CN106904658A - A kind of method of acid content in reduction ferrous slag - Google Patents
A kind of method of acid content in reduction ferrous slag Download PDFInfo
- Publication number
- CN106904658A CN106904658A CN201710092627.8A CN201710092627A CN106904658A CN 106904658 A CN106904658 A CN 106904658A CN 201710092627 A CN201710092627 A CN 201710092627A CN 106904658 A CN106904658 A CN 106904658A
- Authority
- CN
- China
- Prior art keywords
- ferrous slag
- slag
- acid
- iron concentrate
- ferrous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000002893 slag Substances 0.000 title claims abstract description 56
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000002253 acid Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 54
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052742 iron Inorganic materials 0.000 claims abstract description 27
- 239000012141 concentrate Substances 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000004576 sand Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000005864 Sulphur Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 3
- 238000011417 postcuring Methods 0.000 claims description 2
- 238000004094 preconcentration Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000002918 waste heat Substances 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000005611 electricity Effects 0.000 abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 19
- 235000010215 titanium dioxide Nutrition 0.000 description 12
- 239000004408 titanium dioxide Substances 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 2
- 229910052683 pyrite Inorganic materials 0.000 description 2
- 239000011028 pyrite Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 238000010304 firing Methods 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
- XBDUTCVQJHJTQZ-UHFFFAOYSA-L iron(2+) sulfate monohydrate Chemical compound O.[Fe+2].[O-]S([O-])(=O)=O XBDUTCVQJHJTQZ-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention provides a kind of method for reducing acid content in ferrous slag, comprises the following steps：It is secondary raw material by the Iron concentrate that sand acid device is produced during burning ferrous slag is mixed, by Iron concentrate with ferrous slag by a certain percentage carry out premix merges cure certain hour after, it is mixed for sand acid device with sulphur again and mixes burning, after Iron concentrate is carried out premixing and merges curing certain hour by a certain percentage with ferrous slag, sulfuric acid mass percent concentration content is less than 1.0% in mixing slag, after reaction due in the ferrous slag sulfuric acid content it is extremely low, sand acid device electricity dirt, the equipment corrosion problem such as waste heat boiler disappears substantially, has efficient, economical effects to actual production.
Description
Technical field
The present invention relates to ferrous slag process field, and in particular to one kind mixes in burning product Iron concentrate and ferrous using ferrous slag
Slag carries out the method that premixing curing obtains low acid content ferrous slag.
Background technology
During Production By Sulfuric Acid Process titanium white, often producing 1t titanium dioxides will produce the 8~10t of spent acid of 20-25% or so, give up
Except containing main component H in acid2SO4Outward, also 25% or so ferrous sulfate, 1.0% or so solvable titanium, these spent acid
If directly being discharged without treatment, environment is not only polluted, also result in the serious waste of resource.How these spent acid are processed, and economy is closed
Reclaim wherein valuable part in reason ground, it has also become an important technology problem of Production By Sulfuric Acid Process titanium white, be also puzzlement environment
The significant problem that protection develops with titanium dioxide industry.
Most sulfuric acid method titanium pigment producers using concentration or complex acid by the way of carry out concentrate, to improve sulfuric acid concentration in the way of
The ferrous content in spent acid is reduced, is easy to purification and waste acid recovery.Typical way is 25% that the concentrated sulfuric acid is added to metering
In the titanium white waste acid of left and right, the sulfuric acid concentration of mixed acid is adjusted, be sufficiently stirred for, lowered the temperature, by solid-liquid separating equipment such as filter press,
Centrifuge or mole filter etc. are separated ferrous slag and clear liquid, and clear liquid can be directly used for that sulfuric acid is dry to be inhaled, titanium ore acidolysis or
Phosphorus ore is extracted.During the waste acid concentration, the iron in titanium white waste acid, the major impurity such as titanium is substantially completely precipitated into ferrous
Slag.
The main component of traditional ferrous slag is：Sulfuric acid (with 55% or so sulphur acid meter) content 30%；One water ferrous content
60%, 5.0~7.0% or so hydrated titanium dioxide, and a small amount of other impurities hydrate；Most producers are direct by ferrous slag
Neutralized using alkaline matter, while producing a large amount of waste residues, not only operating cost is high but also produces substantial amounts of waste residue, how comprehensive sharp
With ferrous slag for reducing the useless vice processing expense of titanium dioxide, product competitiveness is improved most important.
Most spontaneous pyrite concentrate sulphuric acid plants of titanium powder plant set, by ferrous slag account for the ratio 20-25% of sulfuric acid quality with
Sulphur is mixed, and the standby sulfuric acid of firing is mixed for pyrite concentrate sulphuric acid plant, and ferrous slag is decomposed through high-temperature oxydation, obtains Iron concentrate,
The Iron concentrate can be used for the preparation of rudimentary iron oxide red pigment, but due to containing a large amount of sulfuric acid in ferrous slag, mix serious during burning
Influence boiling furnace combustion effect, and sulfuric acid in raw material easily forms acid mist, severe corrosion equipment (electric dirt, waste heat in rear operation
Boiler), above-mentioned factor is limited by, device maintenance cost is high.
The content of the invention
The present invention combines the Iron concentrate (main component di-iron trioxide) that sand acid device is produced during burning ferrous slag is mixed
Be secondary raw material, by Iron concentrate with ferrous slag by a certain percentage carry out premix merges cure certain hour after, it is residual in mixing slag
Acid content is stayed to be reduced to extremely low level, because the ferrous slag sulfuric acid content is extremely low, sand acid device electricity dirt, the equipment such as waste heat boiler is rotten
Erosion problem disappears substantially, has efficient, economical effects to actual production.
Technical scheme is as follows：
The method of acid content, comprises the following steps in a kind of reduction ferrous slag：Sand acid device is being mixed into burning ferrous slag process
The Iron concentrate of middle generation is secondary raw material, and Iron concentrate is carried out into premix by a certain percentage with ferrous slag merges curing certain hour
Afterwards, then be mixed for sand acid device with sulphur and mix burnings, wherein the mass ratio of described Iron concentrate and ferrous slag be 0.08~
0.12：1, after the mixing of Iron concentrate and ferrous slag, the room temperature curing time is more than 12 hours, and Iron concentrate is cured with the mixing of ferrous slag
Afterwards, sulfuric acid mass percent concentration content is less than 1.0% in mixing slag.
Wherein, ferrous slag is obtained for spent acid pre-concentration, and described Iron concentrate is mixed burning and obtained through sand acid device；Described iron essence
Powder is used for sand acid device and mixes burning with the mixing post curing product of ferrous slag, wherein ferrous sulfate monohydrate is accounted in curing product
90%, ferric sulfate accounts for 10%.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is described in further detail.It should be appreciated that specific embodiment described herein is only used to explain the present invention, do not limit
In the present invention.
Units of percent is in example below：Mass percent.
Embodiment 1
The concentrated sulfuric acid of the spent acid that Producing Titanium Dioxide is produced with 98% is cured by mixing, and cold filtration obtains 55% sulfuric acid
For titanium dioxide acidolysis and phosphate production, filter cake ferrous slag adds sand acid device to mix the iron for burning ferrous generation in 8% ratio
Fine powder, after two kinds of powders are sufficiently mixed, stores up curing 12 hours, free acid content in detection mixing slag.
Embodiment 2
The concentrated sulfuric acid of the spent acid that Producing Titanium Dioxide is produced with 98% is cured by mixing, and cold filtration obtains 55% sulfuric acid
For titanium dioxide acidolysis and phosphate production, filter cake ferrous slag adds sand acid device to mix the iron for burning ferrous generation in 12% ratio
Fine powder, after two kinds of powders are sufficiently mixed, stores up curing 12 hours, free acid content in detection mixing slag.
| Sequence number | Title | Iron concentrate/ferrous slag | Free acid |
| Raw material | Ferrous slag | 0 | 15.0% |
| Embodiment 1 | Mixing slag | 8% | 0.30% |
| Embodiment 2 | Mixing slag | 12% | 0.10% |
Obtained from upper table, free acid concentration is 15% in raw material ferrous slag, by Iron concentrate and ferrous slag by a certain percentage
After carrying out premix merging curing certain hour, sulfuric acid content is less than 1.0% in mixing slag, due to the ferrous slag sulfuric acid content pole
Low, sand acid device electricity dirt, the equipment corrosion problem such as waste heat boiler disappears substantially, has efficient, economic dual effect to actual production
Benefit.
Claims (4)
1. it is a kind of reduce ferrous slag in acid content method, it is characterised in that：Comprise the following steps：Sand acid device is being mixed into burning Asia
The Iron concentrate produced during scum is secondary raw material, and Iron concentrate is carried out into premix by a certain percentage with ferrous slag merges curing one
After fixing time, then with sulphur be mixed for sand acid device mix burning, wherein described Iron concentrate is with the mass ratio of ferrous slag
0.08~0.12：1, after the mixing of Iron concentrate and ferrous slag, the room temperature curing time is more than 12 hours, and Iron concentrate is mixed with ferrous slag
After closing curing, sulfuric acid mass percent concentration content is less than 1.0% in mixing slag.
2. it is according to claim 1 it is a kind of reduce ferrous slag in acid content method, it is characterised in that：Described ferrous slag
For spent acid pre-concentration is obtained.
3. it is according to claim 1 it is a kind of reduce ferrous slag in acid content method, it is characterised in that：Described Iron concentrate
Burning is mixed through sand acid device to obtain.
4. it is according to claim 1 it is a kind of reduce ferrous slag in acid content method, it is characterised in that：Described Iron concentrate
It is used for sand acid device with the mixing post curing product of ferrous slag and mixes burning.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710092627.8A CN106904658A (en) | 2017-02-20 | 2017-02-20 | A kind of method of acid content in reduction ferrous slag |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710092627.8A CN106904658A (en) | 2017-02-20 | 2017-02-20 | A kind of method of acid content in reduction ferrous slag |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106904658A true CN106904658A (en) | 2017-06-30 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710092627.8A Pending CN106904658A (en) | 2017-02-20 | 2017-02-20 | A kind of method of acid content in reduction ferrous slag |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792187A (en) * | 2009-12-30 | 2010-08-04 | 四川龙蟒钛业股份有限公司 | Method for producing feed grade ferrous sulfate monohydrate from titanium pigment waste acid condensed slag |
| CN101913573A (en) * | 2010-08-30 | 2010-12-15 | 攀枝花圣地元科技有限责任公司 | Method for producing sulfuric acid and iron oxide red |
| CN102372306A (en) * | 2011-08-11 | 2012-03-14 | 四川龙蟒钛业股份有限公司 | Method for recycling concentrated slag of wasted acid from titanium white production |
| CN103193278A (en) * | 2013-04-25 | 2013-07-10 | 白银富提拉化工科技有限公司 | Reductive calcining process of ferrous sulfate as byproduct of titanium dioxide |
| CN104876191A (en) * | 2014-12-12 | 2015-09-02 | 荆门新洋丰中磷肥业有限公司 | Method for treating waste ferrous sulphate by sulfide enriched concentrate-based acid making device |
| CN105417502A (en) * | 2015-12-30 | 2016-03-23 | 攀枝花东方钛业有限公司 | Method for preparing acid through high-proportion co-combustion ferrous sulfate |
-
2017
- 2017-02-20 CN CN201710092627.8A patent/CN106904658A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792187A (en) * | 2009-12-30 | 2010-08-04 | 四川龙蟒钛业股份有限公司 | Method for producing feed grade ferrous sulfate monohydrate from titanium pigment waste acid condensed slag |
| CN101913573A (en) * | 2010-08-30 | 2010-12-15 | 攀枝花圣地元科技有限责任公司 | Method for producing sulfuric acid and iron oxide red |
| CN102372306A (en) * | 2011-08-11 | 2012-03-14 | 四川龙蟒钛业股份有限公司 | Method for recycling concentrated slag of wasted acid from titanium white production |
| CN103193278A (en) * | 2013-04-25 | 2013-07-10 | 白银富提拉化工科技有限公司 | Reductive calcining process of ferrous sulfate as byproduct of titanium dioxide |
| CN104876191A (en) * | 2014-12-12 | 2015-09-02 | 荆门新洋丰中磷肥业有限公司 | Method for treating waste ferrous sulphate by sulfide enriched concentrate-based acid making device |
| CN105417502A (en) * | 2015-12-30 | 2016-03-23 | 攀枝花东方钛业有限公司 | Method for preparing acid through high-proportion co-combustion ferrous sulfate |
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Application publication date: 20170630 |