CN108046617A - A kind of high-purity metallurgy lime and preparation method thereof - Google Patents
A kind of high-purity metallurgy lime and preparation method thereof Download PDFInfo
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- CN108046617A CN108046617A CN201711416690.9A CN201711416690A CN108046617A CN 108046617 A CN108046617 A CN 108046617A CN 201711416690 A CN201711416690 A CN 201711416690A CN 108046617 A CN108046617 A CN 108046617A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2/00—Lime, magnesia or dolomite
- C04B2/02—Lime
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2/00—Lime, magnesia or dolomite
- C04B2/02—Lime
- C04B2/04—Slaking
- C04B2/045—After-treatment of slaked lime
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- Organic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Treatment Of Steel In Its Molten State (AREA)
Abstract
The invention discloses a kind of high-purity metallurgy lime and preparation method, chemical component weight percentage is：Calcium oxide CaO：93~98%, silica SiO2：0.01~0.3%, magnesia MgO：0.01~0.3%, sulphur S：0.001~0.02%, carbon C：0.01~0.15%, its preparation method, which have passed through, to be roasted lime stone to obtain calcium oxide, then calcium oxide is digested to obtain calcium hydroxide, slurrying and press filtration are carried out to calcium hydroxide again, most of silica in lime and oxidation magnesium addition are got rid of to obtain pure calcium hydroxide slurry by this process, then slurry is roasted after precipitation is molded, it is natural gas or coal gas to roast the energy used, has prevented influence of the carbon to lime in raw material.
Description
Technical field
The invention belongs to field of steel metallurgy, are related to a kind of high-purity metallurgy lime and preparation method thereof.
Background technology
Lime (CaO) is used as one of Ferrous Metallurgy and the most basic raw material of industry of building material industry, typically by lime stone
(CaCO3) high-temperature calcination is decomposed.It is mainly used for converter slag-making, molten iron pretreatment and external refining in iron and steel metallurgical industry
Etc. multiple stations, usage amount reaches more than 70kg/ tons of steel.But no matter metallurgy industry standard regulation (YB/T042-2004) is gone back
It is existing various techniques and the quality in kind of equipment production lime, all there are silica, magnesia impurity content and carbon to contain
The problem of figureofmerit is higher and reactivity is relatively low (is shown in Table 1).The lime product of prior art production can be used for general smelting
Golden process and building material industry, but for refining some silicon, carbon and sulfur content require very low ultra-clean steel then and do not apply to, stone
Carbon in steel can be increased in sweetening process when silica, magnesia impurity content and higher carbon content index in ash, silicon contains
Amount, the serious implementation for restricting ultra-clean steel smelting process make that the special type steel chemical composition is not up to standard, and ingredient hit rate significantly drops
It is low, very big economic loss is caused to ultra-low-carbon steel manufacturing enterprise.
As typical sedimentary rock type, magnesia and silica mainly symbiosis and stone in the form of impurity in lime stone
In lime stone, it can be enriched with, be remained in metallurgy lime during decomposition of limestone, finally enter steel smelting with metallurgy lime
It refines in slagging process.Wherein magnesia belongs to refractory oxide, and the residual in metallurgy lime can cause different refinings
Slag system viscosity increases, and is not easy to slag making.And silica can then reduce the basicity of slag system, be not easy to ultra-clean steel sweetening process,
And in slag silica presence, can and aluminium in molten steel reduction reaction occurs so that aluminium content reduces in molten steel, influences ultrapure
The smelting of net steel.
And there are two types of existing forms for carbon in lime stone：First, inorganic carbon, i.e., exist in the form of CO32-, be carbon in lime stone
Be primarily present form；Second is that organic carbon contained in the organism being wrapped in during organic carbon, i.e. lime stone diagenesis, only accounts for lime
Few part of stone carbon content.Lime stone is in high-temperature burning process, and inorganic carbon decomposites the effusion of CO2 gases, and organic carbon is then
It is directly volatilized with gaseous state or reacts generation CO2 gases with CO2 and escape, finally obtain the lime based on CaO.
But a part of carbon still can be remained in the lime obtained by high-temperature calcination.Different, the residual carbon according to its origin cause of formation
Three kinds of carbon impurity, primary carbon and regenerative carbon can be divided into：
1) carbon impurity is mainly coal, fuel oil or fuel gas buring in the calcine technology using fuel combustion directly-fired kiln
The free carbon on lime surface not exclusively is attached to, is mainly existed in the form of simple substance carbon；
2) primary carbon is the inorganic carbon and organic carbon contained by incomplete " half-cooked " lime of limestone block calcining and decomposing
Summation, carbon characteristic distributions are the center and the distribution uniform in center for concentrating on block lime, the bulk produced such as shaft furnace
Often there is " half-cooked " phenomenon (also referred to as " raw burn " or " underburnt ") of lime block in lime and the small lump lime of rotary kiln production；
3) regenerative carbon is to generate substantial amounts of CO2 gas using the kiln fuel combustion and decomposition of limestone of direct combustion heating
Body, the CO2 of high concentration can generate CaCO3 with decomposition product CaO again, this part CaCO3 can not possibly be whole when lime cools down
It decomposes, some is still trapped in lime exists in the form of inorganic carbon, and the carbon content on general lime block surface is slightly higher
In inside, concrete content height is different with system CO2 concentration and cooling velocity size.
At present, the production technology of domestic large-scale production active lime mainly has shaft furnace, rotary kiln, mechanical kiln, fuel master
To use coal dust, coal gas, natural gas.It is conventionally produced go out active lime carbon content >=0.5%, silica and magnesia
Content is higher than 0.6%, can not meet ultra-clean steel, high grade silicon steel, pipe line steel, ultra-low-carbon steel quality requirement.
Although the patent of invention in relation to active lime is numerous, it is related to reducing the patent such as Shen of the carbon and sulfur content in lime
Please be number for 200910063811.5 " a kind of preparation methods of low-sulfur low-carbon active lime ", Application No. 200610018345.5
" a kind of production method of active lime ", a kind of " side of the ultralow carbon-lime of rotary kiln baking of Application No. 201210358390.0
Method and its lime product of production ", Application No. 201110408955.7 " a kind of porous granular low carbon lime and its producer
Method ".But its product is largely that lime stone is roasted under different technology conditions, without inherently reducing in lime
Magnesia, silica impurity content, and the situation of carbon content in metallurgy lime is primarily upon, there is no consider titanium dioxide
The situation of the impurity contents such as silicon, magnesia is not particularly suited for the smelting of ultra-clean steel.
Therefore, it is badly in need of developing new method, to prepare the above-mentioned lime for meeting ultra-clean steel smelting requirements, in the present invention
It is middle that Ca (OH) is utilized after roasting using calcium hydroxide2=CaO+H2The mode that O obtains CaO is developed.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of high-purity metallurgy lime and preparation method thereof.That it changes biographies
The lime production technique of system, i.e., obtain the technique of lime by lime stone high-temperature roasting.Its creativeness is proposed lime stone first
It is roasted to obtain calcium oxide, then calcium oxide is digested to obtain calcium hydroxide, then slurrying and pressure are carried out to calcium hydroxide
Most of silica in lime and oxidation magnesium addition are got rid of to obtain pure calcium hydroxide slurry by filter, this process,
Then slurry is roasted after precipitation is molded, it is natural gas or coal gas to roast the energy used, has been prevented in raw material
Influence of the carbon to lime.
The present invention is to solve above-mentioned technical problem by following technical proposals：
The present invention provides a kind of high-purity metallurgy limes, which is characterized in that its chemical component weight percentage is：Calcium oxide
CaO：93~98%, silica SiO2：0.01~0.3%, magnesia MgO：0.01~0.3%, sulphur S：0.001~
0.02%, carbon C：0.01~0.15%.
Invention further provides a kind of preparation methods of high carbonate-free lime, which is characterized in that it comprises the following steps：
(1) exploitation of lime stone will crush, it is 20 that granularity is chosen after crushing with broken after Limestone mining in crusher
The lime stone of~50mm is spare；
(2) roasting of lime stone, by the lime stone in step (1) in revolution roasting in kilns, calcining heat for 1050~
1100 DEG C, obtain active calcium oxide；And impurity is removed, it is refined into the grain size of below 40mm；
(3) digestion of active calcium oxide, by the active calcium oxide in step (2) and water 4~6:1 ratio is digested,
Obtain calcium hydroxide；Impurity is removed in calcium hydroxide；Obtain the calcium hydroxide that purity is more than 93%；
(4) slurrying by the calcium hydroxide in step (3) after cooling, precipitation process, is then added in water, wherein disappearing
The ratio of lime and water is 8~10:1 is made calcium hydroxide slurry；
(5) calcium hydroxide slurry in step (4) is carried out press filtration by press filtration with mechanism filter-pressing pattern, and filter bag mesh number is 100
Mesh；Oxygen calcium and magnesium not soluble in water in slurry, silica impurity are removed, obtains the calcium hydroxide slurry that purity is more than 93%-；
(6) dehydration by the calcium hydroxide slurry in step (5), is injected in centrifuge, the angular speed of centrifuge is
100~120r/min is carried out dehydrating, and obtains powdery calcium hydroxide；
(7) it is molded, by the powdery calcium hydroxide in step (6) by any one in high-pressure ball press or disk balling machine
Kind is processed into the ball bulk calcium hydroxide of 10~40mm；
(8) calcium hydroxide roasts, by the ball bulk calcium hydroxide in step (7) through 1100~1200 DEG C of height in rotary kiln
When temperature roasting 2.0~2.5 is small, high-purity metallurgy lime is obtained.
Weight percent calcium is aoxidized in lime stone described further and is more than or equal to 53%, the weight percent of sulphur is less than or equal to
0.02%.
Further, fuel used in the calcium hydroxide roasting process is natural gas and/or coal gas.
The positive effect of the present invention is：It is creative to propose first to be roasted lime stone and is aoxidized
Then calcium is digested to obtain calcium hydroxide, then slurrying and press filtration is carried out to calcium hydroxide to calcium oxide, this process is by lime
In most of silica and oxidation magnesium addition get rid of to obtain pure calcium hydroxide slurry, then to slurry through precipitation
It is roasted after shaping, it is natural gas or coal gas to roast the energy used, has prevented influence of the carbon to lime in raw material.Using
The technical solution that the present invention narrates has two aspect important improvements：(1) lime for obtaining biscuit firing digested, slurrying with
And press filtration processing, using silica, magnesia is not soluble in water, the atomic feature for being dissolved in alkali, by silica and magnesia from
It is removed in raw material, has achieved the purpose that refine intermediate raw material, obtained the calcium hydroxide middle material of high-purity, be after baking
It obtains high-purity metallurgy lime and creates condition.(2) to carbon-free ball bulk calcium hydroxide Ca (OH) 2 during after baking
Roasted, and it is unconventional limestone CaCO3 is roasted, while using natural gas and/or coal gas as heat source so that
Carbon content is extremely low in finished product metallurgy lime.
Description of the drawings
Fig. 1 is the flow chart of the production method of high-purity metallurgy lime of the present invention.
Specific embodiment
Below in conjunction with the attached drawing in the embodiment of the present invention, the technical solution in the embodiment of the present invention is carried out clear, complete
Site preparation describes, it is clear that described embodiment is only part of the embodiment of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art are obtained every other without making creative work
Embodiment belongs to the scope of protection of the invention.
Present pre-ferred embodiments are given below, with the technical solution that the present invention will be described in detail.
It is as follows using lime stone physical and chemical index used：
Chemical composition：Calcium oxide CaO：54.23wt%；Sulphur S：0.015wt%；Silica SiO2：0.42wt%；Oxidation
Magnesium MgO：0.53wt%.
Granularity：20~50mm.
Embodiment 1：
(1) roasting of lime stone, for the lime stone by in revolution roasting in kilns, calcining heat is 1050 DEG C, obtains activity
Calcium oxide；And impurity is removed, it is refined into the grain size of below 40mm；
(2) active calcium oxide in step (2) is digested, obtains calcium hydroxide (hydroxide by the digestion of active calcium oxide
Calcium)；Active calcium oxide and water 4:1 ratio is digested, and obtains calcium hydroxide；Impurity is removed in calcium hydroxide；It obtains pure
Calcium hydroxide of the degree more than 93%；
(3) calcium hydroxide slurry is made in the calcium hydroxide in step (3) by slurrying；Calcium hydroxide is by cooling, precipitation process
Afterwards, it is then added in water, the ratio of medium-slaking lime and water is 8:1 is made calcium hydroxide slurry；
(4) calcium hydroxide slurry in step (4) is carried out press filtration by press filtration with mechanism filter-pressing pattern, and filter bag mesh number is 100
Mesh；Oxygen calcium and magnesium not soluble in water in slurry, silica impurity are removed, obtains the calcium hydroxide slurry that purity is 93%；
(5) dehydration by the calcium hydroxide slurry in step (5), is injected in centrifuge, the angular speed of centrifuge is
100r/min is carried out dehydrating, and obtains powdery calcium hydroxide；
(6) it is molded, the ball that the powdery calcium hydroxide in step (6) is processed into 10~40mm by high-pressure ball press is block
Calcium hydroxide；
(7) calcium hydroxide roasts, by the ball bulk calcium hydroxide in step (7) through 1120 DEG C of high-temperature roastings in rotary kiln
2.0 it is small when, obtain high-purity metallurgy lime.
Embodiment 2：
(1) roasting of lime stone, for the lime stone by in revolution roasting in kilns, calcining heat is 1100 DEG C, obtains activity
Calcium oxide；
(2) active calcium oxide in step (2) is digested, obtains calcium hydroxide (hydroxide by the digestion of active calcium oxide
Calcium)；Active calcium oxide and water 6:1 ratio is digested, and obtains calcium hydroxide；Impurity is removed in calcium hydroxide；It obtains pure
Spend the calcium hydroxide for 98%；
(3) slurrying by the calcium hydroxide in step (3) after cooling, precipitation process, is then added in water, wherein disappearing
The ratio of lime and water is 10:1 is made calcium hydroxide slurry；
(4) calcium hydroxide slurry in step (4) is carried out press filtration by press filtration with mechanism filter-pressing pattern, and filter bag mesh number is 100
Mesh；Oxygen calcium and magnesium not soluble in water in slurry, silica impurity are removed, obtains the calcium hydroxide slurry of purity 98%；
(5) dehydration by the calcium hydroxide slurry in step (5), is injected in centrifuge, the angular speed of centrifuge is
120r/min is carried out dehydrating, and obtains powdery calcium hydroxide；
(6) it is molded, the powdery calcium hydroxide in step (6) is any one by high-pressure ball press or disk balling machine processing
Plant the ball bulk calcium hydroxide into 10~40mm；
(7) calcium hydroxide roasts, by the ball bulk calcium hydroxide in step (7) through 1140 DEG C of high-temperature roastings in rotary kiln
2.2 it is small when, obtain high-purity metallurgy lime.
Embodiment 3：
(1) roasting of lime stone, for the lime stone by in revolution roasting in kilns, calcining heat is 1080 DEG C, obtains activity
Calcium oxide；
(2) active calcium oxide in step (2) is digested, obtains calcium hydroxide (hydroxide by the digestion of active calcium oxide
Calcium)；Active calcium oxide and water 5:1 ratio is digested, and obtains calcium hydroxide；Impurity is removed in calcium hydroxide；It obtains pure
Spend the calcium hydroxide for 95%；
(3) slurrying by the calcium hydroxide in step (3) after cooling, precipitation process, is then added in water, wherein disappearing
The ratio of lime and water is 10:1 is made calcium hydroxide slurry；
(4) calcium hydroxide slurry in step (4) is carried out press filtration by press filtration with mechanism filter-pressing pattern, and filter bag mesh number is 100
Mesh；Oxygen calcium and magnesium not soluble in water in slurry, silica impurity are removed, obtains the calcium hydroxide slurry of purity 95%；
(5) dehydration by the calcium hydroxide slurry in step (5), is injected in centrifuge, the angular speed of centrifuge is
120r/min is carried out dehydrating, and obtains powdery calcium hydroxide；
(6) it is molded, the powdery calcium hydroxide in step (6) is processed into 10 by high-pressure ball press or disk balling machine~
The ball bulk calcium hydroxide of 40mm；
(7) calcium hydroxide roasts, by the ball bulk calcium hydroxide in step (7) through 1160 DEG C of high-temperature roastings in rotary kiln
2.3 it is small when, obtain high-purity metallurgy lime.
Embodiment 5：
(1) roasting of lime stone, for the lime stone by in revolution roasting in kilns, calcining heat is 1100 DEG C, obtains activity
Calcium oxide；
(2) active calcium oxide in step (2) is digested, obtains calcium hydroxide (hydroxide by the digestion of active calcium oxide
Calcium)；
(3) calcium hydroxide slurry is made in the calcium hydroxide in step (3) by slurrying；
(4) calcium hydroxide slurry in step (4) is carried out press filtration by press filtration, remove oxygen calcium and magnesium not soluble in water in slurry,
The impurity such as silica obtain the calcium hydroxide slurry of high cleanliness；
(5) calcium hydroxide slurry in step (5) is carried out dehydrating, obtains powdery calcium hydroxide by dehydration；
(6) it is molded, the powdery calcium hydroxide in step (6) is processed into 10 by high-pressure ball press or disk balling machine~
The ball bulk calcium hydroxide of 40mm；
(7) calcium hydroxide roasts, by the ball bulk calcium hydroxide in step (7) through 1180 DEG C of high-temperature roastings in rotary kiln
2.5 it is small when, obtain high-purity metallurgy lime.
The final high-purity metallurgy lime product testing value obtained in different embodiments is as shown in table 1：
The detected value of product is obtained under 1 different technology conditions of table
As seen from the above embodiment, using high-purity metallurgy lime prepared by the method for the present invention, calcium oxide content is substantially high
In the superfine requirement of national standard, magnesia, silica want ball well below national standard superfine, while carbon, sulfur content are far below in lime
Product index in national standard and documents.The appearance of the invention, for the high-purity metallurgy lime in China preparation provide it is a kind of high
The method of effect provides the foundation for China's ultra-clean steel and the smelting of the steel grade of particular/special requirement.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned exemplary embodiment, Er Qie
In the case of without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Profit requirement rather than above description limit, it is intended that all by what is fallen within the meaning and scope of the equivalent requirements of the claims
Variation is included within the present invention.Any reference numeral in claim should not be considered as to the involved claim of limitation.
Moreover, it will be appreciated that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
Using specification as an entirety, the technical solutions in each embodiment can also be properly combined, forms those skilled in the art
It is appreciated that other embodiment.
Claims (4)
1. a kind of high-purity metallurgy lime, which is characterized in that its chemical component weight percentage is：Calcium oxide CaO：93~98%,
Silica SiO2：0.01~0.3%, magnesia MgO：0.01~0.3%, sulphur S：0.001~0.02%, carbon C：0.01~
0.15%.
2. a kind of preparation method of high carbonate-free lime, which is characterized in that it comprises the following steps：
(1) exploitation of lime stone will be crushed with broken after Limestone mining in crusher, chosen after crushing granularity for 20~
The lime stone of 50mm is spare；
(2) roasting of lime stone, by the lime stone in step (1) in revolution roasting in kilns, calcining heat is 1050~1100 DEG C,
Obtain active calcium oxide；And impurity is removed, it is refined into the grain size of below 40mm；
(3) digestion of active calcium oxide, by the active calcium oxide in step (2) and water 4~6:1 ratio is digested, and is obtained
Calcium hydroxide；Impurity is removed in calcium hydroxide；Obtain the calcium hydroxide that purity is more than 93%；
(4) slurrying by the calcium hydroxide in step (3) after cooling, precipitation process, is then added in water, medium-slaking lime
Ratio with water is 8~10:1 is made calcium hydroxide slurry；
(5) calcium hydroxide slurry in step (4) is carried out press filtration by press filtration with mechanism filter-pressing pattern, and filter bag mesh number is 100 mesh；
Oxygen calcium and magnesium not soluble in water in slurry, silica impurity are removed, obtains the calcium hydroxide slurry that purity is more than 93%；
(6) dehydration injects the calcium hydroxide slurry in step (5) in centrifuge, the angular speed of centrifuge for 100~
120r/min is carried out dehydrating, and obtains powdery calcium hydroxide；
(7) it is molded, the powdery calcium hydroxide in step (6) is added by any one in high-pressure ball press or disk balling machine
Work is into the ball bulk calcium hydroxide of 10~40mm；
(8) calcium hydroxide roasts, and the ball bulk calcium hydroxide in step (7) is roasted in rotary kiln through 1100~1200 DEG C of high temperature
When burning 2.0~2.5 is small, high-purity metallurgy lime is obtained.
A kind of 3. high-purity metallurgy lime according to claim 2 and preparation method thereof, which is characterized in that the lime stone
Middle oxidation weight percent calcium is more than or equal to 53%, and the weight percent of sulphur is less than or equal to 0.02%.
A kind of 4. high-purity metallurgy lime according to claim 2 and preparation method thereof, which is characterized in that the hydrogen-oxygen
It is natural gas and/or coal gas to change fuel used in calcium roasting process.
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| CN111439769A (en) * | 2020-04-28 | 2020-07-24 | 广西夏阳环保科技有限公司 | Preparation method of high-purity and high-activity nano calcium oxide |
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| CN113735155A (en) * | 2020-05-29 | 2021-12-03 | 广西夏阳环保科技有限公司 | Preparation method of special calcium oxide for plastic moisture-proof master batch |
| CN115043419A (en) * | 2022-01-06 | 2022-09-13 | 贵州长泰源纳米钙业科技有限公司 | Production process of novel calcium hydroxide blender |
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| CN111573705A (en) * | 2020-04-30 | 2020-08-25 | 广西夏阳环保科技有限公司 | Preparation method of high-purity calcium oxide |
| CN113735155A (en) * | 2020-05-29 | 2021-12-03 | 广西夏阳环保科技有限公司 | Preparation method of special calcium oxide for plastic moisture-proof master batch |
| CN115043419A (en) * | 2022-01-06 | 2022-09-13 | 贵州长泰源纳米钙业科技有限公司 | Production process of novel calcium hydroxide blender |
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