/reduction is modified
It is 1:5.
6. the method according to claim 2 for preparing nanometer di-iron trioxide iron oxide red as raw material using rutile mether liquor, special
Sign is, in step (B), heats up and the actual conditions being stirred to react are：Temperature be 95-105 DEG C, mixing speed 800-
10-24h is stirred under the conditions of 1000rpm.
7. the method according to claim 1 for preparing nanometer di-iron trioxide iron oxide red as raw material using rutile mether liquor, special
Sign is, in step (1), the dispersant is that cetyl trimethylammonium bromide, neopelex, three block are total
One or more of polymers F127 and polyethylene glycol；
The precipitating reagent is that ammonium hydroxide, sodium carbonate, sodium bicarbonate and sodium hydroxide are one or more of.
8. the method according to claim 1 for preparing nanometer di-iron trioxide iron oxide red as raw material using rutile mether liquor, special
Sign is, in step (1), a concentration of 1-10M of precipitating reagent, additive amount meets：Rutile mether liquor is with precipitating reagent volume ratio
1:3-8；
A concentration of 0.01-0.1M of dispersant, additive amount meet：Rutile mether liquor is 100 with dispersant volume ratio:1.
9. the method according to claim 1 for preparing nanometer di-iron trioxide iron oxide red as raw material using rutile mether liquor, special
Sign is, in step (1), the pH value of solution controls between 3.0-8.5.
10. the method according to claim 1 for preparing nanometer di-iron trioxide iron oxide red as raw material using rutile mether liquor, special
Sign is that the condition of hydro-thermal reaction is in step (2)：150-220 DEG C of temperature, time 1-3h.
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