CN102560090B - Method for enriching vanadium and selenium in process of producing cement ingredients by using boiling furnace - Google Patents
Method for enriching vanadium and selenium in process of producing cement ingredients by using boiling furnace Download PDFInfo
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- CN102560090B CN102560090B CN2012100010964A CN201210001096A CN102560090B CN 102560090 B CN102560090 B CN 102560090B CN 2012100010964 A CN2012100010964 A CN 2012100010964A CN 201210001096 A CN201210001096 A CN 201210001096A CN 102560090 B CN102560090 B CN 102560090B
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Abstract
The invention relates to a method for enriching vanadium and selenium in the process of producing cement ingredients by using a boiling furnace. The method is characterized by comprising the following operation steps: a, adding calcium and crushing; b, roasting; c, controlling air inlet quantity; 2, enriching vanadium and selenium; and e, removing sulfur from tail gas. Compared with the prior art, the method has the following advantages: roasting is performed according to carbon in stone coal, the tail gas can be treated concentratedly, and metal such as vanadium, selenium and the like is enriched in fine ash and can serve as byproducts to be recovered , so the profit of factories is improved and environmental pollution is avoided.
Description
Technical field
The present invention relates to a kind of method of enrichment vanadium and selenium when producing cement ingredient with fluidizing furnace.
Background technology
Vanadium is important defense strategy goods and materials, and the title of " metal monosodium glutamate " is arranged, and is widely used in metallurgy, chemical industry, space flight and aviation and emerging fields such as vanadium cell.China's vanadium resource is abundanter, and the main vanadium minerals that contains has: vanadium titano-magnetite and contain the scherbinaite coal.Bone coal is a kind of polymetallic carbonaceous shale that contains, and main trace element has the complex ore of symbiosis such as vanadium, selenium, aluminium, molybdenum, iron, and the bone coal reserves in the area of bestowing favour are huge, does not smelt grade requirement but the content of every kind of metal does not all reach industry.In the western Hunan, the cement of western Hubei Province generally all is carbonate cement, because the siliceous height of bone coal, raw ore contains silicon-dioxide 65%-70%, and fired slags contains silicon-dioxide more than 80%, as the cement ingredient fusion, can improve cement mark, so the western Hunan, western Hubei Province are very big to this product consumption, at present owing under the driving of the demand in market and interests, occurred a lot of amorphous burnt in a heap in the open, there is not environmental protection equipment, SO
2Directly discharge Deng gas, environment has been caused very big pollution, large quantities of mountain forest death appear in some places; More seriously the content of tin anhydride is higher in the flue gas of open-air generation burnt in a heap, can cause selenosis after people and animals suck, and the precious metal in the bone coal can't recycle again, has caused the wasting of resources of metals such as vanadium, selenium.Reclaim technology so develop a kind of comprehensive utilization, very urgent environmental protection demand and wide economic outlook are arranged.This technology utilization boiling furnace combustion low heat value bone coal, and common fluidizing furnace transformed: the proportioning by adjusting primary and secondary air and increase multistage air intake, adopt the two-stage deslagging, make bone coal after the burning wherein contained vanadium and selenium in dust, obtain the very enrichment of high level.Adopt simultaneously in bone coal, to add calcium and tail gas and remove sulphur in the flue gas with the method for alkali neutralization, avoided the pollution to atmosphere.
Summary of the invention
The technical problem to be solved in the present invention provides and a kind ofly can fully utilize many metals bone coal ore deposit better, and when producing cement ingredient, flue gas can focus on qualified discharge, and precious metals such as enrichment vanadium, selenium are beneficial to extract and reclaim effectively.
The method of the present invention is a kind of when producing cement ingredient with fluidizing furnace enrichment vanadium and selenium is characterized in that comprising following operation steps:
A, to add calcium powder broken: press that sulphur content adds CaCO in the raw material bone coal
3, when making raw material enter fluidizing furnace in the raw material calcium sulfur ratio be 2, in the bone coal crushing process, add CaCO
3, CaCO
3Be crushed to below the 5mm together with bone coal;
B, roasting: bone coal utilizes the thermal value roasting in fluidizing furnace of self, and the temperature of burner hearth remains between 850 ℃-950 ℃;
C, control air output: at a plurality of blast inlets control air outputs of fluidizing furnace, make fluidizing furnace second oxygen feeder, the 3rd oxygen feeder, be the control of the 4th oxygen feeder air quantity at 6%, 5%, 4% of total blast volume, make to be in the oxidisability state in the burner hearth all the time; The residence time control of material in burner hearth was at 10 seconds-16 seconds;
D, enrichment vanadium and selenium: join section for cement from what fluidizing furnace slag-drip opening, heavy slag slag-drip opening and gravitational precipitator obtained; Vanadium and selenium are oxidized to V in burner hearth
2O
5, SeO
2Enter flue together with thin dirt, be enrichment vanadium and selenium raw material from the dust that reclaims with tornado dust collector;
E, tail gas sulphur removal: tail gas adds one-level silica tube tower before the blowdown stack discharging, with the buck spray, removes a small amount of SO in the tail gas
2, make SO
2Emission concentration control is at 300mg/Nm
3In.
The method of the present invention is a kind of when producing cement ingredient with fluidizing furnace enrichment vanadium and selenium is characterized in that comprising following operation steps:
A, to add calcium powder broken: press that sulphur content adds CaCO in the raw material bone coal
3, when making raw material enter fluidizing furnace in the raw material calcium sulfur ratio be 2, in the bone coal crushing process, add CaCO
3, CaCO
3Be crushed to below the 5mm together with bone coal;
B, roasting: bone coal utilizes the thermal value roasting in fluidizing furnace of self, and the temperature of burner hearth remains between 850 ℃-950 ℃;
C, control air output: at a plurality of blast inlets control air outputs of fluidizing furnace, make fluidizing furnace second oxygen feeder, the 3rd oxygen feeder, be the control of the 4th oxygen feeder air output at 6%, 5%, 4% of total blast volume, make to be in the oxidisability state in the burner hearth all the time; The residence time control of material in burner hearth was at 16 seconds;
D, enrichment vanadium and selenium: join section for cement from what fluidizing furnace slag-drip opening, heavy slag slag-drip opening and gravitational precipitator obtained; Vanadium and selenium are oxidized to V in burner hearth
2O
5, SeO
2Enter flue together with thin dirt, be enrichment vanadium and selenium raw material from the dust that reclaims with tornado dust collector;
E, tail gas sulphur removal: tail gas adds one-level silica tube tower before the blowdown stack discharging, with the buck spray, removes a small amount of SO in the tail gas
2, make SO
2Emission concentration control is at 300mg/Nm
3In.
The present invention has the following advantages compared with the prior art: utilize the carbon content of bone coal itself to carry out roasting, tail gas can focus on, metal such as vanadium, selenium all is enriched in the thin ash, can be reclaimed as byproduct, improved the factory account space, avoided the pollution to environment simultaneously.
Description of drawings
Accompanying drawing 1 is the processing unit synoptic diagram of enrichment vanadium and selenium when producing cement ingredient with fluidizing furnace;
The one-piece construction synoptic diagram of accompanying drawing 2 fluidizing furnaces;
In the accompanying drawing: 1-is the fluidizing furnace body; 2-is first oxygen feeder; 3-is slag-drip opening; 4-is second oxygen feeder; 5-is the 3rd oxygen feeder; 6-is the 4th oxygen feeder; 7-is furnace gas export; 8-is opening for feed; 9-is manhole; 10-is chimney; The 11-slag slag-drip opening of attaching most importance to; 22-is gravitational precipitator; 23-is the old dirt device of whirlwind; 24-is tornado dust collector; 25-is the silica tube tower; 26-is blowdown stack.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but the working of an invention mode is not limited thereto.
The fluidizing furnace that the present invention uses is a kind of fluidizing furnace of four air intakes, and the fluidizing furnace of four air intakes is at fluidizing furnace body 1 chimney 10, opening for feed 8, furnace gas export 7, manhole 9, slag-drip opening 3 and oxygen feeder to be installed; The chimney 10 and the furnace gas export 7 that use when being provided with igniting at fluidizing furnace body 1 top, be provided with the 4th oxygen feeder 6 on fluidizing furnace body 1 top, be provided with the 3rd oxygen feeder 5 at fluidizing furnace body 1 middle part, be provided with second oxygen feeder 4 in fluidizing furnace body 1 bottom, be provided with opening for feed 8, manhole 9, slag-drip opening 3 and first oxygen feeder 2 in fluidizing furnace body 1 bottom; Be provided with fire-resistant silicon layer in fluidizing furnace body 1 inside.
The method of the present invention is a kind of when producing cement ingredient with fluidizing furnace enrichment vanadium and selenium is characterized in that comprising following operation steps:
A, to add calcium powder broken: press that sulphur content adds CaCO in the raw material bone coal
3, when making raw material enter fluidizing furnace 1 in the raw material calcium sulfur ratio be 2, in the bone coal crushing process, add CaCO
3, CaCO
3Be crushed to below the 5mm together with bone coal;
B, roasting: bone coal utilizes the thermal value roasting in fluidizing furnace 1 of self, and the temperature of burner hearth remains between 850 ℃-950 ℃;
C, control air output: at a plurality of blast inlets control air outputs of fluidizing furnace 1, make fluidizing furnace second oxygen feeder 4, the 3rd oxygen feeder 5, be the control of the 4th oxygen feeder 6 air outputs at 6%, 5%, 4% of total blast volume, make to be in the oxidisability state in the burner hearth all the time; The residence time control of material in burner hearth was at 16 seconds;
D, enrichment vanadium and selenium: the slag dirt that obtains from fluidizing furnace slag-drip opening 3, heavy slag slag-drip opening 11 and gravitational precipitator 22 is that cement is joined section; Vanadium and selenium are oxidized to V in burner hearth
2O
5, SeO
2Enter flue together with thin dirt, be enrichment vanadium and selenium raw material from the dust that reclaims with tornado dust collector 23 and tornado dust collector 24;
E, tail gas sulphur removal: tail gas adds one-level silica tube tower 25 before blowdown stack 26 discharging, with the buck spray, removes a small amount of SO in the tail gas
2, make SO
2Emission concentration control is at 300mg/Nm
3In.
Bone coal is that 2 ratio adds CaCO in calcium sulfur ratio when pulverizing
3, be crushed to below the 5mm, enter roasting in the fluidizing furnace together, in roasting process, the temperature of burner hearth is remained between 850 ℃-950 ℃, make S high temperature oxidation generation SO in the bone coal
2CaCO
3Pyrolytic decomposition generates CaO, CaO+SO
2→ CaSO
3+ O
2→ CaSO
4, the CaO of general 100g can absorb the SO of 29.4g in the time of 900 ℃
2, in stove, can remove 70% one 90% SO
2, the CaSO of generation
4It is again the auxiliary material that cement must add.
Vanadium in the bone coal, selenium generally all are distributed in the carbonaceous with adsorbed state, also have a small part to compose and be stored in the pyrite, in roasting process because carbon generates CO
2, metals such as vanadium, selenium enter in the dirt with the gangue mineral in the ore quartzy the separation, open a heavy slag slag-drip opening in the fluidized bed lower end of fluidizing furnace according to this phenomenon, and the gangue in the ore is discharged from this slag-drip opening; An overflow and slag mouth is opened in fluidized bed upper end at fluidizing furnace, and low-grade slag is discharged from this slag-drip opening.The silicon content of two slag-drip opening institute deslagginves directly send the cement mill as cement ingredient more than 80% after the cooling.Establish air intake 2,3,4 times above fluidized bed, by adjusting the air intake ratio, make definitely to be in the state of oxidation in the whole burner hearth, after vanadium, selenium etc. entered burner hearth, oxidation generated V
2O
5And SeO
2Enter flue, the SeO of gaseous state
2By the S O in the flue gas
2Be reduced into simple substance Se and V
2O
5Be enriched in together in the thin dirt.
Flue dust is through the one-level gravitational dust collection, further separate low-grade heavy slag after, reclaim through 2 grades of tornado dust collector again, the enrichment specific energy of vanadium and selenium reaches more than 3 times, the enrichment slag send the smeltery to smelt and obtains vanadium, selenium product.Flue gas is removed remaining a small amount of SO through the silica tube tower behind the buck spray
2Back qualified discharge.
Example 1
The bestow favour bone coal ore deposit in regional Li Jia river, major ingredient is SiO
2: 64.1%; C:13%; S:1.5%; Fe
2O
3: 3.3%; Al
2O
3: 7.8%; CaO0.4%; V
2O
5: 0.34%; Se:0.008%; Mo:0.02%; Other trace element 6.5%.Roasting in the fluidizing furnace of 8.5 tons of roastings per hour per hour blasts 7500m
3Air quantity produces 11000m
3Exhaust gas volumn per hour produces the SO of 216kg according to the sulphur content of ore
2In bone coal fine ore process, add the CaCO that 3% stone quarry is bought
3Powder records the SO before the silica tube tower into when 900 ℃ of fire box temperatures after the roasting
2Content 2200mg/Nm
3Behind silica tube tower liming spray, record the sulphur content 276mg/Nm of tail gas again
3
Slag-drip opening is collected 2.57 tons of heavy slags, contains vanadium 0.18%, contains selenium 0.0001%.Gravitational dust collection is collected 3.26 tons, contains vanadium 0.38%, contains selenium 0.003%, and 0.97 ton of thin slag is collected in cyclone dust removal, contains vanadium 0.95%, contains selenium 0.041%.Together by molybdenum and the aluminium in addition of enrichment.
Example 2
The bestow favour bone coal ore deposit on slope, regional iron field, major ingredient is SiO
2: 65.29%; C:13.3%; S:1.7%; Fe
2O
3: 3.2%; Al
2O
3: 13.3%; CaO0.6%; V
2O
5: 0.47%; Se:0.009%; Mo:0.02%; Other element 2.65%.Roasting in the fluidizing furnace of 7.2 tons of roastings per hour per hour blasts 7300m
3Air quantity produces 10200m
3Exhaust gas volumn per hour produces the SO of 207kg according to the sulphur content of ore
2CaCO is bought in the stone quarry of adding 2.8% in bone coal fine ore process
3Powder records the SO before the silica tube tower into when 900 ℃ of fire box temperatures after the roasting
2Content 2130mg/Nm
3Behind silica tube tower liming spray, record the sulphur content 262mg/Nm of tail gas again
3
Slag-drip opening is collected 1.63 tons of heavy slags, contains vanadium 0.19%, contains selenium 0.001%.Gravitational dust collection is collected 2.53 tons, contains vanadium 0.51%, contains selenium 0.0037%, and 1.24 tons of thin slags are collected in cyclone dust removal, contain vanadium 1.09%, contain selenium 0.032%.Together by molybdenum and the aluminium in addition of enrichment.
Example 3
The bestow favour bone coal ore deposit of regional military outpost, major ingredient is SiO
2: 64.67%; C:12.8%; S:1.9%; Fe
2O
3: 3.5%; Al
2O
3: 11.7%; CaO0.8%; V
2O
5: 0.43%; Se:0.009%; Mo:0.019%; Other element 4.24%.Roasting in the fluidizing furnace of 9.3 tons of roastings per hour per hour blasts 7600m
3Air quantity produces 10900m
3Exhaust gas volumn per hour produces the SO of 299kg according to the sulphur content of ore
2CaCO is bought in the stone quarry of adding 2.9% in bone coal fine ore process
3Powder records the SO before the silica tube tower into when 900 ℃ of fire box temperatures after the roasting
2Content 2210mg/Nm
3Behind silica tube tower liming spray, record the sulphur content 292mg/Nm of tail gas again
3
Slag-drip opening is collected 2.21 tons of heavy slags, contains vanadium 0.17%, contains selenium 0.001%.Gravitational dust collection is collected 3.06 tons, contains vanadium 0.48%, contains selenium 0.0041%, and 1.69 tons of thin slags are collected in cyclone dust removal, contain vanadium 1.07%, contain selenium 0.035%.Together by molybdenum and the aluminium in addition of enrichment.
Claims (2)
1. the method for an enrichment vanadium when producing cement ingredient with fluidizing furnace and selenium is characterized in that comprising following operation steps:
A, to add calcium powder broken: press that sulphur content adds CaCO in the raw material bone coal
3, when making raw material enter fluidizing furnace in the raw material calcium sulfur ratio be 2, in the bone coal crushing process, add CaCO
3, CaCO
3Be crushed to below the 5mm together with bone coal;
B, roasting: bone coal utilizes the thermal value roasting in fluidizing furnace of self, and the temperature of burner hearth remains on 850
oC-950
oBetween the C;
C, control air output: second oxygen feeder (4) on the fluidizing furnace, the 3rd oxygen feeder (5), the 4th oxygen feeder (6) air output are controlled at 6%, 5%, 4% of total blast volume, make to be in the oxidisability state in the burner hearth all the time; The residence time control of material in burner hearth was at 10 seconds-16 seconds;
D, enrichment vanadium and selenium: join section for cement from fluidizing furnace slag-drip opening (3), heavy slag slag-drip opening (11) and gravitational precipitator (22) acquisition; Vanadium and selenium are oxidized to V in burner hearth
2O
5, SeO
2Enter flue together with thin dirt, the dust that reclaims from first tornado dust collector (23) and second tornado dust collector (24) is enrichment vanadium and selenium raw material;
E, tail gas sulphur removal: tail gas adds one-level silica tube tower (25) before blowdown stack (26) discharging, with the buck spray, removes a small amount of SO in the tail gas
2, make SO
2Emission concentration control is at 300mg/Nm
3In;
Described when producing cement ingredient with fluidizing furnace the employed fluidizing furnace of method of enrichment vanadium and selenium be-fluidizing furnace of kind of four air intakes that the fluidizing furnace of four air intakes is at fluidizing furnace body (1) chimney (10), opening for feed (8), furnace gas export (7), manhole (9), slag-drip opening (3) and oxygen feeder to be installed; The chimney (10) and the furnace gas export (7) that use when being provided with igniting at fluidizing furnace body (1) top, be provided with the 4th oxygen feeder (6) on fluidizing furnace body (1) top, be provided with the 3rd oxygen feeder (5) at fluidizing furnace body (1) middle part, be provided with second oxygen feeder (4) in fluidizing furnace body (1) bottom, be provided with opening for feed (8), manhole (9), slag-drip opening (3) and first oxygen feeder (2) in fluidizing furnace body (1) bottom; Be provided with fire-resistant silicon layer in fluidizing furnace body (1) inside.
2. according to the described a kind of method of enrichment vanadium and selenium when producing cement ingredient with fluidizing furnace of claim 1, it is characterized in that comprising following operation steps:
A, to add calcium powder broken: press that sulphur content adds CaCO in the raw material bone coal
3, when making raw material enter fluidizing furnace in the raw material calcium sulfur ratio be 2, in the bone coal crushing process, add CaCO
3, CaCO
3Be crushed to below the 5mm together with bone coal;
B, roasting: bone coal utilizes the thermal value roasting in fluidizing furnace of self, and the temperature of burner hearth remains on 850
oC-950
oBetween the C;
C, control air output: second oxygen feeder (4) on the fluidizing furnace, the 3rd oxygen feeder (5), the 4th oxygen feeder (6) air output are controlled at 6%, 5%, 4% of total blast volume, make to be in the oxidisability state in the burner hearth all the time; The residence time control of material in burner hearth was at 16 seconds;
D, enrichment vanadium and selenium: join section for cement from fluidizing furnace slag-drip opening (3), heavy slag slag-drip opening (11) and gravitational precipitator (22) acquisition; Vanadium and selenium are oxidized to V in burner hearth
2O
5, SeO
2Enter flue together with thin dirt, the dust that reclaims from first tornado dust collector (23) and second tornado dust collector (24) is enrichment vanadium and selenium raw material;
E, tail gas sulphur removal: tail gas adds one-level silica tube tower (25) before blowdown stack (26) discharging, with the buck spray, removes a small amount of SO in the tail gas
2, make SO
2Emission concentration control is at 300mg/Nm
3In;
Described when producing cement ingredient with fluidizing furnace the employed fluidizing furnace of method of enrichment vanadium and selenium be-fluidizing furnace of kind of four air intakes that the fluidizing furnace of four air intakes is at fluidizing furnace body (1) chimney (10), opening for feed (8), furnace gas export (7), manhole (9), slag-drip opening (3) and oxygen feeder to be installed; The chimney (10) and the furnace gas export (7) that use when being provided with igniting at fluidizing furnace body (1) top, be provided with the 4th oxygen feeder (6) on fluidizing furnace body (1) top, be provided with the 3rd oxygen feeder (5) at fluidizing furnace body (1) middle part, be provided with second oxygen feeder (4) in fluidizing furnace body (1) bottom, be provided with opening for feed (8), manhole (9), slag-drip opening (3) and first oxygen feeder (2) in fluidizing furnace body (1) bottom; Be provided with fire-resistant silicon layer in fluidizing furnace body (1) inside.
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|---|---|---|---|
| CN2012100010964A CN102560090B (en) | 2012-01-05 | 2012-01-05 | Method for enriching vanadium and selenium in process of producing cement ingredients by using boiling furnace |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100010964A CN102560090B (en) | 2012-01-05 | 2012-01-05 | Method for enriching vanadium and selenium in process of producing cement ingredients by using boiling furnace |
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|---|---|
| CN102560090A CN102560090A (en) | 2012-07-11 |
| CN102560090B true CN102560090B (en) | 2013-10-02 |
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| CN104911336B (en) * | 2015-06-29 | 2017-05-17 | 北京科技大学 | Method and device for pre-enriching vanadium in downstream stone coal |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1724387A (en) * | 2005-06-22 | 2006-01-25 | 株洲市湘麒科技开发有限公司 | Process for extracting vanadium pentoxide from stone coal vanadium mining |
| CN1752022A (en) * | 2005-08-12 | 2006-03-29 | 岳阳市中湘实业有限公司 | Method of extracting vanadium pentoxide from vanadium ore |
| CN101078064A (en) * | 2007-06-29 | 2007-11-28 | 黎吉星 | Stone-like coal gas phase vanadium extracting method |
-
2012
- 2012-01-05 CN CN2012100010964A patent/CN102560090B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1724387A (en) * | 2005-06-22 | 2006-01-25 | 株洲市湘麒科技开发有限公司 | Process for extracting vanadium pentoxide from stone coal vanadium mining |
| CN1752022A (en) * | 2005-08-12 | 2006-03-29 | 岳阳市中湘实业有限公司 | Method of extracting vanadium pentoxide from vanadium ore |
| CN101078064A (en) * | 2007-06-29 | 2007-11-28 | 黎吉星 | Stone-like coal gas phase vanadium extracting method |
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Inventor after: Wu Hao Inventor after: Li Lingjing Inventor after: Zhu Youge Inventor after: Mi Zedi Inventor before: Zhu Youming Inventor before: Li Lingjing Inventor before: Wu Hao Inventor before: Mi Zedi |
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