CN109715833A - Dephosphorization treatment device and used the dephosphorization treatment device iron liquid dephosphorization method - Google Patents
Dephosphorization treatment device and used the dephosphorization treatment device iron liquid dephosphorization method Download PDFInfo
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- CN109715833A CN109715833A CN201780058172.6A CN201780058172A CN109715833A CN 109715833 A CN109715833 A CN 109715833A CN 201780058172 A CN201780058172 A CN 201780058172A CN 109715833 A CN109715833 A CN 109715833A
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C1/00—Refining of pig-iron; Cast iron
- C21C1/02—Dephosphorising or desulfurising
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/28—Manufacture of steel in the converter
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/28—Manufacture of steel in the converter
- C21C5/285—Plants therefor
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/28—Manufacture of steel in the converter
- C21C5/36—Processes yielding slags of special composition
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- Life Sciences & Earth Sciences (AREA)
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- Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
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Abstract
The present invention is the dephosphorization treatment device for carrying out the dephosphorization treatment of iron liquid, includes converter；Top-blown spray gun, the top-blown spray gun are blown into oxygen into above-mentioned converter；1st gas line, the 1st gas line supply above-mentioned oxygen into above-mentioned top-blown spray gun；1st distributor, the 1st distributor maintain the source CaO sprayed together with above-mentioned oxygen by above-mentioned top-blown spray gun；With the 2nd distributor, the 2nd distributor at least maintains the Al sprayed together with above-mentioned oxygen by above-mentioned top-blown spray gun2O3Source.
Description
Technical field
The present invention relates to can inexpensively and efficiently carry out the dephosphorization treatment device of dephosphorization treatment and use at the dephosphorization
Manage the dephosphorization method of the iron liquid of device.
Background technique
In recent years, the requirement for steel improves, the increase in demand for Low-phosphorus Steel.Currently, the dephosphorization treatment one of iron liquid
As carried out extensively by the method handled under the thermodynamically cryogenic conditions in advantageous iron liquid stage.As progress iron
The device of the dephosphorization treatment of liquid, combined blown converter are suitable.In combined blown converter, as oxidant required for dephosphorization treatment,
Can by the few gas oxygen of the thermal losses compared with solid oxidizer by top-blown spray gun to be ejected into iron liquid at a high speed.
As Dephosphorising agent, mainly use lime stone (CaCO3) be burnt into obtained from quick lime (CaO).However,
Since lime stone is relatively cheap compared with quick lime, so wanting to use lime stone as far as possible as Dephosphorising agent.However, lime stone
There is a problem of following: being thermally decomposed in 900 DEG C or so the endothermic reactions by (1) formula below, bonded hard ferrite magnet reduce and
Generate very big thermal losses.
CaCO3=CaO+CO2 (1)
But in the case where [Si] concentration is high or bonded hard ferrite magnet is high or waste material fit rate is low, due to taking off for iron liquid
Hot nargin in phosphorus processing is got higher, so being able to use cheap lime stone.
But the dephosphorization treatment of iron liquid under the cryogenic conditions in iron liquid stage due to carrying out, so promoting to be used as Dephosphorising agent
The dregsization of the CaO used is important.In order to be 2300 DEG C or more CaO dregsization very high in this way by fusing point, fluorite is used
(CaF2) it is effective.However, in the case where having used fluorite, since the clinker that the dregsization by CaO generates contains fluorine
(F), so the disadvantages such as the recycling destination of clinker is substantially limited are big.Therefore, the CaO dregsization without using fluorite is developed
Promotion method.
As this method, such as disclose following methods: the basicity of the clinker after making dephosphorization treatment (CaO mass concentration/
SiO2Mass concentration) become 1.8~2.6, at least part of refining agent is set as ferro-calcium elements body, is 3mm or less by partial size
Quick lime be ejected into iron liquid together with oxygen (referring to patent document 1) by top-blown spray gun.However, in the method, if not simultaneously
It, then can not be by iron liquid dephosphorization to extremely low [P] concentration ([P]≤0.015 mass %) with the ferro-calcium elements body of high price.Accordingly, there exist want
Spend many cost such problems.
In addition, as in the case where not using fluorite or ferro-calcium elements body, by CaO, efficiently dregsization carrys out melting Low-phosphorus Steel
Method, CaO powder, Al will be contained by top-blown spray gun by disclosing2O3Powder and Fe2O3The mixed powder of powder sprays together with carrier of oxygen jet flow
To the method for the bath face that [Si] concentration is 0.15 mass % iron liquid below (referring to patent document 2).In the method, Al2O3Or
Fe2O3The CaO-Al of low melting point is reacted and is readily formed with CaO2O3- FeO melt, dephosphorisation reaction extremely efficiently carry out.
Although however, CaO powder, Al2O3Powder, Fe2O3The respective unit price of powder is low, but in order to mixed by production such as mixers
Powder is closed, many costs are spent.In addition, if this method is applicable in for the iron liquid that [Si] concentration is more than 0.15 mass %, de-
Blowing first half desilication reaction in phosphorus processing rapidly carries out and generates SiO in large quantities2, so the blowing first half in dephosphorization treatment
Basicity of slag (the CaO additive amount/(SiO of phase2Production quantity+SiO2Additive amount)) it reduces, the frequency for generating spray slag suddenly increases.Due to mixed
The compounding ratio for closing each powder in powder is pre-determined, so also can not neatly be coped with according to iron liquid condition.
On the other hand, a kind of iron liquid dephosphorization method is disclosed, forms the covering slag containing CaO, the protection in blowing first half
Basicity (the weight ratio: CaO/SiO of slag2) it is 0.4~1.5, later by CaO powder and Al2O3Powder and Fe2O3The mixed powder of powder is pushed up
It blows (referring to patent document 3).In the method, the covering slag of low melting point is formed by the blowing first half in dephosphorization treatment,
It can reduce splash object amount.However, since the blowing first half in dephosphorization treatment promotes at low temperature, so if according to basicity at
Block-like CaO is added for 0.4~1.5 mode, then is not completely melt and dephosphorization utilization effect in blowing first half block-like CaO
Rate is lower.In addition, also remaining unfused CaO in clinker after the dephosphorization treatment of iron liquid, it is efficiently applied to by dephosphorization clinker
Become problem whens roadbed material etc..In order to avoid the problem, the case where the ferro-calcium elements body using low melting point is to form covering slag
Under, it leads to the problem of spend many costs as described above.
As described above in the prior art, if there are costs to become mostly in this way using ferro-calcium elements body or production mixed powder
The problem of.In addition, if being also not easy to adjust processing method according to dephosphorization treatment condition using mixed powder.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2010-1536 bulletin
Patent document 2: No. 3525766 bulletins of Japanese Patent No.
Patent document 3: No. 3687433 bulletins of Japanese Patent No.
Summary of the invention
Problems to be solved by the invention
Present invention point in view of the above-mentioned problems, it is therefore an objective to which providing being capable of the inexpensively low-phosphorous iron liquid of melting by dephosphorization treatment
Dephosphorization treatment device and used dephosphorization treatment device iron liquid dephosphorization method.
Means for solving the problems
When completing the present invention, due in order to by CaO powder, Al2O3Powder etc. makes mixed powder by mixer etc. and to spend perhaps
More costs, so the inventors of the present invention are conceived to: if using two or more powder supply distributors, with production mixed powder phase
It is inhibited than cost and trouble.In addition, being also conceived to:, can due to the powder supply distributor by using two or more
To change the ratio of components of each powder in blowing, so becoming able to suitably select the powder in the blowing in the dephosphorization treatment of iron liquid
The mixing of body forms, and can reasonably be handled according to treatment conditions.Then, probe is with treatment conditions corresponding blows
The influence of the variation of the mixing composition of powder in refining.As a result, having found following methods: especially by according in blowing
Loading basicity (CaO charge weight/(SiO2The SiO generated by the oxidation of [Si] in charge weight+iron liquid2Production quantity): mass ratio)
Passage and CaO and Al by top blast powder2O3Mixing compositional optimization, can be avoided the spray slag and low-phosphorous iron liquid of melting ([P]
≤ 0.020 mass %).
The present invention is as described below.
(1) a kind of dephosphorization treatment device, which is characterized in that it is the dephosphorization treatment device for carrying out the dephosphorization treatment of iron liquid,
It is included
Converter；
Top-blown spray gun, the top-blown spray gun are blown into oxygen into above-mentioned converter；
1st gas line, the 1st gas line supply above-mentioned oxygen into above-mentioned top-blown spray gun；
1st distributor, the 1st distributor maintain the source CaO sprayed together with above-mentioned oxygen by above-mentioned top-blown spray gun；With
2nd distributor, the 2nd distributor at least maintain the Al sprayed together with above-mentioned oxygen by above-mentioned top-blown spray gun2O3
Source.
(2) the dephosphorization treatment device according to above-mentioned (1), which is characterized in that it further has and above-mentioned 1st gas
The 2nd different gas line of pipeline, the 2nd gas line is by the above-mentioned source CaO and above-mentioned Al2O3Source mixes and is supplied to above-mentioned top
It blows and sprays in rifle.
(3) a kind of dephosphorization method of iron liquid, which is characterized in that it is to have used dephosphorization treatment described in above-mentioned (1) or (2)
The dephosphorization method of the iron liquid of device, wherein
Iron liquid is packed into above-mentioned converter, on one side by bottom blowing air port by nitrogen with 0.1~0.6Nm3/ minute/ton flow
It is blown into above-mentioned iron liquid and stirs, on one side by above-mentioned top-blown spray gun and 1.0~2.5Nm3The oxygen of/minute/ton flow together,
By since blowing until finishing blowing during total oxygen supply amount be set as 100% in the case where, from blowing
During starting until the oxygen for 50~80% amounts of spraying, the source CaO being held in above-mentioned 1st distributor is only ejected into iron
In liquid, the above-mentioned source CaO is only loaded into basicity as 0.8~1.2 this part, later by above-mentioned top-blown spray gun and above-mentioned oxygen
Together, it includes Al that only injection, which is held in above-mentioned 2nd distributor,2O3The mixed powder in source, Al in the mixed powder2O3Ratio
((Al2O3Quality)/(CaO mass+CaCO3Quality × 0.56+Al2O3Quality) × 100) it is 5~20 mass %, or injection is protected
The source CaO being held in above-mentioned 1st distributor and the Al being held in above-mentioned 2nd distributor2O3The mixed powder in source, the mixed powder
Middle Al2O3Ratio be 5~20 mass %, the loading basicity for handling latter stage is set as 1.5 or more, duration of blast is set as 6
~10 minutes.
(4) dephosphorization method of the iron liquid according to above-mentioned (3), which is characterized in that before blowing starts or blowing starts
Afterwards within 30 seconds, it is 10mm particulate CaO below that only addition, which is equivalent to and is packed into the maximum particle diameter of this part of basicity lower than 0.4,
Source, by since blowing until finishing blowing during total oxygen supply amount be set as 100% in the case where, from blowing
During refining starts until the oxygen for 50~80% amounts of spraying, only the above-mentioned source CaO is ejected into iron liquid, the above-mentioned source CaO is only
Be loaded into basicity and above-mentioned addition the source particulate CaO it is total as 0.8~1.2 this part, later by above-mentioned top-blown spray gun
Above-mentioned mixed powder is sprayed together with above-mentioned oxygen, is added up to the source particulate CaO of above-mentioned addition and is set the loading basicity for handling latter stage
It is set to 1.5 or more.
Invention effect
In accordance with the invention it is possible to provide by dephosphorization treatment can inexpensively the dephosphorization treatment device of the low-phosphorous iron liquid of melting and
The dephosphorization method of the iron liquid of dephosphorization treatment device is used.
Detailed description of the invention
Fig. 1 is the figure for illustrating the dephosphorization treatment device of embodiments of the present invention.
Specific embodiment
Hereinafter, the embodiments of the present invention will be described with reference to the drawings.
In the present invention, relative to iron liquid ([Si] concentration: 0.1~0.7 of the iron liquid or further desiliconization from blast furnace casting
Quality %), in combined blown converter, powder at least is made in a part of refining agent together with gas oxygen via top-blown spray gun and
It is ejected into iron liquid to carry out dephosphorization treatment.In the present embodiment, it " is maintained with what top blast oxygen pipeline was connected using having
The distributor in the source CaO " and " at least maintain Al2O3At least two or more the powders supply distributor of the distributor in source "
Dephosphorization treatment device carries out the dephosphorization treatment of iron liquid.
Fig. 1 is the figure for illustrating the dephosphorization treatment device of present embodiment.
As shown in Figure 1, in converter 1, above-mentioned iron liquid 2 is maintained, when carrying out dephosphorization treatment, via oxygen
Gas pipeline 4 and by top-blown spray gun 3 spray oxygen.In addition, when carrying out dephosphorization treatment, by maintaining the source CaO (CaO, CaCO3Deng)
The distributor 5 of powder maintains Al with what is be different from2O3Source (main Al2O3) powder distributor 6 be suitable for treatment conditions
Opportunity and with blending ratio appropriate supply powder.Wherein, the partial size of each powder preferably at most partial size in terms of conevying efficiency
It is set as 1mm or less.In addition, the powder in the source CaO is preferably set to lime stone (CaCO3Any one of) or quick lime (CaO)
Or their mixed powder, Al2O3The powder in source is preferably aluminous shale or bauxite.It should be noted that in the following description
In, the 1st distributor 5 is set as keeping the distributor of the powder in the source CaO, and the 2nd distributor 6 is set as keeping Al2O3The powder in source
Distributor, but the 2nd distributor 6 can also be kept the powder and Al in the source CaO2O3The powder that the powder in source is obtained by mixing.As this
Sample, the 2nd distributor 6 are set as at least maintaining Al2O3The distributor in source.
In addition, about the source CaO, CaO and CaCO3Total mass concentration be set as 80% or more, in addition to quick lime or stone
It is appropriate for being also mixed with the substance etc. of part dolomite other than lime stone.CaO and CaCO3Total mass concentration be set as 80%
Above reason be due to: if being set to be lower than 80%, become to be mixed into many except CaO or CaCO3Ingredient in addition, in dephosphorization
Slag bloating becomes excessive in processing and clinker overflows from fire door or become the undesirable dangerous raising of dephosphorization.About Al2O3Source,
Al2O3Mass concentration is set as 50% or more, other than bauxite, can also be Al2O3The high clinker of mass concentration or fire resisting
The waste wood etc. of object.Al2O3Mass concentration be set as 50% or more reason be due to: if being set to be lower than 50%, become to be mixed into
Many removes Al2O3Ingredient in addition, slag bloating becomes excessive in dephosphorization treatment and clinker overflows from fire door or becomes de-
The undesirable dangerous raising of phosphorus.It should be noted that Al2O3Mass concentration also can be set as 50% or more reason relatively low in this way
By being due to compared with the usage amount in the source CaO Al2O3The usage amount in source is relatively smaller, so the influence caused by dephosphorization treatment is small.
If starting to blow in dephosphorization treatment, the source CaO is fed into gas line 7 by the 1st distributor 5, the source CaO quilt
It transports in top-blown spray gun 3.For transport at this time with gas (carrier gas), N is used mostly2, but can be CO2Or Ar, it can also be with
It is oxygen.If the source CaO is transported in top-blown spray gun 3, the source CaO is injected into iron together with the oxygen supplied by oxygen pipeline 4
In liquid 2.It should be noted that using N2In the case where, become nitrogen and is also sprayed together with oxygen by top-blown spray gun 3, but by
In compared with oxygen the amount of nitrogen it is few, so can operationally ignore.In addition, in blowing, from not scheming for the bottom of converter 1
The air port shown is blown into nitrogen as bottom blown gas, and iron liquid 2 is stirred.
Then, details is described below, but the opportunity appropriate in blowing, Al2O3Source is also by 6 quilt of the 2nd distributor
It is supplied in gas line 7.Pass through Al2O3Source is fed into gas line 7, thus the source CaO and Al2O3Source is in gas line 7
In be mixed (rear mixing), mixed powder is transported in top-blown spray gun 3 by nitrogen etc..As a result, mixed powder by top-blown spray gun 3 with
Oxygen is injected into together in iron liquid 2.
Here, each powder can also be supplied directly in oxygen pipeline 4 by the 1st distributor 5 and the 2nd distributor 6, but examined
Consider the easiness etc. of the maintenance of distributor or gas line, the powder supplied by each distributor preferably by with oxygen pipeline 4 not
Same gas line 7 is mixed, and is transported in top-blown spray gun 3 via gas line 7 by nitrogen etc..Like this, in gas
These powders are mixed in fluid line 7, are injected into iron liquid 2 together with oxygen by top-blown spray gun 3.It should be noted that
In example shown in Fig. 1, gas line 7 is connected directly with top-blown spray gun 3, but can also make gas line 7 and oxygen pipeline 4
It is connected.
As described above, in the present embodiment, " distribution in the source CaO is maintained using having of being connected with top blast oxygen pipeline
Device " and " at least maintain Al2O3The dephosphorization treatment device of the powder supply distributor of at least two of the distributor in source " come into
The dephosphorization treatment of row iron liquid.Thereby, it is possible to eliminate through mixer etc. the trouble and cost that make mixed powder.In addition, due to
By being used separately distributor like this, to as described later, can simply control the type of the powder sprayed in blowing
And ratio, so being capable of the simply and efficiently low-phosphorous iron liquid of melting.
Then, each condition in the dephosphorization treatment for having used above-mentioned dephosphorization treatment device is illustrated.At dephosphorization
In reason, strongly inhibit in blowing spray slag (blistering clinker overflows or disperses from fire door), is set as [P] in iron liquid that treated
≤ 0.020 mass %.In order to find preferred condition thus, dephosphorization experiment has been carried out with various conditions to project below.
Duration of blast is set as general duration of blast i.e. 6~10 minute due to other process operationally closely related, and presses
Top blast oxygen flow is adjusted according to mode corresponding with the duration of blast of defined.Hereinafter, so-called " top blast oxygen flow " refers in blowing
Average top blast oxygen flow, also comprising adjusting top blast oxygen flow according to the bubblement of clinker and in the range of 0.8~1.2 times
The case where.In addition, " the Al in mixed powder2O3Concentration (Al2O3Ratio) " be set as (Al2O3Quality)/(CaO mass+CaCO3
Quality × 0.56+Al2O3Quality) × 100.
(1) top blast oxygen flow: 0.8~2.7Nm3/ minute/iron liquid ton is (hereinafter, the unit of gas feed speed is expressed as
Nm3/ minute/ton or Nm3/ minute/iron liquid ton)
(2) Bottom Blowing Gas Flow Rate: 0.08~0.7Nm3/ minute/iron liquid ton
(3) the loading basicity in terms of the only source CaO (includes at least Al to beginning to use2O3Loading alkali until the powder of powder
Degree): 0.7~1.3
(4) basicity is packed into from 0.8~1.2 to 1.4~2.7 CaO+Al2O3Al in mixed powder2O3Concentration: 3~25 matter
Measure %
(5) by before blowing or blowing after within 30 seconds be packed into converter in the source particulate CaO (partial size≤10mm) band
The loading basicity come: 0~0.5
(6) duration of blast in dephosphorization treatment: 6~10 minutes
(7) treated bonded hard ferrite magnet: 1300~1350 DEG C
(8) composition of iron liquid: [Si]: 0.4 mass %, [P]: 0.10 mass %
(9) iron liquid amount: 2 tons
Hereinafter, being illustrated based on condition specified in 2 couples of present invention of table 1 and table.It should be noted that in table 1 and table 2
[P] is the P concentration (quality %) of result obtained from being carried out continuously 5Ch test in each condition in iron liquid after the processing of record
Average value.In addition, the evaluation for the case where being 0.015 mass % or less and "None" spray slag by [P] in iron liquid after processing is set as
" ◎ ", by [P] is more than 0.015 mass % and 0.020 matter the case where producing slight spray slag or in treated iron liquid
The evaluation for measuring the situation of % or less is set as "○".So-called slight spray slag is the clinker degree slightly unrestrained from the fire door of converter
Continue the horizontal spray slag of no any obstacle to operation.
Table 1
Table 2
(1) No.1~3 of table 1 and No.31~32 of table 2
It is packed into iron liquid into combined blown converter, is 2.0Nm by top blowing oxygen flow set3/ minute/ton, by bottom blowing N2Flow is set
It is set to 0.25Nm3/ minute/ton, total oxygen supply amount during by since blowing until finishing blowing are set as
In the case where 100%, since blowing until the oxygen of 60% amount of injection, by top-blown spray gun only by the powder spray in the source CaO
It is mapped in iron liquid, CaO+Al is sprayed by top-blown spray gun later2O3Mixed powder (the Al in mixed powder2O3Concentration is 10 mass %), it will
The loading basicity in processing latter stage is set as 1.8.It should be noted that before treatment without the addition source particulate CaO.With above-mentioned item
Part makes to be packed into basicity in 0.7~1.3 variation by the powder bring in the source CaO of only top blast as primary condition.
Experiment as a result, be packed into basicity be lower than 0.8 in the case where, slight spray slag is produced in blowing.It can
Confirmation: if adding Al in the state that the basicity of molten slag is too low2O3Source (CaO+Al2O3Mixed powder), then the Al in clinker2O3
Concentration rises and clinker becomes easy blistering, generates slight spray slag.
In contrast, it is able to confirm that: since the FeO in clinker becomes easy by the C in iron liquid if being fitted into basicity and improving
Reduction, so clinker becomes not easy to foaming.In addition it is possible to confirm: due to clinker if the loading basicity in clinker improves
Dephosphorizing capacity also improves, so [P] concentration reduces in iron liquid after processing.But if being packed into basicity is more than 1.2, in clinker
FeO concentration excessively reduces, and the mobility of clinker reduces and Threshing injury reduces.As a result, being able to confirm that after processing in iron liquid
[P] can not be reduced to 0.015 mass % or less.
Be able to confirm that by above-mentioned result, by the powder bring in the source CaO of only top blast be packed into basicity be preferably 0.8~
1.2。
(2) No.4~7 of table 1 and No.33~34 of table 2
It is packed into iron liquid into combined blown converter, top blowing oxygen supply amount is set as 2.0Nm3/ minute/ton, by bottom blowing N2Flow
It is set as 0.25Nm3/ minute/ton, total oxygen supply amount during by since blowing until finishing blowing are set as
In the case where 100%, since blowing until the oxygen of 60% amount of injection, by top-blown spray gun only by the powder jetting in the source CaO
Into iron liquid, the powder in the above-mentioned source CaO is only loaded into basicity as 1.0 this part, sprays CaO+ by top-blown spray gun later
Al2O3The loading basicity for handling latter stage is set as 1.8 by mixed powder.It should be noted that before treatment without addition particulate CaO
Source.Using above-mentioned condition as primary condition, make the CaO+Al of top blast2O3Al in mixed powder2O3Concentration is in 3~25 mass %
Until change.
The result of experiment is able to confirm that, if the Al in mixed powder2O3Concentration is lower than 5 mass %, then after handling in iron liquid [P]
0.015 mass % can not be reduced to.It is considered that this is because: CaO ingredient in mixed powder point of origin (oxygen of top blast with
The high-temperature portion (2000 DEG C or more) of the collision of iron liquid bath face and generation) it melts and becomes not consumed by dephosphorisation reaction fully.?
Fe in point of origin iron liquid is aoxidized by top blowing oxygen and is generated FeO, and the powder body melting of institute's top blast is formed FeO-CaO in clinker
It is melt.However, since FeO is by the C reduction in iron liquid, so the FeO concentration in above-mentioned melt is easily reduced.Thus it is possible to
Think: since the fusing point of FeO-CaO melt rises and becoming to cannot keep flow regime, so the dephosphorization utilization efficiency of melt drops
It is low.In contrast, if in above-mentioned melt including Al2O3, then since the fusing point of melt significantly reduces, so becoming able to maintain
Molten condition and maintain dephosphorization utilization efficiency higher.However, the Al in mixed powder2O3When concentration is lower than 5 mass %, melt
Decreasing effect of melting point is small, less can be improved the dephosphorization efficiency of melt.
On the other hand, it is able to confirm that: if by the Al in mixed powder2O3Concentration is improved to more than 20 mass %, then due to rising
The mobility for the above-mentioned melt that fire point generates is very high, and the mobility of the blocky furnace slag around point of origin also excessively improves, so
Clinker becomes easy blistering and generates slight spray slag.
It is able to confirm that by above-mentioned result, the Al in mixed powder2O3Concentration is preferably 5~20 mass %.
(3) No.35~36 of the No.2 of table 1,8~10 and table 2
It is packed into iron liquid into combined blown converter, is 2.0Nm by top blowing oxygen flow set3/ minute/ton, by bottom blowing N2Flow is set
It is set to 0.25Nm3/ minute/ton, total oxygen supply amount during by since blowing until finishing blowing are set as
In the case where 100%, since blowing until the oxygen for 60~90% amounts of spraying, by top-blown spray gun only by the powder in the source CaO
It is ejected into iron liquid, the powder in the above-mentioned source CaO is only loaded into basicity as 1.0 this part, is sprayed later by top-blown spray gun
CaO+Al2O3Mixed powder (the Al in mixed powder2O3Concentration is 10 mass %), the loading basicity for handling latter stage is set as 1.8.
It should be noted that before treatment without the addition source particulate CaO.
The result of experiment is able to confirm that, if starting CaO+Al in the period of the oxygen of injection is lower than 50% amount2O3Mixed powder
Top blast, the then Al in this part of clinker2O3Concentration rises and clinker becomes easy blistering, generates slight spray slag.Another party
Face, if starting CaO+Al in the period of the amount of the oxygen of injection is more than 80%2O3The top blast of mixed powder, then after handling in iron liquid [P]
It is not reduced to 0.015 mass % or less.It is able to confirm that: if the powder in the source CaO is only carried out top blast, being unable to fully reduce iron
P concentration in liquid, but CaO+Al2O3It is too short when during the top blast of mixed powder lower than later half the 20% of blowing, iron liquid can not be made extremely low
Phosphatization.
It is able to confirm that by above-mentioned result, total oxygen supply amount during by since blowing until finishing blowing
In the case where being set as 100%, since blowing until the oxygen for 50~80% amounts of spraying, preferably start the top of mixed powder
It blows.
(4) No.37 of No.11~15 of table 1 and table 2
It is packed into iron liquid into combined blown converter, is 2.0Nm by top blowing oxygen flow set3/ minute/ton, by bottom blowing N2Flow is set
It is set to 0.25Nm3/ minute/ton, total oxygen supply amount during by since blowing until finishing blowing are set as
In the case where 100%, since blowing until the oxygen of 60% amount of injection, by top-blown spray gun only by the powder jetting in the source CaO
Into iron liquid, the powder in the above-mentioned source CaO is only loaded into basicity as 1.0 this part, sprays CaO+ by top-blown spray gun later
Al2O3Mixed powder (the Al in mixed powder2O3Concentration is 10 mass %), the loading basicity for handling latter stage is set as 1.4~2.5.
It should be noted that before treatment without the addition source particulate CaO.
The result of experiment is able to confirm that, if making the loading basicity for handling latter stage lower than 1.5, the dephosphorizing capacity of clinker is excessively
It is lower, [P] in iron liquid after processing can not be reduced to 0.015 mass % or less.In addition it is possible to confirm: due to last to blowing
Loading basicity until phase in clinker is low, so slag bloating is violent, generates slight spray slag in blowing latter stage.
On the other hand, though make handle latter stage loading basicity be more than 2, after processing in iron liquid [P] can not also be reduced to it is low
In 0.005 mass %.I.e., it is believed that: if the loading basicity in the clinker in processing latter stage is excessively improved, around point of origin
The mobility of blocky furnace slag is dramatically reduced, so [P] becomes to be not easy to reduce in iron liquid after processing.It should be noted that passing through
The loading basicity for improving processing latter stage, does not generate spray slag.
It being able to confirm that by above-mentioned result, the loading basicity for handling latter stage is preferably 1.5 or more, in addition, economically
Viewpoint is set out, and the upper limit for the loading basicity for handling latter stage is further preferably set as 2.
(5) No.16~18 of table 1 and No.38~39 of table 2
It is packed into iron liquid into combined blown converter, makes top blast oxygen flow in 0.8~2.7Nm3/ minute/ton variation, by bottom blowing N2
Flow set is 0.25Nm3/ minute/ton, total oxygen supply amount during by since blowing until finishing blowing are set
In the case where being set to 100%, since blowing until the oxygen of 60% amount of injection, by top-blown spray gun only by the powder in the source CaO
It is ejected into iron liquid, the powder in the above-mentioned source CaO is only loaded into basicity as 1.0 this part, is sprayed later by top-blown spray gun
CaO+Al2O3Mixed powder (the Al in mixed powder2O3Concentration is 10 mass %), the loading basicity for handling latter stage is set as 1.8.
It should be noted that before treatment without the addition source particulate CaO.
It is able to confirm that by the result tested, if being lower than 1.0Nm by top blowing oxygen flow set3/ minute/ton will then blow
In the case that the refining time is set as 6~10 minutes, [P] in iron liquid after processing is set as required for 0.015 mass % or less
Hypoxgia.On the other hand, it is able to confirm that: if improving top blast oxygen flow to more than 2.5Nm3/ minute/ton, the then Fe in iron liquid
By top blowing oxygen excessive oxidation, the FeO concentration in clinker is excessively improved and is blistered, and generates slight spray slag.In addition it is possible to really
Recognize: if top blast oxygen flow is excessive, the duration of blast existed until terminating to blow oxygen amount required for dephosphorization becomes too short, place
[P] becomes to be not easy to be reduced to 0.015 mass % tendency below in iron liquid after reason.
It is able to confirm that by above-mentioned result, top blast oxygen flow is preferably 1.0~2.5Nm3/ minute/ton.
(6) No.19~22 of table 1 and No.40~41 of table 2
It is 2.0Nm by top blowing oxygen flow set in the iron liquid being fitted into combined blown converter3/ minute/ton makes bottom blowing N2Stream
Amount is in 0.08~0.7Nm3/ minute/ton variation, total oxygen supply amount during by since blowing until finishing blowing
In the case where being set as 100%, since blowing until the oxygen of 60% amount of injection, by top-blown spray gun only by the powder in the source CaO
Body is ejected into iron liquid, and the powder in the above-mentioned source CaO is only loaded into basicity as 1.0 this part, is sprayed later by top-blown spray gun
Penetrate CaO+Al2O3Mixed powder (the Al in mixed powder2O3Concentration is 10 mass %), the loading basicity for handling latter stage is set as
1.8.It should be noted that before treatment without the addition source particulate CaO.
The result of experiment is able to confirm that, if by bottom blowing N2Flow set is lower than 1.0Nm3/ minute/ton, the then P in iron liquid
Substance movement speed significantly reduce, by the blowing of 6~10 minutes such short time, [P] in iron liquid after processing can not be dropped
Down to extremely low concentration i.e. 0.015 mass % or less.On the other hand, if being able to confirm that bottom blowing N2Flow is improved to being more than
0.6Nm3/ minute/ton, then iron liquid is mixed with clinker by excessive agitation, and the FeO concentration in clinker excessively reduces, and can not will be handled
[P] is reduced to 0.015 mass % or less in iron liquid afterwards.
It is able to confirm that by above-mentioned result, the bottom blowing N in blowing2Flow is preferably 0.1~0.6Nm3/ minute/ton.
(7) No.42 of No.23~24 of table 1 and table 2
It is packed into iron liquid into combined blown converter, is equivalent to this portion for being packed into basicity 0~0.5 by hopper addition before blowing
The partial size divided is the source 10mm particulate CaO below.Later, start to blow, be 2.0Nm by top blowing oxygen flow set3/ minute/ton,
By bottom blowing N2Flow set is 0.25Nm3/ minute/ton, total oxygen during by since blowing until finishing blowing supply
In the case where being set as 100% to amount, since blowing until the oxygen of 60% amount of injection, by top-blown spray gun only by the source CaO
Powder jetting into iron liquid, the powder in the above-mentioned source CaO be only loaded into basicity (in this case, CaO charge weight be particulate CaO with
CaO's in powder is total) as 1.0 this part, CaO+Al is sprayed by top-blown spray gun later2O3Mixed powder is (in mixed powder
Al2O3Concentration is 10 mass %), the loading basicity for handling latter stage is set as 1.8.
The result of experiment is able to confirm that the additive amount to the source particulate CaO is to be equivalent to this part for being packed into basicity 0.39
Until, it is sufficiently melted in blowing and can aid in dephosphorization, [P] is reduced to 0.015 mass % or less in iron liquid after processing.
Blowing initially generates SiO due to sharp carrying out desilication reaction by top blowing oxygen gas in large quantities in clinker2, it is possible to it says
Particulate CaO is easy fusing.Due to the situation, in the case where adding particulate CaO within from blowing 30 seconds, particulate CaO
Source is also easy fusing, and same effect can be obtained.
But, additionally it is possible to confirm: if the additive amount in the source particulate CaO is set as to be equivalent to this portion for being packed into basicity 0.4
Point or more, then a part in the source particulate CaO becomes unfused, generates slightly in the blowing practical basicity reduction of clinker on the way
Spray slag.It is considered that: in the case where the source CaO to be made powder and be ejected into iron liquid bath face together with top blast oxygen, rising
The powder in the fire source point CaO promptly melts, and the practical basicity of clinker rises, but sometimes the source particulate CaO also in blowing intial detention
Few with the touch opportunity of the FeO system melt generated in point of origin near furnace wall, fusing needs the long time.
It is able to confirm that by above-mentioned result, by being added before 30 seconds into converter before blowing starts or from blowing
In the case where the source 10mm particulate CaO below more cheap than the powder in the source CaO, preferably addition just corresponds to be packed into basicity lower than 0.4
This part the source particulate CaO.
Embodiment
Then, the present invention is further illustrated based on embodiment, but the condition in embodiment is to confirm this hair
Bright exploitativeness and effect and the condition example used, the present invention is not limited to this condition examples.Without departing from this hair
Bright purport and reach the purpose of the present invention, then various conditions can be used in the present invention.
(embodiment 1)
Into combined blown converter, 280 tons of loading has [Si]: 0.4 mass %, [P]: the iron of the composition of 0.10 mass %
Liquid.Then on one side from bottom blowing air port into iron liquid with flow 0.25Nm3/ minute/ton is blown into nitrogen and is stirred iron liquid, one
Side uses one, distributor for maintaining the powder that maximum particle diameter is the source CaO below 1mm and maintains and mixes in the powder in the source CaO
The Al of 10 mass %2O3Maximum particle diameter obtained from the powder in source is 1mm powder ((Al below2O3Quality)/(CaO mass+CaCO3
Quality × 0.56+Al2O3Quality) × 100=10%, it is shown as (CaO+10%Al below2O3) mixed powder) and one quilt of distributor
The dephosphorization treatment device being connected on top blast oxygen pipeline, by top-blown spray gun and oxygen 2.0Nm3/ minute/ton together, will be from
In the case that the total oxygen supply amount during starting until finishing blowing that blows is set as 100%, to spray since blowing
Until the oxygen for penetrating 75% amount, only the powder in the source CaO is ejected into iron liquid by maintaining the distributor of powder in the source CaO, above-mentioned CaO
The powder in source is only loaded into basicity as 1.0 this part, later by maintaining (CaO+10%Al2O3) mixed powder distributor
Only spray (CaO+10%Al2O3) mixed powder, the loading basicity for handling latter stage is set as 1.8.Duration of blast is 7 minutes, blowing
The bonded hard ferrite magnet in latter stage is 1342 DEG C, and [P] is 0.012 mass % in iron liquid after processing.In addition, without generating spray in blowing
Slag.
(embodiment 2)
Into combined blown converter, 280 tons of loading has [Si]: 0.4 mass %, [P]: the iron of the composition of 0.10 mass %
Liquid.Later, the maximum particle diameter that addition is equivalent to this part for being packed into basicity 0.3 before blowing starts is 10mm particulate below
The source CaO.Then on one side from bottom blowing air port into iron liquid with flow 0.25Nm3/ minute/ton is blown into nitrogen and stirs iron liquid
It mixes, using one, distributor for maintaining the powder that maximum particle diameter is the source CaO below 1mm and maintains maximum particle diameter on one side and be
1mm Al below2O3One, distributor of the powder in source is connected to different from the supply pipeline of oxygen sprayed by top-blown spray gun
Dephosphorization apparatus on nitrogen pipeline, by top-blown spray gun and oxygen 2.0Nm3/ minute/ton together, will be since blowing to blowing
In the case that total oxygen supply amount during until end is set as 100%, to the oxygen of 75% amount of injection since blowing
Until, only the powder in the source CaO is ejected into iron liquid by maintaining the distributor of powder in the source CaO, the powder in the above-mentioned source CaO is only loaded into
This part that basicity (CaO charge weight is the total of the CaO in the source particulate CaO and the source powder CaO) becomes 1.0, later by protecting
Hold the distributor of the powder in the source CaO and maintains Al2O3The distributor of the powder in source becomes according to the powder sprayed by top-blown spray gun
(CaO+10%Al2O3) mode (in gas line carry out then mix) of mixed powder sprayed, the loading alkali in latter stage will be handled
Degree is set as 1.8.Duration of blast is 7 minutes, and the bonded hard ferrite magnet in latter stage of blowing is 1344 DEG C, and [P] is 0.012 in iron liquid after processing
Quality %.In addition, without generating spray slag in blowing.
(embodiment 3)
Into combined blown converter, 280 tons of loading has [Si]: 0.4 mass %, [P]: the iron of the composition of 0.10 mass %
Liquid.Later, the maximum particle diameter that addition is equivalent to this part for being packed into basicity 0.3 before blowing starts is 10mm particulate below
The source CaO.Then on one side from bottom blowing air port into iron liquid with flow 0.25Nm3/ minute/ton is blown into nitrogen and stirs iron liquid
It mixes, using one, distributor for maintaining the powder that maximum particle diameter is the source CaO below 1mm and maintains maximum particle diameter on one side and be
1mm Al below2O3One, distributor of the powder in source is connected to different from the supply pipeline of oxygen sprayed by top-blown spray gun
Dephosphorization apparatus on nitrogen pipeline, by top-blown spray gun and oxygen 2.0Nm3/ minute/ton together, will be since blowing to blowing
In the case that total oxygen supply amount during until end is set as 100%, to the oxygen of 60% amount of injection since blowing
Until, only the powder in the source CaO is ejected into iron liquid by maintaining the distributor of powder in the source CaO, the powder in the above-mentioned source CaO is only loaded into
This part that basicity (CaO charge weight is the total of the CaO in the source particulate CaO and the source powder CaO) becomes 1.0, later by protecting
Hold the distributor of the powder in the source CaO and maintains Al2O3The distributor of the powder in source becomes according to the powder sprayed by top-blown spray gun
(CaO+10%Al2O3) mode (in gas line carry out then mix) of mixed powder sprayed, the loading alkali in latter stage will be handled
Degree is set as 1.8.Duration of blast is 7 minutes, and the bonded hard ferrite magnet in latter stage of blowing is 1350 DEG C, and [P] is 0.006 in iron liquid after processing
Quality %.In addition, without generating spray slag in blowing.
(embodiment 4)
Into combined blown converter, 280 tons of loading has [Si]: 0.4 mass %, [P]: the iron of the composition of 0.10 mass %
Liquid.Then on one side from bottom blowing air port into iron liquid with flow 0.25Nm3/ minute/ton is blown into nitrogen and is stirred iron liquid, one
It is 1mm or less that side, which uses one, the distributor for maintaining the powder that maximum particle diameter is the source CaO below 1mm and maintains maximum particle diameter,
Al2O3One, distributor of the powder in source is connected to the nitrogen tube different from the supply pipeline of oxygen sprayed by top-blown spray gun
Dephosphorization apparatus on line, by top-blown spray gun and oxygen 2.0Nm3/ minute/ton together, will be to finishing blowing since blowing
In the case that total oxygen supply amount during only is set as 100%, since blowing until the oxygen of 60% amount of injection, by
The powder in the source CaO is only ejected into iron liquid by the distributor for maintaining the powder in the source CaO, the powder in the above-mentioned source CaO be only loaded into basicity at
It is a part of for this of 1.3, later by maintaining the distributor of the powder in the source CaO and maintaining Al2O3The distributor of the powder in source, according to
(CaO+10%Al is become by the powder of top-blown spray gun injection2O3) mixed powder mode (in gas line carry out then mix) into
Row injection, is set as 1.8 for the loading basicity for handling latter stage.Duration of blast is 7 minutes, and the bonded hard ferrite magnet in latter stage of blowing is 1345
DEG C, [P] is 0.016 mass % in iron liquid after processing.In addition, without generating spray slag in blowing.
(comparative example 1)
Into combined blown converter, 280 tons of loading has [Si]: 0.4 mass %, [P]: the iron of the composition of 0.10 mass %
Liquid.Then on one side from bottom blowing air port into iron liquid with flow 0.25Nm3/ minute/ton is blown into nitrogen and is stirred iron liquid, one
While one, distributor that has been loaded into the powder that maximum particle diameter is the source CaO below 1mm is connected on oxygen pipeline, by top-blown spray gun
With oxygen 2.0Nm3/ minute/ton sprays the powder in the source CaO since blowing until latter stage of blowing into iron liquid together, will handle
The loading basicity in latter stage is set as 1.8.Duration of blast is 7 minutes, and the bonded hard ferrite magnet in latter stage of blowing is 1344 DEG C, iron liquid after processing
In [P] be 0.025 mass %.In addition, without generating spray slag in blowing.In this example embodiment, since distributor is one, so
It is not available Al2O3The powder in source, therefore dephosphorization utilization efficiency can not be improved.
(comparative example 2)
Into combined blown converter, 280 tons of loading has [Si]: 0.4 mass %, [P]: the iron of the composition of 0.10 mass %
Liquid.Then on one side from bottom blowing air port into iron liquid with flow 0.25Nm3/ minute/ton is blown into nitrogen and is stirred iron liquid, one
While being loaded into, the maximum particle diameter of 10 mass % is mixed in the powder that maximum particle diameter is the source CaO below 1mm is 1mm below
Al2O3One, distributor of mixed powder obtained from the powder in source is connected on oxygen pipeline, by top-blown spray gun and oxygen 2.0Nm3/
Since minute/ton spray mixed powder into iron liquid until latter stage of blowing blowing, the loading basicity for handling latter stage is set together
It is set to 1.8.Duration of blast is 7 minutes, and the bonded hard ferrite magnet in latter stage of blowing is 1340 DEG C, and [P] is 0.010 matter in iron liquid after processing
% is measured, but produces spray slag in blowing.In this example embodiment, in order to reduce [P] and from blowing initially spray
Mixed powder is penetrated, but since distributor is one, so can only be from blowing initially injection mixed powder, therefore the clinker in blowing
Al2O3Concentration rises and clinker becomes easy blistering, generates spray slag.
Industrial availability
According to the present invention, due to be capable of providing by dephosphorization treatment can inexpensively the low-phosphorous iron liquid of melting dephosphorization treatment dress
The dephosphorization method of the iron liquid of dephosphorization treatment device is set and has used, so industrial value is big.
Claims (4)
1. a kind of dephosphorization treatment device, which is characterized in that it is the dephosphorization treatment device for carrying out the dephosphorization treatment of iron liquid, tool
Have:
Converter；
Top-blown spray gun, the top-blown spray gun are blown into oxygen into the converter；
1st gas line, the 1st gas line supply the oxygen into the top-blown spray gun；
1st distributor, the 1st distributor maintain the source CaO sprayed together with the oxygen by the top-blown spray gun；With
2nd distributor, the 2nd distributor at least maintain the Al sprayed together with the oxygen by the top-blown spray gun2O3Source.
2. dephosphorization treatment device according to claim 1, which is characterized in that it further has and the 1st flue
The 2nd different gas line of line, the 2nd gas line is by the source CaO and the Al2O3Source mixes and is supplied to the top blast
In spray gun.
3. a kind of dephosphorization method of iron liquid, which is characterized in that it is to have used dephosphorization treatment device of any of claims 1 or 2
Iron liquid dephosphorization method, wherein
Iron liquid is packed into the converter, on one side from bottom blowing air port by nitrogen with 0.1~0.6Nm3/ minute/ton flow is blown into institute
It states in iron liquid and is stirred, on one side by the top-blown spray gun and 1.0~2.5Nm3The oxygen of/minute/ton flow together,
By since blowing until finishing blowing during total oxygen supply amount be set as 100% in the case where, opened from blowing
During beginning until the oxygen for 50~80% amounts of spraying, the source CaO being held in the 1st distributor is only ejected into iron liquid
In, the source CaO is only loaded into basicity as 0.8~1.2 this part, later by the top-blown spray gun and the oxygen one
Playing only injection and being held in the 2nd distributor includes Al2O3The mixed powder in source, Al in the mixed powder2O3Ratio
((Al2O3Quality)/(CaO mass+CaCO3Quality × 0.56+Al2O3Quality) × 100) it is 5~20 mass %, or injection is protected
The source CaO being held in the 1st distributor and the Al being held in the 2nd distributor2O3The mixed powder in source, the mixed powder
Middle Al2O3Ratio be 5~20 mass %, the loading basicity for handling latter stage is set as 1.5 or more, duration of blast is set as 6
~10 minutes.
4. the dephosphorization method of iron liquid according to claim 3, which is characterized in that before blowing starts or blowing start after 30
Within second, addition just corresponds to be packed into the maximum particle diameter of this part of basicity lower than 0.4 to be the source 10mm particulate CaO below,
By since blowing until finishing blowing during total oxygen supply amount be set as 100% in the case where, from blowing
During starting until the oxygen for 50~80% amounts of spraying, only the source CaO is ejected into iron liquid, the source CaO is only
Be packed into basicity and the addition the source particulate CaO it is total as 0.8~1.2 this part, later by the top-blown spray gun with
The oxygen sprays the mixed powder together, with the total loading basicity setting that will handle latter stage in the source particulate CaO of the addition
It is 1.5 or more.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017-001164 | 2017-01-06 | ||
| JP2017001164 | 2017-01-06 | ||
| PCT/JP2017/046788 WO2018128135A1 (en) | 2017-01-06 | 2017-12-26 | Dephosphorization apparatus and method for dephosphorizing hot metal using dephosphorization apparatus |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109715833A true CN109715833A (en) | 2019-05-03 |
| CN109715833B CN109715833B (en) | 2021-02-26 |
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ID=62789362
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| CN201780058172.6A Active CN109715833B (en) | 2017-01-06 | 2017-12-26 | Dephosphorization apparatus and dephosphorization method for molten iron using same |
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| Country | Link |
|---|---|
| JP (1) | JP6642739B2 (en) |
| KR (1) | KR102164138B1 (en) |
| CN (1) | CN109715833B (en) |
| TW (1) | TWI649427B (en) |
| WO (1) | WO2018128135A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112094980A (en) * | 2020-08-18 | 2020-12-18 | 北京科技大学 | System and method for efficient smelting of converter through top-bottom composite powder injection |
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- 2017-12-26 JP JP2018560381A patent/JP6642739B2/en active Active
- 2017-12-26 CN CN201780058172.6A patent/CN109715833B/en active Active
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| CN112094980A (en) * | 2020-08-18 | 2020-12-18 | 北京科技大学 | System and method for efficient smelting of converter through top-bottom composite powder injection |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102164138B1 (en) | 2020-10-12 |
| WO2018128135A1 (en) | 2018-07-12 |
| KR20190029661A (en) | 2019-03-20 |
| JPWO2018128135A1 (en) | 2019-06-27 |
| CN109715833B (en) | 2021-02-26 |
| TWI649427B (en) | 2019-02-01 |
| JP6642739B2 (en) | 2020-02-12 |
| TW201829789A (en) | 2018-08-16 |
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