CN109928414A - A method of it is synchronized using aluminium ash sintering imurity-removal and prepares the steel desulfurization agent of calcium aluminate system - Google Patents
A method of it is synchronized using aluminium ash sintering imurity-removal and prepares the steel desulfurization agent of calcium aluminate system Download PDFInfo
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- aluminium ash
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Abstract
The method for preparing the steel desulfurization agent of calcium aluminate system is synchronized using aluminium ash sintering imurity-removal the invention discloses a kind of, this method is to mix aluminium ash and calcic raw material, is pressed into agglomerate；Gained agglomerate is after drying, roasting in air atmosphere is sequentially placed into carry out one section of low-temperature bake, be placed in two sections of medium temperature roasts of progress in strong oxidizing property atmosphere, be placed in three sections of high-temperature fusions roastings of progress in air atmosphere, product of roasting is crushed through supercooling to get with 12CaO7Al2O3For the preliminary melting type calcium aluminate fimily desulfurizing agent of main phase；This method is primary raw material using industrial residue, and raw material sources are wide, at low cost, generates higher added value, and it is easy to operate, production cost is low, environmental-friendly, meet industrialization production requirements.
Description
Technical field
The present invention relates to a kind of methods for preparing the steel desulfurization agent of calcium aluminate system using aluminium ash, and in particular to high using aluminium ash
The method that temperature sintering imurity-removal element synchronization prepares the steel desulfurization agent of calcium aluminate system, belongs to mineral processing and Ferrous Metallurgy neck
Domain.
Background technique
Aluminium ash is the Aluminiferous waste slag generated in alumina eltrolysis, aluminium product and conservation process, according to incompletely statistics,
One ton of electrolytic aluminium of every production will form 30-50kg aluminium ash, and China generates aluminium ash total amount every year and is up to ten thousand tons of 100-200.In aluminium ash
Metallic aluminium containing 30-70% has high recovery value, in addition, also containing impurity such as nitrogen, chlorine, fluorine, potassium, sodium in aluminium ash
Element.Aluminium nitride in aluminium ash is to react generation in metallic aluminium pyroprocess with nitrogen, and aln structure is stable, fusing point is high, but
It is that aluminium nitride reacts during stockpiling with rainwater, slowly generates ammonia, seriously pollute environment.Therefore, " National Hazard waste name
Record " it is classified as aluminium ash to endanger waste, aluminium ash per ton is discharged by 1000 yuan of collection of environmentally friendly tax.
Aluminium content is much higher than natural aluminous ore in aluminium ash, has high comprehensive utilization value.To realize the comprehensive of aluminium ash
It closes and utilizes, researcher develops rotary kiln facture of fascinating, gravity separation method, electrical concentration, centrifugal process, mechanical picker point-score etc..It is de-
Except nitrogen in aluminium ash, the pernicious gases such as processed middle generation ammonia are avoided, aluminium ash is carried out under catalyst and lye effect
Denitrogenation promotes ammonia to overflow and recycle and prepares ammonium hydroxide by heating；But wet processing needs to put into high airtightness large size reaction
Equipment increases production cost.
Sulphur is one of main harmful element of steelmaking process, and sulfur content height will lead to steel red brittleness and anisotropic, generally
Stainless steel production requirement sulfur content is lower than 0.005% or even 0.001%.For the element sulphur in removing molten steel, need in electric furnace smelting
Deoxidier slag making is added during refining, when the pre-melted type steel desulfurization agent of calcium aluminate system has fusing point low (1450 DEG C), forms liquid phase
Between the short, advantages such as ingredient is uniform, desulphurizing ability is strong, fluorine content is low.But aluminic acid is prepared with mineral such as quality oxide aluminium, bauxites
When calcium, wherein the impurity such as silicon, titanium are difficult to remove, and especially silica may be reduced into elemental silicon in electric furnace, into molten steel
Influence steel quality.Aluminium ash in silicone content it is lower, be a kind of good containing a source of aluminum, but the prior art and have no utilize aluminium ash make
The relevant report of calcium aluminate system steel desulfurization agent is prepared for silicon source.
Summary of the invention
For in the prior art, generally existing high production cost, complex process in aluminium ash comprehensive utilization process are easy to produce
The silicon sources such as aluminium oxide, bauxite are miscellaneous in the defects of raw secondary pollution and existing calcium aluminate system steel desulfurization agent preparation process
Matter is difficult to the defects of removing, and the object of the present invention is to provide a kind of using aluminium ash as silicon source, by control temperature and atmosphere into
The method that row high temperature sintering gradually removes the steel desulfurization agent of impurity element synchronization gain high-quality calcium aluminate system, this method are grey by aluminium
Nitrogen in middle aluminium nitride component is converted into environmentally friendly nitrogen, avoids the formation of NOx and causes secondary environmental pollution, while removing aluminium
The harmful elements such as sodium chloride, potassium chloride in ash, and aluminium component is made to be converted into calcium aluminate, the steel-making for being prepared into high added value is de-
Sulphur agent, this method is easy to operate, production cost is low, environmental-friendly, meets industrialization production requirements.
In order to achieve the above technical purposes, the present invention provides a kind of synchronized using aluminium ash sintering imurity-removal to prepare aluminic acid
The method of calcium system steel desulfurization agent, this method are to mix aluminium ash and calcic raw material, are pressed into agglomerate；Gained agglomerate passes through drying
Afterwards, be sequentially placed into air atmosphere roasting carry out one section of low-temperature bake, be placed in strong oxidizing property atmosphere carry out two sections of medium temperature roasts,
It is placed in air atmosphere and carries out three sections of high-temperature fusion roastings, product of roasting is crushed through supercooling to get calcium aluminate fimily desulfurizing agent.
The ratio control Al:Ca elemental mole ratios of preferred scheme, aluminium ash and calcic raw material are 1:1.02~1:1.1.
More preferably scheme, the calcic raw material include at least one of quick lime, calcium hydroxide, lime stone, steel slag.
The dioxide-containing silica of more preferably scheme, the calcic raw material is lower than 3.0%.More preferably two in calcic raw material
Silica content is lower than 1.0%.
Preferred scheme, the condition of one section of low-temperature bake are as follows: temperature be 300~500 DEG C, the time be 120~
180min.It is preferred that carrying out oxidizing roasting in relative low temperature condition and air atmosphere, main purpose is metallic aluminium phase oxygen in aluminium ash
Turn to active aluminum oxide.
Preferred scheme, the condition of two sections of medium temperature roasts are as follows: temperature be 800~1000 DEG C, the time be 90~
150min, volume percent oxygen is O in calcination atmosphere2/(O2+N2)=40~65%.It is preferred that in high temperature and strong oxidizing atmosphere into
Row two-stage calcination main purpose is that calcium-containing material is promoted to decompose production active calcium oxide, recycles the nitridation in calcium oxide and aluminium ash
Aluminium reacts at high temperature and in oxidizing atmosphere, and aluminium nitride is promoted to be converted into N2, while sodium chloride and chlorination are realized at high temperature
The volatilization of potassium removes, and reduces the impurity element in component, before the component containing aluminium in aluminium ash is converted into orthoaluminic acid calcium mostly at this time
Drive body.
Preferred scheme, the condition of three sections of high-temperature fusions roasting are as follows: temperature is 1480~1620 DEG C, the time 180
~240min.It is preferred that frit reaction at high temperature, it is therefore an objective to promote to react thorough between aluminium, calcium oxide.
Preferred scheme, the diameter of agglomerate are 15mm or so.
Preferred scheme, product of roasting are crushed to 5mm or less.
During technology of the invention prepares calcium aluminate fimily desulfurizing agent as silicon source using aluminium ash, it is important to be to carry out each
The efficient removal of kind impurity element and the Efficient Conversion of aluminium.The present invention carries out in relative low temperature condition and air atmosphere first
Oxidizing roasting, by control temperature and atmosphere to promote metallic aluminium phase oxidation in aluminium ash to avoid as aluminum oxide because of aluminium simple substance
Melting causes system elements segregation, reaction uneven；On this basis, two sections are carried out by increasing temperature and adjusting oxidizing atmosphere
Roasting promotes calcium-containing material to decompose production active calcium oxide, and calcium oxide reacts at high temperature with the aluminium nitride in aluminium ash, ties
Strong oxidizing property atmosphere is closed, aluminium nitride is promoted to be converted into N2, while realizing that the volatilization of sodium chloride and potassium chloride removes at high temperature, drop
Impurity element in low component, the component containing aluminium in aluminium ash is converted into orthoaluminic acid calcium presoma mostly at this time；The present invention passes through
Three sections of high-temperature fusion roastings of progress are further heated up, reaction between aluminium, calcium oxide is promoted to carry out thoroughly, improving the benefit of aluminum feedstock
With rate.
Compared with the prior art, technical solution of the present invention bring the utility model has the advantages that
1) technical solution of the present invention has the destruction of aluminium ash internal structure and the conversion ratio for improving aluminium using calcic raw material
There is apparent facilitation, calcic raw material can strengthen the oxygenolysis of aluminium nitride stable phase, and promote the conversion of component containing aluminium
For calcium aluminate, to be prepared into 12CaO7Al2O3For the steel desulfurization agent of main phase.
2) technical solution of the present invention is roasted by gas regulating multistage, promotes the removing of potassium, sodium, chlorine element, strengthens nitrogen
Change aluminium oxygenolysis, wherein nitrogen is converted mainly into environmentally friendly nitrogen, and NOx generation amount meets discharge standard.
3) aluminium ash comprehensive utilization technique method of the invention is easy to operate, low energy consumption, at low cost, it is easy to accomplish industrial metaplasia
It produces.
Specific embodiment
Following embodiment is intended to further illustrate the content of present invention, rather than limits the protection model of the claims in the present invention
It encloses.
Comparative example 1:
With certain metallurgy of aluminium factory aluminium grey (aluminium content 65.6%, nitrogen content 7.2%, chlorinity 4.6%) for raw material, first by aluminium
According to aluminium calcium constituent ratio 1:1.02 progress ingredient, raw material mixes the agglomerate for being then pressed into diameter 15mm for ash and calcium hydroxide；Agglomerate
Sufficiently after drying, places it in air atmosphere and roasted, 1580 DEG C of maturing temperature, calcining time 360min；Roasting terminates
It is afterwards that product of roasting is cooling, be crushed to 5mm hereinafter, obtaining with 12CaO7Al2O3For the desulfurization of main phase (theoretical content 43.2%)
Agent product, fusing point are 1525 DEG C, and the main harmful element removal efficiency of nitrogen, chlorine is respectively 75.3% and 73.5% in preparation process.
Comparative example 2:
With certain metallurgy of aluminium factory aluminium grey (aluminium content 65.6%, nitrogen content 7.2%, chlorinity 4.6%) for raw material, first by aluminium
According to aluminium calcium constituent ratio 1:1.02 progress ingredient, raw material mixes the agglomerate for being then pressed into diameter 15mm for ash and calcium hydroxide；Agglomerate
It sufficiently after drying, places it in air atmosphere and carries out one section of roasting, maturing temperature is 300 DEG C, calcining time 180min；Two
Section maturing temperature is 800 DEG C, and calcining time 150min, calcination atmosphere is air；Three sections 1550 DEG C of maturing temperature of melting, roasting
Time 180min, calcination atmosphere are air；It is after roasting that product of roasting is cooling, be crushed to 5mm hereinafter, obtain with
12CaO·7Al2O3For the desulfurizing agent product of main phase (theoretical content 88.2%), fusing point is 1495 DEG C, nitrogen, chlorine master in preparation process
Wanting harmful element removal efficiency is respectively 99.3% and 53.5%.
Embodiment 1:
With certain metallurgy of aluminium factory aluminium grey (aluminium content 65.6%, nitrogen content 7.2%, chlorinity 4.6%) for raw material, first by aluminium
According to aluminium calcium constituent ratio 1:1.02 progress ingredient, raw material mixes the agglomerate for being then pressed into diameter 15mm for ash and calcium hydroxide；Agglomerate
It sufficiently after drying, places it in air atmosphere and carries out one section of roasting, maturing temperature is 300 DEG C, calcining time 180min；Two
Section maturing temperature is 800 DEG C, calcining time 150min, calcination atmosphere O2/(O2+N2)=65%；Three sections of melting maturing temperatures
1580 DEG C, calcining time 180min, calcination atmosphere is air；It is after roasting that product of roasting is cooling, be crushed to 5mm hereinafter,
It obtains with 12CaO7Al2O3For the desulfurizing agent product of main phase (theoretical content 93.2%), fusing point is 1425 DEG C, in preparation process
The main harmful element removal efficiency of nitrogen, chlorine is respectively 99.3% and 98.5%.
Embodiment 2:
With certain metallurgy of aluminium factory aluminium grey (aluminium content 65.6%, nitrogen content 7.2%, chlorinity 4.6%) for raw material, first by aluminium
Ash carries out ingredient according to aluminium calcium constituent ratio 1:1.05 with lime stone (dioxide-containing silica is lower than 1%), then raw material, which mixes, to be suppressed
At the agglomerate of diameter 15mm；After agglomerate is sufficiently dried, places it in air atmosphere and carry out one section of roasting, maturing temperature 500
DEG C, calcining time 120min；Two-stage calcination temperature is 1000 DEG C, calcining time 90min, calcination atmosphere O2/(O2+N2)
=40%；Three sections 1480 DEG C of maturing temperature of melting, calcining time 240min, calcination atmosphere is air；It will roasting after roasting
Product is cooling, is crushed to 5mm hereinafter, obtaining with 12CaO7Al2O3For the desulfurizing agent product of main phase (theoretical content 90.2%),
Fusing point is 1380 DEG C, and the main harmful element removal efficiency of nitrogen, chlorine is respectively 99.0% and 98.1% in preparation process.
Embodiment 3:
With certain metallurgy of aluminium factory aluminium grey (aluminium content 65.6%, nitrogen content 7.2%, chlorinity 4.6%) for raw material, first by aluminium
Ash carries out ingredient according to aluminium calcium constituent ratio 1:1.1 with steel slag (dioxide-containing silica is lower than 1%), and raw material mixing is then pressed into straight
The agglomerate of diameter 15mm；It after agglomerate is sufficiently dried, places it in air atmosphere and carries out one section of roasting, maturing temperature is 450 DEG C, roasting
The burning time is 150min；Two-stage calcination temperature is 900 DEG C, calcining time 120min, calcination atmosphere O2/(O2+N2)=
55%；Three sections 1600 DEG C of maturing temperature of melting, calcining time 180min, calcination atmosphere is air；Roasting is produced after roasting
Object is cooling, is crushed to 5mm hereinafter, obtaining with 12CaO7Al2O3For the desulfurizing agent product of main phase (theoretical content 90.1%), melt
Point is 1450 DEG C, and nitrogen, the main harmful element removal efficiency of chlorine are respectively 99.5% and 98.7% in preparation process.
Embodiment 4:
With certain metallurgy of aluminium factory aluminium grey (aluminium content 58.6%, nitrogen content 6.9%, chlorinity 6.9%) for raw material, first by aluminium
Ash carries out ingredient, raw material according to aluminium calcium constituent ratio 1:1.08 with lime stone, quick lime, steel slag (dioxide-containing silica is lower than 1%)
Mix the agglomerate for being then pressed into diameter 15mm；After agglomerate is sufficiently dried, places it in air atmosphere and carry out one section of roasting, roasting
Burning temperature is 405 DEG C, calcining time 150min；Two-stage calcination temperature is 925 DEG C, calcining time 120min, calcination atmosphere
For O2/(O2+N2)=50%；Three sections 1620 DEG C of maturing temperature of melting, calcining time 180min, calcination atmosphere is air；Roasting knot
It is after beam that product of roasting is cooling, be crushed to 5mm hereinafter, obtaining with 12CaO7Al2O3For the de- of main phase (theoretical content 92.1%)
Sulphur agent product, fusing point are 1450 DEG C, and the main harmful element removal efficiency of nitrogen, chlorine is respectively 99.7% and 98.9% in preparation process.
Claims (6)
1. a kind of synchronize the method for preparing the steel desulfurization agent of calcium aluminate system using aluminium ash sintering imurity-removal, it is characterised in that: will
Aluminium ash and calcic raw material mix, and are pressed into agglomerate；Gained agglomerate is sequentially placed into roasting in air atmosphere and carries out one after drying
Section low-temperature bake is placed in two sections of medium temperature roasts of progress in strong oxidizing property atmosphere, is placed in three sections of high-temperature fusions of progress in air atmosphere
Roasting, product of roasting are crushed through supercooling to get calcium aluminate fimily desulfurizing agent.
2. a kind of synchronized using aluminium ash sintering imurity-removal according to claim 1 prepares the steel desulfurization agent of calcium aluminate system
Method, it is characterised in that: it is 1:1.02~1:1.1 that the ratio of aluminium ash and calcic raw material, which controls Al:Ca elemental mole ratios,.
3. a kind of synchronized using aluminium ash sintering imurity-removal according to claim 2 prepares the steel desulfurization agent of calcium aluminate system
Method, it is characterised in that: the calcic raw material includes at least one of quick lime, calcium hydroxide, lime stone, steel slag；The calcic
The dioxide-containing silica of raw material is lower than 3.0%.
4. a kind of described in any item synchronized using aluminium ash sintering imurity-removal prepare the refining of calcium aluminate system according to claim 1~3
The method of steel desulfurizing agent, it is characterised in that: the condition of one section of low-temperature bake are as follows: temperature is 300~500 DEG C, the time 120
~180min.
5. a kind of described in any item synchronized using aluminium ash sintering imurity-removal prepare the refining of calcium aluminate system according to claim 1~3
The method of steel desulfurizing agent, it is characterised in that: the condition of two sections of medium temperature roasts are as follows: temperature is 800~1000 DEG C, the time 90
~150min, volume percent oxygen is O in calcination atmosphere2/(O2+N2)=40~65%.
6. a kind of described in any item synchronized using aluminium ash sintering imurity-removal prepare the refining of calcium aluminate system according to claim 1~3
The method of steel desulfurizing agent, it is characterised in that: the condition of three sections of high-temperature fusions roasting are as follows: temperature is 1480~1620 DEG C, when
Between be 180~240min.
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Cited By (10)
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| CN110451542A (en) * | 2019-09-20 | 2019-11-15 | 宁夏正丰环保建材有限公司 | A kind of technique and production system using aluminium ash production calcium aluminate powder |
| CN112076618A (en) * | 2020-09-17 | 2020-12-15 | 刘保成 | Denitration agent and method for desulfurization and denitration of refractory brick by using denitration agent |
| CN112267018A (en) * | 2020-09-29 | 2021-01-26 | 朱广东 | Aluminum magnesium co-production process |
| CN112680564A (en) * | 2020-12-18 | 2021-04-20 | 中南大学 | Method for preparing calcium aluminate steelmaking desulfurizer by melting high magnesium aluminum ash |
| CN112723400A (en) * | 2020-12-18 | 2021-04-30 | 中南大学 | Method for melting calcium aluminate by synchronously activating, inerting, impurity removing and low-magnesium aluminum ash |
| CN113683108A (en) * | 2021-09-28 | 2021-11-23 | 兰溪市博远金属有限公司 | Method for preparing calcium aluminate product by using secondary aluminum ash |
| CN113913619A (en) * | 2021-10-11 | 2022-01-11 | 北京科技大学 | Method for efficiently removing nitrogen from secondary aluminum ash and preparing premelted calcium aluminate refining agent |
| CN114455617A (en) * | 2022-02-24 | 2022-05-10 | 肇庆南都再生铝业有限公司 | Method for producing calcium aluminate by using aluminum ash |
| CN114875194A (en) * | 2022-04-25 | 2022-08-09 | 武汉钢铁有限公司 | Molten iron lime-based KR high-efficiency desulfurizing agent and preparation method thereof |
| CN114871240A (en) * | 2022-03-30 | 2022-08-09 | 湖南博一环保科技有限公司 | Electrolytic manganese filter-press residue for removing ammonia nitrogen and desulfurization as well as preparation method and application thereof |
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| CN110451542A (en) * | 2019-09-20 | 2019-11-15 | 宁夏正丰环保建材有限公司 | A kind of technique and production system using aluminium ash production calcium aluminate powder |
| CN112076618B (en) * | 2020-09-17 | 2022-08-09 | 刘保成 | Method for desulfurization and denitrification of refractory bricks by using denitrification agent |
| CN112076618A (en) * | 2020-09-17 | 2020-12-15 | 刘保成 | Denitration agent and method for desulfurization and denitration of refractory brick by using denitration agent |
| CN112267018A (en) * | 2020-09-29 | 2021-01-26 | 朱广东 | Aluminum magnesium co-production process |
| CN112680564A (en) * | 2020-12-18 | 2021-04-20 | 中南大学 | Method for preparing calcium aluminate steelmaking desulfurizer by melting high magnesium aluminum ash |
| CN112723400A (en) * | 2020-12-18 | 2021-04-30 | 中南大学 | Method for melting calcium aluminate by synchronously activating, inerting, impurity removing and low-magnesium aluminum ash |
| CN112723400B (en) * | 2020-12-18 | 2022-02-11 | 中南大学 | Method for melting calcium aluminate by synchronously activating, inerting, impurity removing and low-magnesium aluminum ash |
| CN113683108A (en) * | 2021-09-28 | 2021-11-23 | 兰溪市博远金属有限公司 | Method for preparing calcium aluminate product by using secondary aluminum ash |
| CN113913619A (en) * | 2021-10-11 | 2022-01-11 | 北京科技大学 | Method for efficiently removing nitrogen from secondary aluminum ash and preparing premelted calcium aluminate refining agent |
| CN114455617A (en) * | 2022-02-24 | 2022-05-10 | 肇庆南都再生铝业有限公司 | Method for producing calcium aluminate by using aluminum ash |
| CN114871240A (en) * | 2022-03-30 | 2022-08-09 | 湖南博一环保科技有限公司 | Electrolytic manganese filter-press residue for removing ammonia nitrogen and desulfurization as well as preparation method and application thereof |
| CN114871240B (en) * | 2022-03-30 | 2023-05-30 | 湖南博一环保科技有限公司 | Electrolytic manganese filter pressing slag for ammonia nitrogen removal and desulfurization as well as preparation method and application thereof |
| CN114875194A (en) * | 2022-04-25 | 2022-08-09 | 武汉钢铁有限公司 | Molten iron lime-based KR high-efficiency desulfurizing agent and preparation method thereof |
| CN114875194B (en) * | 2022-04-25 | 2023-11-14 | 武汉钢铁有限公司 | Molten iron lime-based KR efficient desulfurizing agent and preparation method thereof |
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