CN106673071A - Method for removing iron from laterite nickel ore pickling liquid and producing iron oxide black pigment at the same time - Google Patents

Method for removing iron from laterite nickel ore pickling liquid and producing iron oxide black pigment at the same time Download PDF

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Publication number
CN106673071A
CN106673071A CN201611205574.8A CN201611205574A CN106673071A CN 106673071 A CN106673071 A CN 106673071A CN 201611205574 A CN201611205574 A CN 201611205574A CN 106673071 A CN106673071 A CN 106673071A
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China
Prior art keywords
iron oxide
nickel ore
iron
black
pickle liquor
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CN201611205574.8A
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CN106673071B (en
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李梅彤
张柯
张响
张影
袁文蛟
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Tianjin University of Technology
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Tianjin University of Technology
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    • 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
    • C01G49/08—Ferroso-ferric oxide (Fe3O4)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/40—Magnesium sulfates

Abstract

A method for removing iron from a laterite nickel ore pickling liquid and producing iron oxide black pigment at the same time solves the problem that iron in a laterite nickel ore pickling liquid is removed through a sodium jarosite method or a goethite method in the prior art, a great deal of iron-containing waste residue is generated, the land occupation is large, the cost is high and environmental pollution is generated. In the method, a reduction process is combined with an oxidation process, so that iron is removed from the laterite nickel ore pickling liquid and the iron oxide black pigment conforming to the national standard is produced at the same time, and the wastewater is used for recycling magnesium sulfate. Compared with other wet methods for producing iron oxide black, the method allows waste iron resources to be reasonably utilized and makes the relative unit cost reduced by more than 30%. The method has innovative significance on resource treatment of iron in a laterite nickel ore wet process, and belongs to technology of clean production.

Description

A kind of method that lateritic nickel ore pickle liquor produces black iron oxide pigment simultaneously except ferrum
Technical field
The present invention relates to a kind of method that lateritic nickel ore pickle liquor produces black iron oxide pigment except ferrum, belongs to resource ring simultaneously Border field.
Background technology
During laterite nickel wet production nickel, commonly use sulphuric acid (or hydrochloric acid) acidleach, pickle liquor contain dissolving a large amount of iron sulfate, Ferrous sulfate (or iron chloride, ferrous chloride), at the same solution also have substantial amounts of magnesium sulfate, aluminum sulfate, nickel sulfate, silicon etc. into Point；Existing pickle liquor is mainly yellow sodium ferrum vanadium process or goethite process except ferrum mode, all produces substantial amounts of iron slag, takes big Area soil, wastes iron resource and pollutes environment.Requirement raising and people environmental protection recently as country to clean manufacturing The enhancing of consciousness, progressively implements both at home and abroad with regard to every regulation of waste process and regeneration, and treatment of wastes produced is required More and more higher, causes wet method Ye Nie enterprise to dispose waste residue and seriously bears.By the ferrum element recycling in pickle liquor, except ferrum it is same When produce black iron oxide pigment, can both reduce waste residue disposal costs, significant benefit can be produced again, meet recycling economy Theory and promotion law on cleaner production are required.
Iron oxide black is referred to as iron black, and molecular formula is FeO or FeOFeO, and chemical name is ferroso-ferric oxide.Iron oxide black Indigo plant ink light black with saturation, covering power and tinting strength, tinting power it is very high, be widely used in building materials, cement, ink, printing, plastics Deng coloring field.In recent years, the demand of China's iron oxide black is continuously increased, and annual rate of growth is up to 107%, significantly larger than entirely The rate of increase of iron oxide pigment 36.6%, is the iron pigment for being only second to iron oxide red and iron oxide yellow.The method for producing iron oxide black at present There is the big class of dry and wet two, dry method mainly has iron scale comminuting method, reduction iron cement method etc., and wet method has using ferrous sulfate, chlorination Ferrous irons etc. are sodium alkali, ammonia-soda process of raw material etc..Dry method iron oxide black is of low quality, and use range is narrow；Wet method, the numerous length of technique, cost Height, needs substantial amounts of acid solution or alkali liquor to participate in reaction, while discharging a large amount of brine wastes, to enterprise serious burden is brought, Environment is exerted heavy pressures on.
Lateritic nickel ore pickle liquor component is born miscellaneous, and solution concentration is very high, and containing a large amount of Fe3+ and Fe2+ ions, often Fe3+ contains Amount>Fe2+ contents, with conventional wet lay process, it is impossible to obtain the black iron oxide pigment of coloration compliance；Simultaneously because add a large amount of sodium, Ammonium ion, brings the burden of a large amount of waste water dis posals；Low cost solves problem above, and output is qualified while pickle liquor removes ferrum Black iron oxide pigment, there is distinct economic and social benefit.
The content of the invention
The purpose of the present invention is for above-mentioned existing problems, there is provided a kind of lateritic nickel ore pickle liquor produces oxidation simultaneously except ferrum The method of iron oxide black pigment, using magnesium salt as nertralizer, addition reducing agent adjusts pickle liquor Fe3+ and Fe2+ concentration to the method, then By the technique of oxidation adjustment black iron oxide pigment form and aspect, the method is injected capital into less, reliable product quality, and waste liquid can be reclaimed Magnesium sulfate, there is significant economic benefit, belongs to process for cleanly preparing.
Technical scheme：
A kind of method that lateritic nickel ore pickle liquor produces black iron oxide pigment simultaneously except ferrum, step is as follows：
1) in PH<Reducing agent is added in 5 lateritic nickel ore pickle liquor, lateritic nickel ore pickle liquor reducing solution, reducing solution is obtained The mol ratio of middle Fe3+ and Fe2+ is 0.3-1.1：1；
2) steam is passed through in lateritic nickel ore pickle liquor reducing solution and is heated to 60-90 DEG C, add magnesium oxide or magnesium hydroxide Regulation pH be 6-10, air oxidation is passed through at a temperature of 60-90 DEG C, to black iron oxide pigment color reach standard require after stop Oxidation；
3) the qualified pickle liquor of above-mentioned oxidation is entered into Filter Press, solidss are iron oxide black filter cake, filter cake 3- 20wt% sodium hydrate aqueous solutions carry out beating washing, 3wt% of the sodium hydroxide concentration less than or equal to filter cake quality；Aoxidized Iron black filter cake, filtrate enters subsequent recovery magnesium sulfate operation；
4) by above-mentioned iron oxide black filter cake at 80-150 DEG C dewatered drying；
5) through crushing, production meets the oxygen of GB/T1863-2008 (A classes) standard requirement to the black iron oxide pigment after drying Change iron oxide black pigment.
The step 1) in reducing agent be sulfur dioxide, magnesium sulfite, ferrous sulfate and ferrous chloride in one kind or two Plant the mixture of any of the above ratio；Reducing agent is 0.1-1.5 with the mol ratio of Fe3+：1.
The invention has the beneficial effects as follows：
1) Fe3 concentration when lateritic nickel ore pickle liquor is normal>Fe2+ concentration, the present invention adjusts Fe3+ and Fe2+ using reducing agent Concentration ratio, is conducive to controlling iron oxide black form and aspect, it is ensured that product quality；Simultaneously iron slag is not produced, ring is greatly reduced Protect disposal costs；
2) present invention adjusts pH using magnesium salt, does not introduce other impurities ion, is conducive to subsequent recovery magnesium sulfate, makes wet method Smelting nickel system synthesis cost is greatly reduced；
3) present invention design reduction and oxidation technology are combined, and lateritic nickel ore pickle liquor is realized except production meets while ferrum The black iron oxide pigment of GB, waste water is used for subsequent recovery magnesium sulfate；Relative to other wet oxidation iron oxide black techniques, this technique is Discarded iron resource is utilized, and relative unit cost can reduce by more than 30%, the ferrum element resource to lateritic nickel ore wet processing Place is equipped with great innovative significance, belongs to process for cleanly preparing.
Description of the drawings
Fig. 1 is present invention process schematic flow sheet.
Specific embodiment
Further illustrate by the following examples, but be not construed as limiting the invention.
Embodiment 1：
A kind of method that lateritic nickel ore pickle liquor produces black iron oxide pigment simultaneously except ferrum, step is as follows：
1) 1000Kg lateritic nickel ore pickle liquor pH=4, Fe are added in the reactor203Content is 6.0wt%, adds SO2 also Former agent 15Kg, makes Fe3+:Fe2+ is adjusted to 0.7:1；
2) in the reactor lateritic nickel ore pickle liquor reducing solution is passed through into steam and is heated to 90 DEG C, plus magnesium oxide 30kg is adjusted PH=6.5, temperature of reactor keep 90 DEG C, be passed through air oxidation 30 minutes, to black iron oxide pigment color reach standard will Stop oxidation after asking；
3) aoxidize qualified pickle liquor and enter Filter Press, solidss are iron oxide black filter cake, filter cake 5wt% hydroxides 10 kilograms of sodium solution carries out beating washing, and into baking operation, filter liquid enters other operations；
4) iron oxide black filter cake enters drying system, in 100 DEG C of condition dewatered dryings；
5) black iron oxide pigment after drying produces 59.5kg and meets GB/T1863-2008 (A classes) standard through crushing The black iron oxide pigment of requirement.Fig. 1 is present invention process schematic flow sheet.
Embodiment 2：
A kind of method that lateritic nickel ore pickle liquor produces black iron oxide pigment simultaneously except ferrum, step is as follows：
1) 1000Kg lateritic nickel ore pickle liquors, pH=4, Fe are added in the reactor203Content is 4.5wt%, is added FeSO4Reducing agent 10Kg, makes Fe3+:Fe2+ is adjusted to 0.9:1.
2) in the reactor lateritic nickel ore pickle liquor reducing solution is passed through into steam and is heated to 80 DEG C, plus magnesium oxide 20kg is adjusted PH=6.2, temperature of reactor keep 80 DEG C, be passed through air oxidation 40 minutes, to black iron oxide pigment color reach standard will Stop oxidation after asking；
3) aoxidize qualified pickle liquor and enter Filter Press, solidss are iron oxide black filter cake, filter cake 3wt% hydrogen-oxygens Changing 10 kilograms of sodium solution carries out beating washing, and into baking operation, filter liquid enters other operations.
4) iron oxide black filter cake enters drying system, in 110 DEG C of condition dewatered dryings.
5) black iron oxide pigment after drying produces 49.2kg and meets GB/T1863-2008 (A classes) standard through crushing The black iron oxide pigment of requirement.Fig. 1 is present invention process schematic flow sheet.
Embodiment 3：
A kind of method that lateritic nickel ore pickle liquor produces black iron oxide pigment simultaneously except ferrum, step is as follows：
1) 1000Kg lateritic nickel ore pickle liquors, pH=4.3, Fe are added in the reactor20Content is5.0wt%, adds FeSO4 Reducing agent 8Kg, makes Fe3+:Fe2+ is adjusted to 0.6:1.
2) in the reactor lateritic nickel ore pickle liquor reducing solution is passed through into steam and is heated to 90 DEG C, hydro-oxidation magnesium 30kg is adjusted Section pH=6.8, temperature of reactor is kept for 90 DEG C, is passed through air oxidation 60 minutes, and the color to black iron oxide pigment reaches standard Stop oxidation after requirement；
3) aoxidize qualified pickle liquor and enter Filter Press, solidss are iron oxide black filter cake, filter cake 3wt% hydroxides 10 kilograms of sodium solution carries out beating washing, and into baking operation, filter liquid enters other operations.
4) iron oxide black filter cake enters drying system, in 120 DEG C of condition dewatered dryings.
5) black iron oxide pigment after drying produces 53.1kg and meets GB/T1863-2008 (A classes) standard through crushing The black iron oxide pigment of requirement.

Claims (2)

1. a kind of method that lateritic nickel ore pickle liquor produces black iron oxide pigment simultaneously except ferrum, it is characterised in that step is as follows：
1) in PH<Reducing agent is added in 5 lateritic nickel ore pickle liquor, lateritic nickel ore pickle liquor reducing solution, Fe3 in reducing solution is obtained + with the mol ratio of Fe2+ it is 0.3-1.1：1；
2) steam is passed through in lateritic nickel ore pickle liquor reducing solution and is heated to 60-90 DEG C, add magnesium oxide or magnesium hydroxide to adjust PH is 6-10, and air oxidation is passed through at a temperature of 60-90 DEG C, to black iron oxide pigment color reach standard require after stop oxygen Change；
3) the qualified pickle liquor of above-mentioned oxidation is entered into Filter Press, solidss are iron oxide black filter cake, filter cake 3- 20wt% sodium hydrate aqueous solutions carry out beating washing, 3wt% of the sodium hydroxide concentration less than or equal to filter cake quality；Aoxidized Iron black filter cake, filtrate enters subsequent recovery magnesium sulfate operation；
4) by above-mentioned iron oxide black filter cake at 80-150 DEG C dewatered drying；
5) through crushing, production meets the ferrum oxide of GB/T1863-2008 (A classes) standard requirement to the black iron oxide pigment after drying Mineral black.
2. the method that according to claim 1 lateritic nickel ore pickle liquor produces black iron oxide pigment simultaneously except ferrum, its feature exists In：The step 1) in reducing agent be sulfur dioxide, magnesium sulfite, ferrous sulfate and ferrous chloride in one or more The mixture of arbitrary proportion；Reducing agent is 0.1-1.5 with the mol ratio of Fe3+：1.
CN201611205574.8A 2016-12-23 2016-12-23 A kind of method that lateritic nickel ore pickle liquor produces black iron oxide pigment simultaneously except iron Active CN106673071B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108919585A (en) * 2018-06-29 2018-11-30 东华大学 A kind of grading-hole NiO/C electrochromic display device and its preparation and application
WO2020062964A1 (en) * 2018-09-25 2020-04-02 眉山顺应动力电池材料有限公司 Method for treating low-magnesium limonite type laterite nickel ore

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1807262A (en) * 2006-02-13 2006-07-26 上海一品颜料有限公司 Method for preparing ferriferrous oxide black pigment
CN102181638A (en) * 2011-04-30 2011-09-14 广西师范大学 Method for removing iron from leachate of nickel oxide ores
CN104120259A (en) * 2014-07-30 2014-10-29 广西师范大学 Nickel oxide ore acid leaching solution two-step iron removal method
CN104203830A (en) * 2012-03-19 2014-12-10 住友金属矿山株式会社 Production method for hematite for iron production
CN104831061A (en) * 2014-12-31 2015-08-12 金川集团股份有限公司 Method of recycling nickel, cobalt and iron from low-grade laterite-nickel ore
CN104831087A (en) * 2014-12-31 2015-08-12 金川集团股份有限公司 Method of recycling nickel, cobalt, iron and silicon from low-grade laterite nickel ore through combined leaching process

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1807262A (en) * 2006-02-13 2006-07-26 上海一品颜料有限公司 Method for preparing ferriferrous oxide black pigment
CN102181638A (en) * 2011-04-30 2011-09-14 广西师范大学 Method for removing iron from leachate of nickel oxide ores
CN104203830A (en) * 2012-03-19 2014-12-10 住友金属矿山株式会社 Production method for hematite for iron production
CN104120259A (en) * 2014-07-30 2014-10-29 广西师范大学 Nickel oxide ore acid leaching solution two-step iron removal method
CN104831061A (en) * 2014-12-31 2015-08-12 金川集团股份有限公司 Method of recycling nickel, cobalt and iron from low-grade laterite-nickel ore
CN104831087A (en) * 2014-12-31 2015-08-12 金川集团股份有限公司 Method of recycling nickel, cobalt, iron and silicon from low-grade laterite nickel ore through combined leaching process

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108919585A (en) * 2018-06-29 2018-11-30 东华大学 A kind of grading-hole NiO/C electrochromic display device and its preparation and application
CN108919585B (en) * 2018-06-29 2021-08-10 东华大学 Hierarchical pore NiO/C electrochromic display device and preparation and application thereof
WO2020062964A1 (en) * 2018-09-25 2020-04-02 眉山顺应动力电池材料有限公司 Method for treating low-magnesium limonite type laterite nickel ore

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