CN110396593A - A kind of method of high phosphorus iron ore concentrate high-temperature vapor roasting-acidleach dephosphorization - Google Patents
A kind of method of high phosphorus iron ore concentrate high-temperature vapor roasting-acidleach dephosphorization Download PDFInfo
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- CN110396593A CN110396593A CN201910835955.1A CN201910835955A CN110396593A CN 110396593 A CN110396593 A CN 110396593A CN 201910835955 A CN201910835955 A CN 201910835955A CN 110396593 A CN110396593 A CN 110396593A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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- C—CHEMISTRY; METALLURGY
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
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Abstract
A kind of method of high phosphorus iron ore concentrate high-temperature vapor roasting-acidleach dephosphorization sequentially includes the following steps: (1) for the levigate screening of high phosphorus iron ore concentrate and obtains high phosphorus iron ore concentrate powder；(2) primary cyclone is transported to through screw(-type) feeder；It opens air-introduced machine and forms negative pressure；(3) the level-one solid material that gas solid separation is formed enters suspension roaster；(4) high-temperature vapor is generated by burner combustion and enters suspension roaster, level-one solid material is heated；(5) material after being heated enters secondary cyclone, and secondary gas solid separation forms the discharge of second level solid material；(6) second level solid material enters stirred leaching tank leaching, leaches material and is separated by filtration.Method of the invention is superfine suitable for the disseminated grain size that conventional beneficiation method can not be handled, and the high phosphorus refractory iron ore of symbiosis complexity has reached in product Iron grade, iron recovery and dephosphorization rate everyway compared with high target so that iron ore deposit is fully used.
Description
Technical field
The invention belongs to technical field of mineral processing, in particular to a kind of high phosphorus iron ore concentrate high-temperature vapor roasting-acidleach
The method of dephosphorization.
Background technique
High-phosphorus iron ore is important one of Refractory iron ore resource, high-phosphorus iron ore is high with Iron grade, reserves are big,
But phosphorus content also high feature, therefore the efficient Utilizing question for solving high-phosphorus iron ore is of great significance；The high ferrophosphorus in China
Ore reserve is up to 74.5 hundred million tons, and it is domestic to be mainly distributed on the Yangtze river basin and Yunnan Province, such as Mei Shanhan fosfosiderite, Hubei Ningxiang formula
Iron ore etc.；These height belong to weakly magnetic iron ore containing fosfosiderite, mainly there is hot-liquid type and appositional pattern bloodstone and siderite two major classes,
Wherein the occurrence status of phosphorus is mainly based on apatite in hot-liquid type iron ore, and the occurrence status of phosphorus is main in appositional pattern iron ore
Exist in the form of preparing granular collophane.
Currently, high-phosphorus iron ore mentions iron method for reducing phosphorus mainly and has the modes such as magnetic separation, flotation, acidleach, Microorganism Leaching, but
The generally existing phosphorus content of the iron ore concentrate that distinct methods obtain is high (P > 0.25%), can not be as the acceptable material of blast furnace ironmaking；I.e.
Make to obtain qualified iron ore concentrate, but the disadvantages such as that there are process costs is high, iron recovery is low；Therefore, high phosphorus iron ore concentrate high efficiency dephosphorating
Technology and technique there are also yet-to-be developed.
Summary of the invention
The problem of utilizing method for the above high phosphorus iron ore concentrate dephosphorization, it is high that the present invention provides a kind of high phosphorus iron ore concentrate
Temperature steam roasting-acidleach dephosphorization method, by high-temperature vapor roast cooperation acidleach dephosphorization, improve iron the rate of recovery and
Concentrate iron product grade, while reducing the phosphorus content in concentrate.
Method of the invention sequentially includes the following steps:
(1) the levigate part to -0.074mm of high phosphorus iron ore concentrate is accounted for into gross mass >=65%, then screens out partial size≤0.8mm
Part as high phosphorus iron ore concentrate powder；
(2) high phosphorus iron ore concentrate powder is placed in feed bin, is transported in primary cyclone through screw(-type) feeder；Level-one
The discharge port of cyclone separator is connected to the feed inlet of suspension roaster lower part, the top of suspension roaster by upper channel with
The feed inlet of secondary cyclone is connected to；The feed inlet connection that the gas outlet of secondary cyclone is separated with one cyclonic,
The gas outlet of primary cyclone is connected to the feed inlet of cleaner, and the gas outlet of cleaner is connected to air-introduced machine；It opens
Air-introduced machine is opened, forms negative pressure in primary cyclone, suspension roaster and secondary cyclone；
(3) under the action of negative pressure, after high phosphorus iron ore concentrate powder carries out gas solid separation in primary cyclone, formation
Level-one solid material；Level-one solid material enters suspension roasting furnace bottom；
(4) bottom of suspension roaster is equipped with burner；It is passed through combustion gas and combustion air into burner, and passes through burning
Device burning generates high-temperature vapor；High-temperature vapor enters suspension roaster from suspension roasting furnace bottom, by level-one solid material
Heating；
(5) material after being heated enters secondary cyclone from upper channel, carries out in secondary cyclone
After secondary gas solid separation, the second level solid material of formation is discharged from the discharge port of secondary cyclone under the effect of gravity；
(6) discharge port of secondary cyclone is opposite with stirred leaching tank, and sulfuric acid solution is placed in stirred leaching tank；
Second level solid material enters stirred leaching tank through discharge port and is stirred leaching, and the leaching material of generation is separated by filtration, then right
Solid phase is washed and is dried, and dephosphorization iron ore concentrate is obtained.
Above-mentioned high phosphorus iron ore concentrate contains P 0.5~1.5%, Iron grade 55~63% by mass percentage.
Above-mentioned combustion gas is natural gas, liquefied petroleum gas or coal gas.
In the above method, the volume flow ratio of the combustion gas and combustion air that are passed through burner is 1:12~1:15, high-temperature water
H in steam2Percent by volume >=10% of O.
In the above method, high-temperature vapor and bulk mass flow ratio of the level-one solid material within the unit time be 4~
6m3/kg。
In the above method, the temperature in suspension roaster is 1050~1200 DEG C, and level-one solid material is in suspension roaster
The interior residence time is 15~30s.
In the above method, after carrying out gas solid separation in primary cyclone, the level-one tail gas of generation enters cleaner,
It is discharged after dedusting by air-introduced machine.
In the above method, after carrying out secondary gas solid separation in secondary cyclone, the second level tail gas of generation enters level-one
Cyclone separator.
In the above method, the initial concentration of sulfuric acid solution is 0.05~0.3mol/L, when being stirred leaching, sulfuric acid solution
Liquid-solid ratio with second level solid material is 4~6L/kg, and the temperature of leaching is 10~35 DEG C, and the time is 15~30min.
In the above method, mixing speed when leaching is 15~30r/min.
The Iron grade 63~65% of above-mentioned dephosphorization iron ore concentrate contains P≤0.1% by mass percentage.
In the above method, the rate of recovery >=92% of iron..
The principle of the present invention is: the phosphorus in high phosphorus iron ore concentrate mainly exists in the form of apatite, and apatite is a kind of calcic
Phosphate mineral general name, particularly may be divided into fluor-apatite, chlorapatite and hydroxyapatite, chemical component can be abbreviated as
Ca10(PO4)6(F,Cl,OH)2；Apatite is mainly fluor-apatite Ca10(PO4)6F2；Natural gas, liquefied petroleum gas, coal gas etc. contain
Hydrogen ingredient (such as methane, ethane, propane, hydrogen) generates high-temperature vapor (H after burning in burner2O), in suspension roasting
In furnace with fluor-apatite Ca10(PO4)6F2It is reacted below equal generations:
Ca10(PO4)6F2+2H2O=Ca10(PO4)6(OH)2+2HF
With
Ca10(PO4)6(OH)2=3Ca3(PO4)2+CaO+H2O；
Fluor-apatite is transformed to thermal stability poor hydroxyapatite Ca under the action of high-temperature vapor10(PO4)6
(OH)2, hydroxyapatite continues to decompose at high temperature, generates the tricalcium phosphate Ca for being easy to leach3(PO4)2, and make ore particles
Loose porous state is presented in internal structure, to enhance the effect of high phosphorus iron ore concentrate acidleach dephosphorization.
Compared with prior art, outstanding feature of the invention is:
1, using high phosphorus iron ore concentrate as raw material, it is superfine to be particularly suitable for the disseminated grain size that conventional beneficiation method can not be handled, altogether
The high phosphorus refractory iron ore of raw relationship complexity, so that iron ore deposit is fully used；
2, Iron grade >=63%, iron recovery >=92%, the qualified iron ore concentrate of phosphorus content≤0.1% can be produced；
3, each stage process equipment is mature, and the high phosphorus iron ore concentrate obtained to common beneficiation method is adaptable, in product iron
Grade, iron recovery and dephosphorization rate everyway have reached compared with high target.
Detailed description of the invention
Fig. 1 is high phosphorus iron ore concentrate high-temperature vapor roasting-acidleach dephosphorization apparatus structure signal in the embodiment of the present invention
Figure；
In figure, 1, feed bin, 2, screw(-type) feeder, 3, primary cyclone, 4, cleaner, 5, air-introduced machine, 6, burning
Device, 7, suspension roaster, 8, upper channel, 9, secondary cyclone, 10, stirred leaching tank.
Specific embodiment
Embodiment below is only limitted to explain the present invention.
Washing is to be washed to washing lotion as neutrality in the embodiment of the present invention, and drying temperature is 120 ± 5 DEG C, is dried to the matter of water
Measure percentage≤0.1%.
The dephosphorization rate and iron recovery of the embodiment of the present invention be respectively increased 10~20% and 5 relative to traditional approach~
20%, for the dosage and calcining time of the species characteristics adjustment natural gas of different Iron Ore Powders, optimal reinforcing effect can be reached
Fruit.
The Iron grade TFe 47~51% of high phosphorus iron ore concentrate in the embodiment of the present invention, by mass percentage containing FeO 7~
15%, SiO29~16%, Al2O34.6~5%, CaO 2~5%, MgO 0.4~0.7%, P 0.5~1.5%, S≤
0.05%, MnO20.4~1.1%, TiO20.2~0.4%.
High phosphorus iron ore concentrate high-temperature vapor roasting-acidleach dephosphorization apparatus structure in the embodiment of the present invention as shown in Figure 1,
Including feed bin 1, screw(-type) feeder 2, primary cyclone 3, suspension roaster 7, secondary cyclone 9 and stirred leaching tank
10；2 inlet communications of feed bin 1 outlet and screw(-type) feeder, the outlet of screw(-type) feeder 2 and the charging of primary cyclone 3
Mouth connection, the discharge port of primary cyclone 3 are connected to the feed inlet of 7 lower part of suspension roaster, the top of suspension roaster 7
It is connected to by upper channel 8 with the feed inlet of secondary cyclone 9, the discharge port of secondary cyclone 9 and leaching
Slot 10 is opposite；Wherein the bottom of suspension roaster 7 is equipped with burner 6, the gas outlet of secondary cyclone 9 and one cyclonic point
Feed inlet connection from 3, the gas outlet of primary cyclone 3 is connected to the feed inlet of cleaner 4, dedusting set 4 it is standby out
Port is connected to air-introduced machine 5.
Mixing speed in the embodiment of the present invention when leaching is 15~30r/min.
Embodiment 1
The high phosphorus iron ore concentrate used is certain domestic high-phosphorus iron ore, Iron grade 50.65%, iron and phosphorus part symbiosis, by quality
Percentage contains P 0.83%, FeO 14.35%, SiO29.48%, Al2O34.78%, CaO 2.15%, MgO 0.48%, P
0.83%, S 0.042%, MnO21.03%, TiO20.38%；
Method is sequentially included the following steps: using high phosphorus iron ore concentrate high-temperature vapor roasting-acidleach dephosphorization device
The levigate part to -0.074mm of high phosphorus iron ore concentrate is accounted for into gross mass 70%, then screens out the portion partial size≤0.8mm
It is allocated as high phosphorus iron ore concentrate powder；
High phosphorus iron ore concentrate powder is placed in feed bin, is transported in primary cyclone through screw(-type) feeder；It opens at this time
Air-introduced machine is opened, forms negative pressure in primary cyclone, suspension roaster and secondary cyclone；
Under the action of negative pressure, after high phosphorus iron ore concentrate powder carries out gas solid separation in primary cyclone, the one of formation
Grade solid material；Level-one solid material enters suspension roasting furnace bottom；After carrying out gas solid separation in primary cyclone, generate
Level-one tail gas enter cleaner, be discharged after dedusting by air-introduced machine；
It is passed through combustion gas and air into burner, and high-temperature vapor is generated by burner combustion；High-temperature vapor from
Suspension roasting furnace bottom enters suspension roaster, and level-one solid material is heated；Combustion gas is natural gas；The volume of combustion gas and air
Flow-rate ratio 1:12, H in high-temperature vapor2The percent by volume 18% of O；High-temperature vapor and level-one solid material are in the unit time
Interior bulk mass flow ratio 5.8m3/kg；Temperature in suspension roaster is 1050 DEG C, and level-one solid material is in suspension roasting
Residence time 28s in furnace；
Material after being heated enters secondary cyclone from upper channel, carries out in secondary cyclone secondary
After gas solid separation, the second level solid material of formation is discharged into stirring from the discharge port of secondary cyclone under the effect of gravity
Leaching tanks；After carrying out secondary gas solid separation in secondary cyclone, the second level tail gas of generation enters primary cyclone；
Sulfuric acid solution is placed in stirred leaching tank；Second level solid material enters stirred leaching tank and is stirred leaching,
The initial concentration of middle sulfuric acid solution is 0.1mol/L, when being stirred leaching, the liquid-solid ratio of sulfuric acid solution and second level solid material
For 6L/kg, the temperature of leaching is 28 DEG C, time 20min；The leaching material of generation is separated by filtration, then to solid phase water
It is dried after washing, obtains dephosphorization iron ore concentrate, Iron grade 64.36% contains P 0.09% by mass percentage；The rate of recovery of iron
93.89%..
Embodiment 2
The high phosphorus iron ore concentrate used is certain domestic high-phosphorus iron ore, iron and phosphorus part symbiosis, Iron grade 47.35%, by quality
Percentage contains P 0.9%, FeO 7.81%, SiO215.80%, Al2O34.67%, CaO 4.63%, MgO 0.49%, P
0.90%, S 0.03%, MnO20.41%, TiO20.20%.
With embodiment 1, difference is method:
(1) the levigate part to -0.074mm of high phosphorus iron ore concentrate is accounted for into gross mass 80%；
(2) combustion gas is liquefied petroleum gas；The volume flow ratio 1:15 of combustion gas and air, H in high-temperature vapor2The volume of O
Percentage 20%；High-temperature vapor and bulk mass flow ratio 4.3m of the level-one solid material within the unit time3/kg；It suspends
1100 DEG C of temperature in roaster, residence time 17s of the level-one solid material in suspension roaster；
(3) when leaching sulfuric acid solution initial concentration be 0.08mol/L, when being stirred leaching, sulfuric acid solution with
The liquid-solid ratio of second level solid material is 4L/kg, and the temperature of leaching is 20 DEG C, time 30min；
(4) Iron grade 63.99% of dephosphorization iron ore concentrate contains P 0.08% by mass percentage；The rate of recovery of iron
94.24%.
Embodiment 3
The high phosphorus iron ore concentrate used is certain domestic high-phosphorus iron ore, iron and phosphorus part symbiosis, Iron grade 49.35%, by quality
Percentage contains P 0.79%, FeO 12.19%, SiO210.50%, Al2O35.00%, CaO 2.48%, MgO 0.64%, P
0.79%, S 0.05%, MnO20.64%, TiO20.36%.
With embodiment 1, difference is method:
(1) the levigate part to -0.074mm of high phosphorus iron ore concentrate is accounted for into gross mass 75%；
(2) combustion gas is coal gas；The volume flow ratio 1:13 of combustion gas and air, H in high-temperature vapor2The percent by volume of O
19%；High-temperature vapor and bulk mass flow ratio 5.5m of the level-one solid material within the unit time3/kg；Suspension roaster
1200 DEG C of interior temperature, residence time 22s of the level-one solid material in suspension roaster；
(3) when leaching sulfuric acid solution initial concentration be 0.15mol/L, when being stirred leaching, sulfuric acid solution with
The liquid-solid ratio of second level solid material is 5L/kg, and the temperature of leaching is 25 DEG C, time 25min；
(4) Iron grade 63.56% of dephosphorization iron ore concentrate contains P0.06% by mass percentage；The rate of recovery 92.59% of iron.
Claims (10)
1. a kind of method of high phosphorus iron ore concentrate high-temperature vapor roasting-acidleach dephosphorization, it is characterised in that sequentially include the following steps:
(1) the levigate part to -0.074mm of high phosphorus iron ore concentrate is accounted for into gross mass >=65%, then screens out the portion partial size≤0.8mm
It is allocated as high phosphorus iron ore concentrate powder；
(2) high phosphorus iron ore concentrate powder is placed in feed bin, is transported in primary cyclone through screw(-type) feeder；One cyclonic
The discharge port of separator is connected to the feed inlet of suspension roaster lower part, and the top of suspension roaster passes through upper channel and second level
The feed inlet of cyclone separator is connected to；The feed inlet connection that the gas outlet of secondary cyclone is separated with one cyclonic, level-one
The gas outlet of cyclone separator is connected to the feed inlet of cleaner, and the gas outlet of cleaner is connected to air-introduced machine；Unlatching is drawn
Blower, primary cyclone, suspension roaster and secondary cyclone are interior to form negative pressure；
(3) under the action of negative pressure, after high phosphorus iron ore concentrate powder carries out gas solid separation in primary cyclone, the level-one of formation
Solid material；Level-one solid material enters suspension roasting furnace bottom；
(4) bottom of suspension roaster is equipped with burner；It is passed through combustion gas and combustion air into burner, and is fired by burner
It burns and generates high-temperature vapor；High-temperature vapor enters suspension roaster from suspension roasting furnace bottom, and level-one solid material is heated；
(5) material after being heated enters secondary cyclone from upper channel, carries out in secondary cyclone secondary
After gas solid separation, the second level solid material of formation is discharged from the discharge port of secondary cyclone under the effect of gravity；
(6) discharge port of secondary cyclone is opposite with stirred leaching tank, and sulfuric acid solution is placed in stirred leaching tank；Second level
Solid material enters stirred leaching tank through discharge port and is stirred leaching, and the leaching material of generation is separated by filtration, then to solid phase
It washes and dries, obtain dephosphorization iron ore concentrate.
2. a kind of method of high phosphorus iron ore concentrate high-temperature vapor roasting-acidleach dephosphorization according to claim 1, feature exist
Contain P 0.5~1.5%, Iron grade 55~63% by mass percentage in the high phosphorus iron ore concentrate.
3. a kind of method of high phosphorus iron ore concentrate high-temperature vapor roasting-acidleach dephosphorization according to claim 1, feature exist
In the combustion gas be natural gas, liquefied petroleum gas or coal gas.
4. a kind of method of high phosphorus iron ore concentrate high-temperature vapor roasting-acidleach dephosphorization according to claim 1, feature exist
In step (4), the volume flow ratio of the combustion gas and combustion air that are passed through burner is 1:12~1:15, in high-temperature vapor
H2Percent by volume >=10% of O.
5. a kind of method of high phosphorus iron ore concentrate high-temperature vapor roasting-acidleach dephosphorization according to claim 1, feature exist
In step (4), high-temperature vapor and bulk mass flow ratio of the level-one solid material within the unit time are 4~6m3/kg。
6. a kind of method of high phosphorus iron ore concentrate high-temperature vapor roasting-acidleach dephosphorization according to claim 1, feature exist
In step (4), the temperature in suspension roaster is 1050~1200 DEG C, stop of the level-one solid material in suspension roaster
Time is 15~30s.
7. a kind of method of high phosphorus iron ore concentrate high-temperature vapor roasting-acidleach dephosphorization according to claim 1, feature exist
In step (6), the initial concentration of sulfuric acid solution is 0.05~0.3mol/L, when being stirred leaching, sulfuric acid solution and second level
The liquid-solid ratio of solid material is 4~6L/kg, and the temperature of leaching is 10~35 DEG C, and the time is 15~30min.
8. a kind of method of high phosphorus iron ore concentrate high-temperature vapor roasting-acidleach dephosphorization according to claim 1, feature exist
In step (6), mixing speed when leaching is 15~30r/min.
9. a kind of method of high phosphorus iron ore concentrate high-temperature vapor roasting-acidleach dephosphorization according to claim 1, feature exist
In the Iron grade 63~65% of the dephosphorization iron ore concentrate, contain P≤0.1% by mass percentage.
10. a kind of method of high phosphorus iron ore concentrate high-temperature vapor roasting-acidleach dephosphorization according to claim 1, feature
It is the rate of recovery >=92% of iron.
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| CN201910835955.1A CN110396593B (en) | 2019-09-05 | 2019-09-05 | Method for high-temperature steam roasting-acid leaching dephosphorization of high-phosphorus iron concentrate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111304408A (en) * | 2020-03-25 | 2020-06-19 | 中国科学院过程工程研究所 | Method for refining ferrophosphorus |
| CN118326168A (en) * | 2024-06-14 | 2024-07-12 | 辽宁新都黄金有限责任公司 | Mixed slurry mixing device of concentrate powder solid and liquid for gold smelting roasting furnace |
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| JPS63270427A (en) * | 1987-04-24 | 1988-11-08 | Chiyoda Chem Eng & Constr Co Ltd | Method for removing deposited solid matter containing gallium |
| CN1283222A (en) * | 1997-12-26 | 2001-02-07 | 日本钢管株式会社 | Refining method of molten iron and reduction smelting method for producing molten iron |
| CN102230075A (en) * | 2011-06-20 | 2011-11-02 | 江苏大学 | Dephosphorizing process of molybdenum nickel ore |
| CN108707746A (en) * | 2018-06-27 | 2018-10-26 | 东北大学 | The method that two-stage roasting-magnetic separation-leaching high-phosphor oolitic hematite carries iron drop phosphorus |
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2019
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63270427A (en) * | 1987-04-24 | 1988-11-08 | Chiyoda Chem Eng & Constr Co Ltd | Method for removing deposited solid matter containing gallium |
| CN1283222A (en) * | 1997-12-26 | 2001-02-07 | 日本钢管株式会社 | Refining method of molten iron and reduction smelting method for producing molten iron |
| CN102230075A (en) * | 2011-06-20 | 2011-11-02 | 江苏大学 | Dephosphorizing process of molybdenum nickel ore |
| CN108707746A (en) * | 2018-06-27 | 2018-10-26 | 东北大学 | The method that two-stage roasting-magnetic separation-leaching high-phosphor oolitic hematite carries iron drop phosphorus |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111304408A (en) * | 2020-03-25 | 2020-06-19 | 中国科学院过程工程研究所 | Method for refining ferrophosphorus |
| CN118326168A (en) * | 2024-06-14 | 2024-07-12 | 辽宁新都黄金有限责任公司 | Mixed slurry mixing device of concentrate powder solid and liquid for gold smelting roasting furnace |
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| CN110396593B (en) | 2020-10-23 |
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