CN108002447A - A kind of method that magnetic ferroferric oxide is prepared by titanium white waste acid - Google Patents
A kind of method that magnetic ferroferric oxide is prepared by titanium white waste acid Download PDFInfo
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- CN108002447A CN108002447A CN201711378255.1A CN201711378255A CN108002447A CN 108002447 A CN108002447 A CN 108002447A CN 201711378255 A CN201711378255 A CN 201711378255A CN 108002447 A CN108002447 A CN 108002447A
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- titanium
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- titanium white
- white waste
- waste acid
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- 239000002253 acid Substances 0.000 title claims abstract description 120
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 89
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000002699 waste material Substances 0.000 title claims abstract description 73
- 235000010215 titanium dioxide Nutrition 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 43
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 77
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000010936 titanium Substances 0.000 claims abstract description 49
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 229910052742 iron Inorganic materials 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000001914 filtration Methods 0.000 claims abstract description 26
- 239000000047 product Substances 0.000 claims abstract description 24
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000002893 slag Substances 0.000 claims abstract description 12
- 239000012153 distilled water Substances 0.000 claims abstract description 10
- 238000005352 clarification Methods 0.000 claims abstract description 9
- 239000000706 filtrate Substances 0.000 claims abstract description 9
- 238000002955 isolation Methods 0.000 claims abstract description 9
- 239000002002 slurry Substances 0.000 claims abstract description 9
- 239000006228 supernatant Substances 0.000 claims abstract description 9
- 238000004062 sedimentation Methods 0.000 claims abstract description 8
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 48
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 11
- -1 iron ions Chemical class 0.000 claims description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 9
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 9
- 239000004571 lime Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 239000000908 ammonium hydroxide Substances 0.000 claims description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 8
- 238000004513 sizing Methods 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 4
- 229910001447 ferric ion Inorganic materials 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims 1
- 229940056319 ferrosoferric oxide Drugs 0.000 abstract description 28
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 13
- 230000008569 process Effects 0.000 description 12
- 238000012545 processing Methods 0.000 description 8
- 235000011007 phosphoric acid Nutrition 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000005389 magnetism Effects 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 241000219095 Vitis Species 0.000 description 3
- 235000009754 Vitis X bourquina Nutrition 0.000 description 3
- 235000012333 Vitis X labruscana Nutrition 0.000 description 3
- 235000014787 Vitis vinifera Nutrition 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 239000001038 titanium pigment Substances 0.000 description 3
- 229910017906 NH3H2O Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910010298 TiOSO4 Inorganic materials 0.000 description 2
- LCPUDZUWZDSKMX-UHFFFAOYSA-K azane;hydrogen sulfate;iron(3+);sulfate;dodecahydrate Chemical compound [NH4+].O.O.O.O.O.O.O.O.O.O.O.O.[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LCPUDZUWZDSKMX-UHFFFAOYSA-K 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- KADRTWZQWGIUGO-UHFFFAOYSA-L oxotitanium(2+);sulfate Chemical compound [Ti+2]=O.[O-]S([O-])(=O)=O KADRTWZQWGIUGO-UHFFFAOYSA-L 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910000628 Ferrovanadium Inorganic materials 0.000 description 1
- 241000165940 Houjia Species 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 1
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 229910001037 White iron Inorganic materials 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical class [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method 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
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000011553 magnetic fluid Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical class [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 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
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
-
- 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)
- Inorganic Chemistry (AREA)
- Compounds Of Iron (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The present invention relates to a kind of method that magnetic ferroferric oxide is prepared by titanium white waste acid.This method includes：Titanium white waste acid is collected, neutralizer is added and is once neutralized, clarification spent acid is obtained after sedimentation filtration；After gained spent acid is heated up, the material for adding phosphorous acid group carries out removing titanium, obtains removing the spent acid after titanium after filtering titanium slag；Secondary neutralization is carried out toward except the spent acid after titanium, and is passed through air or oxygen, heavy iron is kept the temperature under fixed temperature；Filtering solution after the completion of heavy iron, filtrate obtain sulfate product by concentrating and separating, add water after filter residue is washed and reducing agent is sized mixing；Heavy scum slurry is placed in closed reactor, control reaction atmosphere carries out closed thermal synthesis reaction；Washed after the completion of reaction using distilled water or absolute ethyl alcohol, Magnetic Isolation, outwell supernatant, it is dry to obtain ferroso-ferric oxide.The present invention using titanium white waste acid prepares magnetic ferroferric oxide, have the advantages that cost it is low, can be with large-scale production, added value of product height, environment and remarkable in economical benefits.
Description
Technical field
The invention belongs to metallurgical field of waste liquid treatment, and in particular to a kind of to prepare magnetic ferroferric oxide by titanium white waste acid
Method.
Background technology
Titanium dioxide industry production method mainly has chloridising and sulfuric acid process.Sulfuric acid process is ripe, the adaptation to titanium material
Property is strong, production cost is low, technology maturation, it can not only produce anatase titanium dioxide product, but also can produce rutile-type product, be existing titanium white
A kind of method generally used in the powder mode of production.But sulfuric acid process often produces 1 ton of titanium dioxide, to discharge concentration is about
8~10 tons of the spent acid of 20% (mass concentration), is known as titanium white waste acid.In titanium white waste acid in addition to containing main component sulfuric acid, also
There are the ferrous sulfate of 25% (mass concentration) left and right, the solvable titanium of 1.0% (mass concentration) left and right, if titanium white waste acid is without processing
Directly discharge, not only pollute environment, also result in the serious waste of resource.These spent acid how are handled, economically recycle it
In valuable part, it has also become an important technology problem of sulfate process titanium dioxide production, and puzzlement environmental protection and titanium white
The significant problem of powder industry development.
The common titanium white waste acid processing method of industry has vacuum concentration, lime to neutralize, leach phosphorus ore tricresyl phosphate kind at present
Technique.Main problem is that processing cost is excessive in titanium white waste acid processing procedure, in terms of the lime neutralisation minimum by processing cost,
The expense of 1 ton of titanium white waste acid is often handled just more than 60 yuan.Most sulfuric acid method titanium pigment producers are by the way of concentration or complex acid
Concentrate is carried out, the ferrous content in spent acid is reduced in a manner of improving sulfuric acid concentration, easy to purify and waste acid recovery.Typically do
Method is that the concentrated sulfuric acid is added in the titanium white waste acid of 25% (mass concentration) left and right of metering, adjusts the sulfuric acid concentration of mixed acid,
Fully reaction, cooling, by solid-liquid separating equipment such as filter press, centrifuge or mole filter etc. carry out ferrous slag and clear liquid
Separation, clear liquid can be directly used for sulfuric acid and do suction, titanium ore acidolysis or phosphorus ore extraction.During the waste acid concentration, in titanium white waste acid
Iron, largely precipitation is separated the major impurity such as titanium, obtains ferrous slag, then ferrous slag is directly neutralized using alkaline matter.
Not only operating cost is high but also produces substantial amounts of waste residue for this method, how to comprehensively utilize ferrous resource and reduces at titanium pigment waste acid
Reason expense, the competitiveness for improving product are most important.
Magnetic ferroferric oxide is the magnetic black crystals of tool, belongs to cubic system, because it has the physico of uniqueness
Learn property and to be widely used in magnetic storage, magnetic recording, magnetic fluid material, nano-magnetic medicinal, electric wave absorbing materials etc. many
Field.Natural ferroso-ferric oxide is steel raw material, and a large amount of import magnetic iron ores in China are produced for steel, and annual import volume reaches
2~300,000,000 tons.It is super that the ferroso-ferric oxide major product of synthesis has the iron oxide black as pigment, the magnetic powder of magnetic material and magnetic flocculation to use
Thin ferroso-ferric oxide etc., synthesizes these ferroso-ferric oxide products and uses sodium hydroxide high as neutralizer, its production cost.
Therefore, there is an urgent need for proposing a kind of method that magnetic ferroferric oxide is prepared by titanium white waste acid, can make full use of a large amount of
Titanium white waste acid, reduce the discharge of titanium white waste acid, reduce titanium pigment waste acid processing cost, can realize scale utilizes titanium white
Iron resource in spent acid, reduces the production cost of ferroso-ferric oxide.
The content of the invention
(1) technical problems to be solved
Present invention aim to address current domestic titanium white waste acid processing difficulty and the existing production of magnetic ferroferric oxide
Complex process and problem of high cost, there is provided a kind of method that magnetic ferroferric oxide is prepared by titanium white waste acid, this method is with titanium
White spent acid is raw material, and technological process is simple, and the product purity of production is big, can fully utilize substantial amounts of titanium white waste acid, is reduced
It is discharged, and can realize the low-cost industrial production of magnetic ferroferric oxide.
(2) technical solution
In order to achieve the above object, the main technical schemes that the present invention uses are as follows：
A kind of method that magnetic ferroferric oxide is prepared by titanium white waste acid, comprises the following steps：
(1) titanium white waste acid of iron content is collected, a neutralizer is added and is once neutralized, it is useless that clarification is obtained after sedimentation filtration
Acid；
(2) after gained spent acid is heated up, the material for adding phosphorous acid group carries out removing titanium, is obtained after filtering titanium slag after removing titanium
Spent acid；
(3) secondary neutralization is carried out toward except the spent acid after titanium adds secondary neutralizer, and is passed through air or oxygen, then in fixation
At a temperature of keep the temperature heavy iron；
(4) filtering solution after the completion of heavy iron, filtrate obtains sulfate product by concentrating and separating, after filter residue is washed,
Add water and reducing agent is sized mixing；
(5) the heavy scum system after sizing mixing is placed in reaction vessel, and control reaction atmosphere carries out closed thermal synthesis reaction；
(6) washed after reaction using distilled water or absolute ethyl alcohol, Magnetic Isolation, outwells supernatant, is obtained by drying
Obtain ferroso-ferric oxide product.
Preferably, the titanium white waste acid includes 150~350g/L free sulfuric acids, the total iron ions of 10~75g/L and 4~9g/L
Dissolubility titanium, total iron ion include ferrous ion and ferric ion.
Preferably, a neutralizer is the one or more in lime, ammonium hydroxide, hydroxide, carbonate；
Sulfuric acid content after the once neutralization is controlled in 80~110g/L.
Preferably, the material of the phosphorous acid group is the one or more in phosphoric acid, phosphate, phosphoric acid industrial residue.
Preferably, it is described remove titanium during the molar ratio of titanium and phosphate radical be 1:1.5~1:3, reaction temperature is 50~105
DEG C, the reaction time is 0.5~2h.
Preferably, the secondary neutralizer is the one or more in lime, ammonium hydroxide, hydroxide, carbonate；
The pH of reaction system is controlled 1.0~3.0 after the secondary neutralization.
Preferably, the reaction temperature during the heavy iron is 85~105 DEG C, and soaking time is 2~5h.
Preferably, the reducing agent in the step (4) for formaldehyde, formic acid, hydrazine hydrate, glucose, one kind in oxalic acid or
It is a variety of.
Preferably, the reaction atmosphere in the step (5) is oxygen-containing atmosphere, and oxygen content is 15%~65%.
Preferably, the thermal synthesis reaction condition in the step (5) is that the pH of slurry is 7~14, reducing agent and heavy scum
Mass ratio be 0.5:1~10:1, reaction temperature is 120~260 DEG C, and the reaction time is 3~10h.
Reaction process according to the present invention is as follows：
The neutralization reaction that titanium white waste acid occurs is as follows：
CaO+2H+→Ca2++H2O
NH3H2O+H+→NH4 ++H2O
OH-+H+→H2O
CO3 2-+2H+→CO2+H2O
Except titanium reacts：
TiOSO4+2n H3PO4→TiO2·n P2O4·mH2O+H2SO4
Heavy iron reaction：
4Fe2++O2+4H+→4Fe3++2H2O
3Fe3++2SO4 2-+M++6H2O→MFe3(SO4)2(OH)6+6H+
Wherein, M NH4, Na, H2O etc.
Thermal synthesis is reacted：
(3) beneficial effect
The prior art is contrasted, the present invention has following remarkable advantage：
The present invention is using the spent acid after ilmenite acidolysis as raw material, forms siderotil by neutralizing, except titanium, heavy iron, then by iron
Alum reduces to form ferroso-ferric oxide.Present invention process flow is simple, and it is difficult and magnetic to solve domestic titanium white waste acid processing at present
The existing complex production process of ferroso-ferric oxide and problem of high cost, can make full use of substantial amounts of titanium white waste acid, reduce titanium
The discharge of white spent acid, at the same can scale utilize iron resource in titanium white waste acid, turn waste into wealth, overcome existing process preparation
The problem of magnetic ferroferric oxide material process is various, heavy workload, realizes the low-cost industrial of magnetic ferroferric oxide
Production.
, can be with since the acidity that siderotil is formed is relatively low during magnetism four is prepared using titanium white waste acid and aoxidizes three bodies
The content of foreign ion is controlled, this improves the purity of ferroso-ferric oxide, purity reaches more than 98%, the magnetism four of generation
Fe 3 O serves not only as iron-smelting raw material, it is also possible to makees the basic material of other industry.
Brief description of the drawings
Fig. 1 is a kind of flow for method that magnetic ferroferric oxide is prepared by titanium white waste acid that embodiment of the present invention provides
Figure.
Embodiment
In order to preferably explain the present invention, in order to understand, with reference to specific experiment example and attached drawing, the present invention is made detailed
Thin description, but the present invention is not limited to following embodiments.
As shown in Figure 1, the present invention proposes a kind of method that magnetic ferroferric oxide is prepared by titanium white waste acid, including following step
Suddenly：
(1) titanium white waste acid of iron content is collected, a neutralizer is added and is once neutralized, it is useless that clarification is obtained after sedimentation filtration
Acid.
The titanium white waste acid used in present embodiment include 150~350g/L free sulfuric acids, the total iron ions of 10~75g/L and
4~9g/L dissolubility titaniums.Wherein, total iron ion includes ferrous ion and ferric ion.
During a neutralization reaction, the neutralizer used is in lime, ammonium hydroxide, hydroxide, carbonate
One or more, can occur neutralization reaction with the acid ion (mainly including sulfuric acid) in titanium white waste acid.Due to titanium white waste acid
Acidity is excessive, it is therefore desirable to first carries out neutralization reaction to reduce its acidity, the sulfuric acid content control after a final neutralization reaction
In 80~110g/L scopes, for it is follow-up provides except titanium needed for acidity, and be unlikely to make titanium in titanium white waste acid solution and iron to sink
Form sediment.Wherein, according to the volume of sulfuric acid content and titanium white waste acid initial in the sulfuric acid content after a neutralization reaction, titanium white waste acid
To determine the additive amount of a neutralizer.
The neutralization reaction that titanium white waste acid occurs is as follows：
CaO+2H+→Ca2++H2O
NH3H2O+H+→NH4 ++H2O
OH-+H+→H2O
CO3 2-+2H+→CO2+H2O。
Through the filter residue containing solids is obtained by filtration and dissolved with sulfate, titanyl sulfate, ferrous iron after neutralization reaction
The clarification waste acid liquor of ion.
(2) after gained spent acid is heated up, the material for adding phosphorous acid group carries out removing titanium, is obtained after filtering titanium slag after removing titanium
Spent acid.
During except titanium, the material of the phosphorous acid group used is one in phosphoric acid, phosphate, phosphoric acid industrial residue
Kind is a variety of.Except the molar ratio of titanium and phosphate radical is 1 during titanium:1.5~1:3, reaction temperature is 50~105 DEG C, during reaction
Between be 0.5~2h, meet these Parameter Conditions could be formed titanium precipitation.
By taking phosphoric acid as an example, the sulfate containing titanium is except titanium reacts with what phosphoric acid occurred in spent acid：
TiOSO4+2n H3PO4→TiO2·n P2O4·mH2O+H2SO4
Except titanium products obtain TiO after filtering2·n P2O4·mH2O titanium slags and sulfur acid, sulfate, ferrous ion it is useless
Acid.
(3) secondary neutralization is carried out toward except the spent acid after titanium adds secondary neutralizer, and is passed through air or oxygen, then in fixation
At a temperature of keep the temperature heavy iron.
During secondary neutralization reaction, the secondary neutralizer used is in lime, ammonium hydroxide, hydroxide, carbonate
One or more, can with except in the spent acid after titanium acid ion (mainly including sulfuric acid) occur neutralization reaction.According to addition two
Secondary neutralizer controls the pH of reaction system to meet the condition in the range of 1.0~3.0 to determine two after secondary neutralization reaction occurs
The additive amount of secondary neutralizer.
On the one hand reaction system can be beneficial to heavy iron and react, on the other hand can control containing for foreign ion well in acidity
Amount, so as to improve the purity of final ferroso-ferric oxide product.
, it is necessary to be kept the temperature under conditions of being 85~105 DEG C in oxygen-containing atmosphere, acid condition and reaction temperature during heavy iron
Heavy iron reaction, generation ferrovanadium MFe occur for 2~5h3(SO4)2(OH)6Solids and the solution dissolved with sulfate.Ferrous ion
The heavy iron reaction occurred with ferric ion is as follows：
4Fe2++O2+4H+→4Fe3++2H2O
3Fe3++2SO4 2-+M++6H2O→MFe3(SO4)2(OH)6+6H+
Wherein, M NH4, Na, H2O etc..
(4) filtering solution after the completion of heavy iron, filtrate obtains sulfate product by concentrating and separating, after filter residue is washed,
Add water and reducing agent is sized mixing.
Product after heavy iron is filtered to be obtained including MFe3(SO4)2(OH)6Filter residue and filtrate dissolved with sulfate, filter
The concentrated decomposition of liquid obtains sulfate, and filter residue is washed using distilled water, removes the sulfate of filter residue remained on surface, Zhi Houjia
Enter water and reducing agent and modulate the slurry that pH is 7~14, to pass through the magnetic ferroso-ferric oxide of follow-up thermal synthesis reaction production
Product.
Wherein, the above-mentioned reducing agent used is the one or more in formaldehyde, formic acid, hydrazine hydrate, glucose, oxalic acid, this
A little reducing agents can be by MFe3(SO4)2(OH)6In high price iron be reduced to ferroso-ferric oxide.The additive amount of reducing agent meets following
It is required that：The mass ratio of reducing agent and heavy scum is 0.5:1~10:1, reducing agent selects this scope to be greatly improved four oxidations three
The purity of iron.And the additive amount of water is to be met according to the pH of slurry after the reducing agent for adding water and above-mentioned content in 7~14 scopes
Interior condition determines.
(5) the heavy scum system after sizing mixing is placed in reaction vessel, and control reaction atmosphere carries out closed thermal synthesis reaction.
Ferroso-ferric oxide product is formed in order to control, the heavy scum system after sizing mixing is placed in closed reactor, control
Oxygen content gas is 15%~65%.It is 120~260 DEG C to regulate and control reaction temperature, and the reaction time is 3~10h, to realize thermal synthesis
Reaction, obtains the mixed liquor of ferroso-ferric oxide and sulfate.The thermal synthesis of generation is reacted：
(6) washed after reaction using distilled water or absolute ethyl alcohol, Magnetic Isolation, outwells supernatant, is obtained by drying
Obtain ferroso-ferric oxide product.
Solid impurity using distilled water or absolute ethyl alcohol washing in the mixed liquor containing ferroso-ferric oxide and sulfate, then pass through
The removing and drying process of Magnetic Isolation, supernatant, obtain the high magnetic ferroferric oxide product of purity.
The prior art is contrasted, the present invention has following remarkable advantage：
The present invention is using the spent acid after ilmenite acidolysis as raw material, forms siderotil by neutralizing, except titanium, heavy iron, then by iron
Alum reduces to form ferroso-ferric oxide.Present invention process flow is simple, and it is difficult and magnetic to solve domestic titanium white waste acid processing at present
The existing complex production process of ferroso-ferric oxide and problem of high cost, can make full use of substantial amounts of titanium white waste acid, reduce titanium
The discharge of white spent acid, at the same can scale utilize iron resource in titanium white waste acid, turn waste into wealth, overcome existing process preparation
The problem of magnetic ferroferric oxide material process is various, heavy workload, realizes the low-cost industrial of magnetic ferroferric oxide
Production.
, can be with since the acidity that siderotil is formed is relatively low during magnetism four is prepared using titanium white waste acid and aoxidizes three bodies
The content of foreign ion is controlled, this improves the purity of ferroso-ferric oxide, purity reaches more than 98%, the magnetism four of generation
Fe 3 O serves not only as iron-smelting raw material, it is also possible to makees the basic material of other industry.
Referring to following preferred embodiment：
Embodiment 1
A kind of method that magnetic ferroferric oxide is prepared by titanium white waste acid, comprises the following steps：Collect titanium white waste acid 1L, warp
It is 350g/L free sulfuric acids to analyze its main component, the total iron ions of 75g/L, 9g/L dissolubility titaniums.Add in lime progress once
With it is 110g/L to be neutralized to sulfuric acid content.Clarification spent acid is obtained after sedimentation filtration.After gained spent acid is warming up to 105 DEG C, add
50g phosphatase reaction 0.5h, obtain removing the spent acid after titanium after filtering insoluble titanium slag.Air is passed through to spent acid again, adds ammonium hydroxide, is adjusted
PH value is to 3.0, and control temperature maintains 105 DEG C, soaking time 2h.Filtering solution after heavy iron, filtrate pass through concentrating and separating
Ammonium sulfate product is obtained, after filter residue is washed, (mass ratio of hydrazine hydrate and heavy scum is 0.5 for addition water and hydrazine hydrate:1) into
Row is sized mixing, and the pH for adjusting slurry is 14, and the heavy scum system after sizing mixing is placed in closed reactor, controls the oxygen content gas to be
15%, reaction temperature is 260 DEG C, reaction time 3h, carries out closed thermal synthesis reaction.Adopt and be washed with distilled water after reaction
2 times, Magnetic Isolation, outwells supernatant, obtains ferroso-ferric oxide powder by dry, after testing, the purity of ferroso-ferric oxide is
99%.
Embodiment 2
A kind of method that magnetic ferroferric oxide is prepared by titanium white waste acid, comprises the following steps：Collect titanium white waste acid 1L, warp
It is 150g/L free sulfuric acids to analyze its main component, the total iron ions of 10g/L, 4g/L dissolubility titaniums.Add in ammonium hydroxide progress once
With it is 80g/L to be neutralized to sulfuric acid content.Clarification spent acid is obtained after sedimentation filtration.After gained spent acid is warming up to 55 DEG C, add
20g ammonium hydrogen phosphates react 2h, obtain removing the spent acid after titanium after filtering insoluble titanium slag.Air is passed through to spent acid again, it is molten to add caustic soda
Liquid, adjusts pH value to 1.0, control temperature maintains 85 DEG C, soaking time 5h.Filtering solution after heavy iron, filtrate is through overrich
Contract isolated sodium sulphate product, and after filter residue is washed, (mass ratio of formaldehyde and heavy scum is 10 for addition water and formaldehyde:1)
Size mixing, the pH for adjusting slurry is 7, and the heavy scum system after sizing mixing is placed in closed reactor, controls oxygen content gas
For 65%, reaction temperature is 120 DEG C, reaction time 10h, carries out closed thermal synthesis reaction.Distilled water is used after reaction
Washing 2 times, Magnetic Isolation, outwells supernatant, and ferroso-ferric oxide powder is obtained by dry, after testing, ferroso-ferric oxide it is pure
Spend for 98%.
Embodiment 3
A kind of method that magnetic ferroferric oxide is prepared by titanium white waste acid, comprises the following steps：Collect titanium white waste acid 1L, warp
It is 250g/L free sulfuric acids to analyze its main component, the total iron ions of 55g/L, 6g/L dissolubility titaniums.Lime stone is added to carry out once
Neutralize, it is 100g/L to be neutralized to sulfuric acid content.Clarification spent acid is obtained after sedimentation filtration.After gained spent acid is warming up to 80 DEG C, add
Enter 25g phosphoric acids waste residue reaction 1.5h, obtain removing the spent acid after titanium after filtering insoluble titanium slag.Oxygen is passed through to spent acid again, is added
Soda ash, adjusts pH value to 2.0, control temperature maintains 95 DEG C, soaking time 4h.Filtering solution after heavy iron, filtrate are passed through
Concentrating and separating obtains sodium sulphate product, after filter residue is washed, adds water, formic acid and oxalic acid (mass ratio 1:1) mixed liquor
(mass ratio of the mixed liquor of formic acid and oxalic acid and heavy scum is 5:1) size mixing after, the pH for adjusting slurry is 10, after sizing mixing
Heavy scum system be placed in closed reactor, it is 50% to control oxygen content gas, and reaction temperature is 200 DEG C, and the reaction time is
6h, carries out closed thermal synthesis reaction.Adopt and be washed with distilled water 3 times after reaction, Magnetic Isolation, outwells supernatant, through overdrying
Dry acquisition ferroso-ferric oxide powder, after testing, the purity of ferroso-ferric oxide is 98%.
Embodiment 4
A kind of method that magnetic ferroferric oxide is prepared by titanium white waste acid, comprises the following steps：Collect titanium white waste acid 1L, warp
It is 300g/L free sulfuric acids to analyze its main component, the total iron ions of 40g/L, 5g/L dissolubility titaniums.Potassium carbonate is added to carry out once
Neutralize, it is 88g/L to be neutralized to sulfuric acid content.Clarification spent acid is obtained after sedimentation filtration.After gained spent acid is warming up to 65 DEG C, add
30g sodium phosphates react 1h, obtain removing the spent acid after titanium after filtering insoluble titanium slag.Air is passed through to spent acid again, adds potassium carbonate, is adjusted
PH value is saved to 2.5, control temperature maintains 90 DEG C, soaking time 4h.Filtering solution after heavy iron, filtrate pass through concentrating and separating
Obtain potassium product, after filter residue is washed, add water, hydrazine hydrate and grape acid (hydrazine hydrate and grape acid and mass ratio
For 2:1) (mass ratio of the mixed liquor of hydrazine hydrate and grape acid and heavy scum is 2 to mixed liquor:1) size mixing after, adjust slurry
It is 8 to expect pH, and the heavy scum system after sizing mixing is placed in closed reactor, and it is 20% to control oxygen content gas, and reaction temperature is
160 DEG C, reaction time 8h, carry out closed thermal synthesis reaction.Adopt and be washed with distilled water 2 times after reaction, Magnetic Isolation, falls
Fall supernatant, ferroso-ferric oxide powder is obtained by dry, after testing, the purity of ferroso-ferric oxide is 99%.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, the change or replacement that can readily occur in,
It should be covered by the protection scope of the present invention.
Claims (10)
- A kind of 1. method that magnetic ferroferric oxide is prepared by titanium white waste acid, it is characterised in that comprise the following steps：(1) titanium white waste acid of iron content is collected, a neutralizer is added and is once neutralized, clarification spent acid is obtained after sedimentation filtration；(2) after gained spent acid is heated up, the material for adding phosphorous acid group carries out removing titanium, is obtained after filtering titanium slag except useless after titanium Acid；(3) secondary neutralization is carried out toward except the spent acid after titanium adds secondary neutralizer, and is passed through air or oxygen, then in fixed temperature The lower heavy iron of insulation；(4) filtering solution after the completion of heavy iron, filtrate obtains sulfate product by concentrating and separating, after filter residue is washed, adds Water and reducing agent are sized mixing；(5) the heavy scum system after sizing mixing is placed in reaction vessel, and control reaction atmosphere carries out closed thermal synthesis reaction；(6) washed after reaction using distilled water or absolute ethyl alcohol, Magnetic Isolation, outwells supernatant, and four are obtained by dry Fe 3 O product.
- A kind of 2. method that magnetic ferroferric oxide is prepared by titanium white waste acid according to claim 1, it is characterised in that institute Stating titanium white waste acid includes 150~350g/L free sulfuric acids, the total iron ions of 10~75g/L and 4~9g/L dissolubility titaniums, total iron Ion includes ferrous ion and ferric ion.
- A kind of 3. method that magnetic ferroferric oxide is prepared by titanium white waste acid according to claim 1, it is characterised in that institute A neutralizer is stated as the one or more in lime, ammonium hydroxide, hydroxide, carbonate；Sulfuric acid content after the once neutralization is controlled in 80~110g/L.
- A kind of 4. method that magnetic ferroferric oxide is prepared by titanium white waste acid according to claim 1, it is characterised in that institute The material for stating phosphorous acid group is phosphoric acid, the one or more in phosphate, phosphoric acid industrial residue.
- A kind of 5. method that magnetic ferroferric oxide is prepared by titanium white waste acid according to claim 4, it is characterised in that institute State except the molar ratio of titanium and phosphate radical is 1 during titanium:1.5~1:3, reaction temperature is 50~105 DEG C, the reaction time 0.5 ~2h.
- A kind of 6. method that magnetic ferroferric oxide is prepared by titanium white waste acid according to claim 3, it is characterised in that institute Secondary neutralizer is stated as the one or more in lime, ammonium hydroxide, hydroxide, carbonate；The pH of reaction system is controlled 1.0~3.0 after the secondary neutralization.
- A kind of 7. method that magnetic ferroferric oxide is prepared by titanium white waste acid according to claim 6, it is characterised in that institute The reaction temperature stated during heavy iron is 85~105 DEG C, and soaking time is 2~5h.
- A kind of 8. method that magnetic ferroferric oxide is prepared by titanium white waste acid according to claim 7, it is characterised in that institute The reducing agent stated in step (4) is formaldehyde, the one or more in formic acid, hydrazine hydrate, glucose, oxalic acid.
- A kind of 9. method that magnetic ferroferric oxide is prepared by titanium white waste acid according to claim 8, it is characterised in that institute It is oxygen-containing atmosphere to state the reaction atmosphere in step (5), and oxygen content is 15%~65%.
- 10. according to a kind of method that magnetic ferroferric oxide is prepared by titanium white waste acid of claim 1-9 any one of them, it is special Sign is that the thermal synthesis reaction condition in the step (5) is that the pH of slurry is 7~14, the mass ratio of reducing agent and heavy scum For 0.5:1~10:1, reaction temperature is 120~260 DEG C, and the reaction time is 3~10h.
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