CN109073575A - The analysis method of clinker and the method for refining of molten iron - Google Patents

The analysis method of clinker and the method for refining of molten iron Download PDF

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CN109073575A
CN109073575A CN201780022352.9A CN201780022352A CN109073575A CN 109073575 A CN109073575 A CN 109073575A CN 201780022352 A CN201780022352 A CN 201780022352A CN 109073575 A CN109073575 A CN 109073575A
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clinker
molten iron
refining
analysis
furnace
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CN109073575B (en
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猪濑匡生
石田智治
城代哲史
山田克美
小笠原泰志
前田孝彦
涩田直哉
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JFE Steel Corp
JFE Engineering Corp
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NKK Corp
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
    • 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
    • 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
    • C21C1/04—Removing impurities other than carbon, phosphorus or sulfur
    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
    • G01N23/223—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
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  • Analysing Materials By The Use Of Radiation (AREA)
  • Carbon Steel Or Casting Steel Manufacturing (AREA)

Abstract

The present invention provides a kind of analysis method of the clinker of composition that can rapidly and accurately measure the clinker generated in the refining of molten iron.The analysis method of clinker of the invention is a kind of analysis method of clinker generated in the refining of molten iron, has following process: the process that the clinker sample acquired from clinker is crushed；10% partial size (the D for being zero with the side of thin particle and in the curve that rises to the right and the cumulative grain-size distribution curve indicated with quality percentage will be made up of the size distribution of the clinker particle of sieve from acquiring in the clinker particle of crushing10) it is 0.1mm or more and 90% partial size (D90) be 2.0mm clinker particle below process；By the particle-filled process to measurement container of clinker collected；The process for measuring the fluorescent X-ray intensity from the clinker particle group filled；And the fluorescent X-ray intensity by being measured to forms the process for carrying out quantitative analysis to clinker.

Description

The analysis method of clinker and the method for refining of molten iron
Technical field
The present invention relates to a kind of for rapidly and accurately measuring the composition of the clinker generated in the refining of molten iron Clinker analysis method, and be related to a kind of composition analysis result based on the analysis method to determine adding for slag former appropriate The method of refining of the molten iron of dosage.Here, molten iron indicates molten iron or molten steel, when the difference of molten iron or molten steel is clear, note Carry is molten iron or molten steel.
Background technique
In recent years, from discharge limitation for needing to take into account carbon dioxide gas etc. to the care of environment and it is large-duty in terms of Consider, has developed the preconditioning technique of various molten iron and the carbonization treatment technology of molten iron.Wherein, it is pre-processed as new molten iron One of technology proposes a kind of 1 converter type refining furnace of use, clips the deslagging process of midway and continuously carry out the de- of molten iron The Liquid Iron Pretreatment Technology of silicon processing and dephosphorization treatment.
For example, proposing following Liquid Iron Pretreatment Technology in patent document 1: firstly, with the basicity of clinker (basicity= (quality %CaO)/(quality %SiO2)) fall into 0.3~1.3 in the range of mode adjust the additive amount of CaO system fluxing agent, In converter type refining furnace carry out desiliconization processing, thereafter, make converter type refining furnace tilt and by the clinker generated in furnace (at desiliconization The clinker generated in reason is known as " desiliconization clinker ") it is discharged from fire door, then, CaO system fluxing agent is added, remain in furnace The dephosphorization treatment of molten iron.
Wherein, generally, the SiO that the basicity reason desiliconization processing of clinker when desiliconization is handled generates2And change, therefore The basicity that clinker is likely to occur in patent document 1 is detached from above range and is difficult to that the feelings of clinker are discharged in the deslagging of midway Condition.In addition, in patent document 1, in dephosphorization treatment heel row slag discharging, though seldom but still molten iron, the molten iron are remained in furnace Also it is discharged together with clinker, leads to the reduction of iron yield rate.
In addition, about the carbonization treatment by cast iron melting molten steel, it is also proposed that use 1 converter type refining furnace, clip The deslagging process on way and continuously carry out the dephosphorization treatment of molten iron and the processing technique of carbonization treatment.
For example, proposing following refining techniques in patent document 2: 1 converter type refining furnace is used, firstly, carrying out iron The dephosphorization treatment of water then makes tilting furnace and clinker generated is discharged, and thereafter, carries out the de- of the molten iron remained in furnace Carbon processing.It, will to remain the state of the clinker generated in carbonization treatment by the molten steel of melting after the tapping of converter type refining furnace Next time, the molten iron of charging was encased in converter type refining furnace, carry out in the order described above the molten iron of next charging dephosphorization treatment and Carbonization treatment.According to patent document 2, by intentionally remaining the clinker after carbonization treatment, subtracting for CaO system fluxing agent can be realized Less, the raising of iron yield rate, clinker in low temperature and dephosphorization treatment in dephosphorization treatment low alkalinity.It should be noted that such as The deslagging carried out between 2 refinings in patent document 1 and 1 converter type disclosed Patent Document 2 refining is also referred to as " intermediate deslagging ", " intermediate deslagging process ".
However, in patent document 1 and patent document 2, in intermediate deslagging process, by tilting converter type refining furnace And the clinker in furnace is discharged, but when only tilting converter type refining furnace, because of the composition of clinker, be unable to fully discharge clinker.Therefore, In patent document 1 and patent document 2, it is possible to be influenced by the clinker remained in converter type refining furnace and generate rephosphorization Etc. undesirable phenomenon.Here, " rephosphorization " refers to the phosphorous oxides (P contained in clinker2O5) reduction and phosphorous oxides in phosphorus turn The phenomenon that moving to molten iron or molten steel and increase the phosphorus concentration of molten iron or molten steel.
In this context, following technology is proposed in patent document 3: being taken off using 1 converter type refining furnace When phosphorus processing, intermediate deslagging process, carbonization treatment, for the purpose for sufficiently carrying out deslagging in the intermediate deslagging process of midway, It is blown into non-active gas from the air port for the bosh for being set to converter type refining furnace, makes clinker on one side to fire door using non-active gas Side movement is discharged on one side.
In addition, proposing following technology in patent document 4: being made in the dephosphorization treatment of molten iron using 1 converter type refining furnace A part residual of the clinker of generation and when carrying out the dephosphorization treatment of the molten iron of next charging, for make to generate in dephosphorization treatment The specified amount of clinker remains on the purpose in furnace, the pass of the residual quantity of the tilt angle and clinker of measured in advance converter type refining furnace System, makes tilting furnace based on the measurement result and remains the clinker of specified amount.
However, the composition for understanding clinker is that conditio sune qua non widely carries out when carrying out the refining of molten iron in the past Utilize the quantitative analysis of the intensity of fluorescent X-ray.The quantitative approach for utilizing the clinker of fluorescent x-ary analysis to form is as follows. That is, a part of acquisition clinker, is transported to analysis room for the clinker of acquisition and is prepared into assay sample, thereafter, to prepared Assay sample X-ray irradiation (primary X-ray), the fluorescent X-ray generated to each element measurement by assay sample is (secondary X-ray) intensity, each element is found out by the measured value of fluorescent X-ray intensity using the standard curve of ready-made each element Content.
In fluorescent x-ary analysis, in order to be quantified with high precision, need to make the aspect of measure of assay sample flat It is sliding.As the preparation method of assay sample thus, it is substantially carried out this 3 kinds of glass bead method, briquetting method, direct method.
Glass bead method is by clinker Na collected2B4O7、Li2B4O7Equal flux melting and vitrifying simultaneously will be vitrified Method of the substance as assay sample.The assay sample obtained by glass bead method rich in homogenieity, can accurately into Row analysis.But until understanding fully assay value, 1 hour or so long-time is needed, therefore can not feed back to operation.
Briquetting method is that the clinker of crushing is mixed and is press-formed into organic systems binders such as a small amount of starch, celluloses Discoid preparation method of sample.Although the analysis carried out using briquetting method analysis precision compared with glass bead method is poor, have The advantages of sample preparation time capable of being shorten to about half.
Patent document 5 proposes following method: shortening analysis time for analysis precision is not reduced in briquetting method Purpose, using jet mill by clinker ultramicron to 10 μm of average grain diameter hereinafter, by the ultramicron binder free shape It is press-formed into discoid under state and is analyzed.It is 10 points that the average analysis time is described in the embodiment of patent document 5 The content of clock.
Direct method is the method by the clinker coupons of acquisition with the state kept intact for fluorescent x-ary analysis, It is able to carry out the analysis of the short time of or so a few minutes.But smooth aspect of measure is needed in fluorescent x-ary analysis, because This, smooth aspect of measure, patent document 6 and patent document 7 propose and are pressed into sampler simultaneously into the clinker of melting in order to obtain Clinker is quenched using sampler and acquires the method with the clinker coupons of even surface.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 10-152714 bulletin
Patent document 2: Japanese Unexamined Patent Publication 4-72007 bulletin
Patent document 3: Japanese Unexamined Patent Publication 5-140627 bulletin
Patent document 4: Japanese Unexamined Patent Publication 6-200311 bulletin
Patent document 5: Japanese Unexamined Patent Publication 11-23496 bulletin
Patent document 6: Japanese Unexamined Patent Publication 9-166589 bulletin
Patent document 7: Japanese Unexamined Patent Publication 11-304675 bulletin
Summary of the invention
The inventors of the present invention confirmed to implement to remain on furnace in the converter type refining furnace using a part for remaining clinker The refining of the subsequent processing of interior molten iron or using the molten iron that is newly encased in furnace charging next time molten iron refining In the case of, basicity ((quality %CaO)/(matter of clinker is difficult to control in the refining of refining or charging next time of subsequent processing Measure %SiO2)).I.e., it is thus identified that be not easy to add the CaO system fluxing agent of appropriate amount.Generally, by the way that the basicity control of clinker exists 1.20 or so, dephosphorization treatment appropriate can be carried out to molten iron, but the CaO system fluxing agent for adding necessary amount or more will lead to cost Increase.
That is, in the above-mentioned method of refining of the molten iron proposed so far, in order to be further reduced cost, need by The additive amount of the slag formers such as CaO system fluxing agent is suppressed to the amount of required bottom line.Moreover, in order to realize the purpose, needing standard Really hold the composition and residual quantity of the clinker in the furnace before adding slag former.For example, in patent document 1, at desiliconization When adding CaO system fluxing agent after the deslagging after reason, in order to calculate the additive amount of CaO system appropriate fluxing agent, need to hold residual In the basicity of the clinker in furnace and the residual quantity of clinker.
Patent document 4 remains on the clinker of specified amount in furnace, but by tilt angle when molten iron is not present in furnace Clinker residual quantity is found out with the relationship of clinker residual quantity.As the intermediate deslagging process of patent document 1 or patent document 2, There are when molten iron in furnace, the iron water amount itself in furnace changes, so even using the technology of patent document 4, it also can not be accurate Hold the clinker residual quantity in furnace in ground.
On the other hand, as the method for accurately evaluating the composition of residual clinker in furnace, method disclosed in Patent Document 5 Since it is desired that proceeding to the horizontal crushing that can be press-formed, so being difficult to terminate analysis use before intermediate deslagging process terminates The preparation of sample.In addition, method disclosed in patent document 6,7, because being quenched to clinker, assay sample is easy Segregation is generated, there are problems on analysis precision.As described previously for the side for the composition for remaining clinker in accurately analytical furnace Method does not find detailed record in the past patent document including Patent Documents 1 to 7.
Therefore, it usually carries out forming the method estimated to clinker by calculating.But due to so that the clinker generated Part or all remain on the state in furnace carry out subsequent processing refining or next time charging molten iron refining, therefore For method based on calculating, the precision of the clinker composition or slag amount estimated is reduced.Therefore, actual clinker It forms the deviation with calculated value to become larger, it is possible to sink into be difficult to be carried out continuously the pretreated situation of molten iron.
In addition, further relating to many-sided demand for learning clinker composition rapidly other than basicity.Such as the MgO in clinker The refractory material service life of concentration and furnace body is closely related.Its reason is: if the MgO concentration in clinker is too low, furnace wall fire resisting The damage of object becomes obvious.On the other hand, if the MgO concentration in clinker is excessively high, Waste Slag is used for roadbed material etc. When generate expansion etc. worry, it is thus not preferred.Therefore, the MgO concentration in clinker has range appropriate, it is expected that carrying out rapid The analysis of clinker composition.As long as MgO concentration in clinker can promptly be evaluated in refining procedure, not only by appropriate The control of MgO concentration and the extension for realizing converter life, and assuming that being biased to high concentration side, can by with can The differentiation of the clinker of recycling and the raising for being related to productivity.
Present invention is made in view of the above circumstances, and its purpose is to provide can rapidly and accurately measure molten Melt the analysis method of the clinker of the composition of the clinker generated in the refining of iron, additionally, it is provided a kind of point according to using the clinker Result is analyzed obtained from analysis method to determine the method for refining of the molten iron of the additive amount of slag former appropriate.
The gist of the invention in order to solve the above problems is as follows.
[1] a kind of analysis method of clinker is the analysis method of the clinker generated in the refining of molten iron, is had as follows Process:
The process that the clinker sample acquired from clinker is crushed；
It is acquired from the clinker particle of crushing and the size distribution of the clinker particle by sieve is made with thin particle Side be zero and the curve that rises to the right and the cumulative grain-size distribution curve indicated with quality percentage in 10% partial size (D10) For 0.1mm or more and 90% partial size (D90) be 2.0mm clinker particle below process；
By the particle-filled process to measurement container of clinker collected；
The process that fluorescent X-ray intensity from the clinker particle group filled is measured；And
The process for carrying out quantitative analysis is formed to clinker by the fluorescent X-ray intensity being measured to.
[2] analysis method of the clinker according to above-mentioned [1], wherein in the process for measuring above-mentioned fluorescent X-ray intensity In the fluorescent X-ray intensity of the element of more than two kinds comprising calcium (Ca) and silicon (Si) is measured.
[3] a kind of method of refining of molten iron, so that clinker caused by the refining of the molten iron in converter type refining furnace A part remain on the state of above-mentioned converter type refining furnace and carry out the next of the molten iron for remaining on above-mentioned converter type refining furnace The refining of process or the refining of the next molten iron to charge using the molten iron for being newly encased in above-mentioned converter type refining furnace,
Analysis method using the clinker recorded in above-mentioned [1] or above-mentioned [2] is upper to what is generated in the refining of molten iron The composition for stating clinker carries out quantitative analysis,
According to its analysis as a result, determine carried out in the above-mentioned converter type refining furnace for remaining clinker, remain in furnace Molten iron subsequent processing refining or using the molten iron being newly encased in furnace next time charging molten iron refining essence The amount of the slag former added before refining and/or in refining.
[4] method of refining of the molten iron according to above-mentioned [3], wherein the refining of above-mentioned molten iron is turned using 1 Type of furnace refining furnace carries out multiple refining procedures to molten iron and between multiple refining procedure so that a part of molten iron and clinker The pretreatment of molten iron for remaining on the remainder of the state discharge clinker of above-mentioned converter type refining furnace and carrying out,
The composition of above-mentioned clinker is analyzed in the discharge of the remainder of above-mentioned clinker,
According to its analysis as a result, determining the amount of the slag former added in the refining procedure of subsequent processing.
[5] method of refining of the molten iron according to above-mentioned [3], wherein the refining of above-mentioned molten iron is turned using 1 Type of furnace refining furnace carries out pretreated refining to molten iron,
Molten iron pre-processes so that part or all of the clinker generated remains on the state of above-mentioned converter type refining furnace Pretreated molten iron is discharged and is newly packed into molten iron into furnace and implements the pretreatment of next charging,
When part or all of above-mentioned clinker being made to remain on above-mentioned converter type refining furnace, to the composition of remaining clinker into Row analysis,
According to its analysis as a result, determining the amount of the slag former added in the pretreatment of charging next time.
[6] a kind of method of refining of molten iron carries out following processes according to following sequences using 1 converter type refining furnace And molten iron is implemented to pre-process, there is following process:
Desiliconization treatment process carries out desiliconization processing to from the molten iron of blast furnace casting,
Intermediate deslagging process, so that the state that the molten iron handled through desiliconization remains in above-mentioned converter type refining furnace will be by upper The desiliconization clinker for stating the generation of desiliconization treatment process is discharged from above-mentioned converter type refining furnace,
Dephosphorization treatment process carries out dephosphorization treatment to the molten iron for remaining on above-mentioned converter type refining furnace, and
Molten iron through dephosphorization treatment is discharged molten iron discharging process from above-mentioned converter type refining furnace；
Wherein, in above-mentioned intermediate deslagging process, using the analysis method for the clinker recorded in above-mentioned [2] to desiliconization clinker Composition carry out quantitative analysis,
Basicity ((quality %CaO)/(quality %SiO of desiliconization clinker is found out according to its analysis result2)),
According to basicity ((quality %CaO)/(the quality %SiO found out2)) determine to add in above-mentioned dephosphorization treatment process The amount of the slag former added.
[7] method of refining of the molten iron according to any one of above-mentioned [3]~[6], wherein above-mentioned slag former is CaO system fluxing agent.
[8] method of refining of the molten iron according to any one of above-mentioned [3]~[7], wherein fluxing using MgO system The a part of agent as above-mentioned slag former,
The analysis result of above-mentioned clinker includes the content of MgO in clinker,
The additive amount of above-mentioned MgO system fluxing agent is determined according to the analysis result of above-mentioned clinker.
[9] method of refining of the molten iron according to any one of above-mentioned [3]~[8], wherein helped using iron oxide The a part of flux as above-mentioned slag former,
The analysis result of above-mentioned clinker includes the iron oxide content in clinker,
The additive amount of above-mentioned iron oxide fluxing agent is determined according to the analysis result of above-mentioned clinker.
According to the present invention, using by 10% partial size (D in cumulative grain-size distribution curve10) it is 0.1mm or more and 90% Diameter (D90) it is that the clinker of 2.0mm partial size below particle-filled uses material obtained by container as x-ray fluorescence analysis to measurement Assay sample in method, therefore can rapidly and accurately the composition to the clinker generated in the refining of molten iron carry out Quantitative analysis.In addition, so that part or all of the clinker generated in the refining of molten iron remains on converter type refining furnace State using the converter type refining furnace carry out molten iron subsequent processing refining or next time charging molten iron refining when, As determining the additive amount of slag former according to result is analyzed obtained from the analysis method of clinker of the invention, can determine Determine the additive amount appropriate of slag former.
Detailed description of the invention
Fig. 1 is the figure of the partial size for indicating clinker particle and the relationship of basicity of slag measured value.
Fig. 2 is the basicity of the desiliconization clinker found out by slag assay method of the invention to be indicated in a manner of comparing and by benefit The figure of the basicity for the desiliconization clinker that the assay value of the assay sample prepared by briquetting method is found out.
Fig. 3 is to indicate that being discharged to molten iron receiving after dephosphorization treatment in example 1 of the present invention and comparative example 1 holds in a manner of comparing The figure of phosphorus concentration in the molten iron of device.
Specific embodiment
The inventors of the present invention in order to solve the above problems, study the shortening of the analysis time of clinker, Jin Erzhen It is applied to the refining of subsequent processing to the clinker generated including intentionally remaining the refining by molten iron and by remaining clinker Or the refining procedure of the molten iron of the process of the refining of the molten iron of charging next time, detailed survey its feature, environment.As a result, conduct Solve the means of the above subject, it was found that promptly refine the furnace generated to by molten iron in the machine side of converter type refining furnace The method that the composition of slag carries out quantitative analysis.Here, it " intentionally remains clinker " and refers to without by the furnace of converter type refining furnace Mouth operates the deslagging of converter type refining furnace handstand towards underface, adjusts the tilt angle of converter type refining furnace and furnace is discharged Slag simultaneously remains in clinker in furnace.
That is, for example, as disclosed in Patent Document 1, the desiliconization after treatment in molten iron pretreatment, there are logical Cross the intermediate deslagging process for tilting converter type refining furnace and clinker being discharged from fire door.It was found that by from desiliconization, processing terminate During moment to intermediate row slag process, the clinker in furnace or in deslagging or after deslagging is acquired, in the machine of converter type refining furnace Device side is analyzed, and the composition of clinker can be analyzed in intermediate deslagging activity time, and can be used for down the analysis result The dephosphorization treatment process of one process.
Hereinafter, the present invention is described in detail.Firstly, being illustrated to the analysis method of clinker composition.
In clinker composition, due to basicity ((quality %CaO)/(quality %SiO of clinker2)) viscous to the clinker in refining Property, dephosphorization efficiency etc. bring big influence, therefore it is also big to analyze demand.Can converter type refining furnace machine side it is rapidly and fixed The basicity of amount ground evaluation clinker, not only makes the required bottom line of slag former of addition, but also be able to carry out efficient as a result, Dephosphorization treatment etc., so that industrial meaning is big.
In order to quantitatively evaluate the basicity of clinker, the CaO content and SiO to clinker are needed2Content is quantified Analysis.In general, calcium (Ca) and silicon (Si) are in clinker in deslagging with oxide (CaO and SiO2) form exist, in deslagging When clinker in there is no other forms other than the oxide of deliming and silicon.As long as that is, by the element of calcium and silicon in clinker Form quantification, it will be able to the CaO content and SiO of clinker2Content carries out quantitative analysis.Consider from the viewpoint, as clinker Quantitative analysis method, preferred fluorescent x-ary analysis.In addition, the stability of fluorescent x-ary analysis, operability, swiftness Also excellent, from this side considerations, it is also preferred that the analysis means as the machine side in converter type refining furnace etc..
For fluorescent x-ray analyzer, as detection system, there are energy dispersion types and wavelength-dispersion type, any Mode can measure clinker composition.The detector of energy dispersion type as the detector of wavelength-dispersion type without scanning light splitting Crystal, it is thus possible to be measured with shorter time.Therefore, from minute it is swiftness from the viewpoint of, detection system is more Preferably energy dispersion type.In addition, if considering the analysis in the machine side of converter type refining furnace, then preferably without using cooling The simple fluorescent x-ray analyzer of compositions such as handheld of water, liquid nitrogen etc..
The element of analysis object be preferably include two or more of necessary calcium and silicon in the evaluation of basicity, as removing Analysis object elements other than calcium and silicon can enumerate magnesium (Mg), iron (Fe), titanium (Ti), manganese (Mn), phosphorus (P), sulphur (S) etc..
In order to evaluate the basicity of clinker, need to measure CaO content and SiO in clinker2Content.Utilize fluorescent X-ray point When analysis method is analyzed, in order to eliminate the influence of coexistence elements, using with the mark of the component system production same with target clinker Quasi- g of slag sample pre-production standard curve carries out oxide conversion to the quantitative values of calcium, silicon etc., and thus, it is possible to find out in clinker CaO content and SiO2Content (referred to as " calibration curve method ").In addition, using by the strong of X-ray absorption coefficient or primary X-ray The physical constant of degree distribution etc. carries out quantitative fundamental parameters method based on theoretical strength formula, can also find out in clinker CaO content and SiO2Content is able to carry out the evaluation of basicity.In the present invention, calibration curve method and fundamental parameters method can be used Any one of.
Next, the preparation method to assay sample is illustrated.
Bulk gas can be generated in the refining of the desiliconization treatment process of molten iron, dephosphorization treatment process etc., therefore is acquired Clinker coupons be cellular and gap it is more.Therefore, even if in order to make slag surface using grinding etc. using direct method Smoothing, can also have fine hole, the basicity meeting based on assay value obtained by analyzing the sample directly acquired everywhere Deviation is big due to locating.In addition, the problem of basicity found out by direct method becomes high level there is also measured value.It is thought that It declines due to the air in the gap due to the fluorescent X-ray intensity from the silicon for belonging to grenz ray region because being present in clinker coupons Subtract, thus apparent basicity is got higher.
The inventors of the present invention for preventing the air because of the gap for being present in clinker coupons caused by silicon fluorescent X-ray it is strong The decaying of degree is studied, it is believed that needs for clinker particle to be crushed to the fluorescent X-ray intensity that can ignore from silicon thus Decaying size, and carried out research experiment.
For research experiment, coarse crushing is carried out to clinker coupons, the clinker sample through coarse crushing is sieved with sieve, Investigate influence of the clinker partial size to Basicity Determination value.Screening is set as following 6 grades:
(1)；The clinker particle directly acquired,
(2)；Partial size 9.5mm or more,
(3)；Partial size 4.8mm more than and less than 9.5mm,
(4)；Partial size 2.0mm more than and less than 4.8mm,
(5)；Partial size 1.2mm more than and less than 2.0mm,
(6)；Partial size 0.1mm is more than and less than 1.2mm.
Here, for example, the partial size of clinker particle is that 0.1mm or more refers to and remains on the sieve that mesh size is 0.1mm Particle, the partial size of clinker particle refer to the particle by the sieve that mesh size is 2.0mm less than 2.0mm.That is, clinker particle The partial size that partial size is determined and being the screening by being carried out using sieve.
By screened each clinker particle group be filled into cylindric (the culture dish shape) of internal diameter 90mm measurement container and Assay sample is made, using hand-held fluorescence x-ray analysis equipment (Olympus DELTA) in the measurement container Clinker particle group X-ray irradiation (primary X-ray), (secondary X is penetrated the fluorescent X-ray of calcium and silicon of the measurement from assay sample Line) intensity, basicity of slag is found out using fundamental parameters method.The output of x-ray source be tube voltage 50kV, tube current 0.2mA, And every 1 point of fluorescence X-ray counting time is set as 25 seconds.Measurement points are set as at 6 points to each assay sample, also to survey The deviation (standard deviation) of definite value is evaluated.
It should be noted that as long as the thickness of the clinker particle group in measurement container is completely covered by the bottom of measurement container Thickness, just enough.In addition, when to measurement vessel filling, there is also the inclination of the surface of clinker particle group or as chevron Situation, in this case, as long as giving vibration etc. with container to measurement can ensure to make hand to flatten into flat condition Hold the part of the seamless unoccupied place contact in x-ray bombardment position of formula fluorescent x-ray analyzer.As long as that is, can ensure to make The part for unoccupied place contact that the x-ray bombardment position of hand-held fluorescence x-ray analysis equipment is seamless, does not just make fill method About.
As a comparison, prepare assay sample using briquetting method and glass bead method (procedure analysis method), and with it is upper State identical condition measurement basicity of slag.
The measurement result of the basicity of slag of each assay sample is shown in FIG. 1.As shown in Figure 1, by briquetting method and glass Pearl method and the basicity of the clinker of assay sample prepared may each be about 1.20, it is known that the basicity of the clinker for test is about 1.20.In contrast, the measured value of the basicity of slag of the assay sample directly acquired is about 2.40, and along with clinker particle Partial size become smaller and reduce, the partial size of clinker particle be 0.1mm more than and less than 1.2mm when and be 1.2mm more than and less than When 2.0mm, become the basicity almost equal with the assay sample by briquetting method and glass bead method preparation.In addition, about basicity Measured value deviation, also for it is following good as a result, i.e. partial size be 0.1mm more than and less than 1.2mm when and partial size be When 1.2mm is more than and less than 2.0mm, indicate that the standard deviation of analysis precision is 0.1 or less (coefficient of variation Cv:10% or less).
According to the above experiment, show by the way that the partial size of clinker particle is prepared into 2.0mm hereinafter, caused by make because of gap The decaying of fluorescent X-ray intensity of silicon reduce to insignificant level, analysis precision improves, and the assay value of basicity becomes as a result, It obtains and is almost equal with the assay value found out by briquetting method or glass bead method.
In addition, the influence of the clinker particle for partial size greater than 2.0mm, has carried out research experiment as follows.
Same clinker is crushed, is operated using screening and prepares the sample as clinker partial size for following 5 grades:
(1)；It will be made up of the size distribution of the clinker particle of sieve and be zero with thin particle side and rise to the right (mass accumulation percentage reaches 100% to 100% partial size in curve and the cumulative grain-size distribution curve indicated with quality percentage Partial size, be also denoted as " D100"), that is, the mass accumulation percentage under sieve reaches 100% partial size for the sample (examination of 2.0mm Sample A),
(2)；(mass accumulation percentage reaches 95% partial size in the cumulative grain-size distribution curve indicated with quality percentage 95% partial size, is also denoted as " D95"), that is, the mass accumulation percentage under sieve reaches 95% partial size for the sample of 2.0mm (sample B),
(3)；(mass accumulation percentage reaches 90% partial size in the cumulative grain-size distribution curve indicated with quality percentage 90% partial size, is also denoted as " D90"), that is, the mass accumulation percentage under sieve reaches 90% partial size for the sample of 2.0mm (sample C),
(4)；(mass accumulation percentage reaches 85% partial size in the cumulative grain-size distribution curve indicated with quality percentage 85% partial size, is also denoted as " D85"), that is, the partial size that the mass accumulation percentage under sieve reaches 85% is the (examination of 2.0mm sample Sample D),
(5)；(mass accumulation percentage reaches 80% partial size in the cumulative grain-size distribution curve indicated with quality percentage 80% partial size, is also denoted as " D80"), that is, the mass accumulation percentage under sieve reaches 80% partial size for the sample of 2.0mm (sample E).
Each clinker particle group of preparation is filled into the cylindric (culture dish of internal diameter 90mm in the same manner as experiment above-mentioned Shape) measurement container and assay sample is made, the basicity of clinker is measured using hand-held fluorescence x-ray analysis equipment (6 points of measuring point) is simultaneously evaluated.
The measurement result of basicity is shown in table 1.
[table 1]
* 1: zero；Can be analyzed rapidly suitable for basicity, ×；It can not be suitable for basicity to analyze rapidly
Basicity by the clinker of glass bead method measurement is 1.18, and Sample A, the assay value of B, C, D are measured with by glass bead method Basicity it is substantially equivalent.The basicity that sample E is measured is 1.24, and slightly higher value is shown as compared with glass bead method.For analysis Precision, in Sample A, B, C, standard deviation is 0.05 hereinafter, in contrast, in sample D, E, standard deviation is each about 0.1。
Should the result shows that: in sample D, although obtained from 6 point analysis basicity average value close to utilize glass Assay value obtained from pearl method, but it is big there are the deviation of assay value and a possibility that accurate basicity may not be obtained.In addition, showing In sample E, the basicity not only measured is high level relative to glass bead method, but also deviation is also big, is unsuitable for the analysis of basicity.
As its reason, it is believed that sample D, E include the clinker greater than 2.0mm of 15 mass % or more in analysis sample Particle, as a result, the gap or bumps that generate by the clinker particle for being greater than 2.0mm impact assay value.That is, being shown to be Measurement accuracy is good and accurate basicity, the clinker sample of Basicity Determination object cannot include in the range more than 10 mass % The clinker particle of 2.0mm or more.I.e., it is known that the clinker sample for measuring basicity needs to make 90% partial size i.e. D90For 2.0mm with Under.
The partial size by preparing clinker particle as described above is known, thus the fluorescent X-ray of the silicon caused by making because of gap The decaying of intensity is reduced to insignificant level, and analysis precision improves, and the assay value of basicity becomes and by briquetting method or bead The assay value that method is found out is almost equivalent.Be made until crushing clinker particle and being sieved analysis sample until needed for when Between be 30 seconds or so, even if can with also be plus analysis time thereafter about 1 minute short time measurement clinker basicity.
As long as clinker can be crushed to above-mentioned partial size, breaking method is not restricted, for example, by breaking jaw The gap width of broken machine is adjusted to setting value appropriate and is crushed, and can obtain meeting D90The clinker of the partial size of≤2.0mm Particle.
It should be noted that as described above, by making clinker sample D90≤ 2.0mm can be obtained and by briquetting method or glass The basicity that pearl method is found out it is almost equivalent good as a result, but further progress study repeatedly, as a result known to: if micro mist shape Clinker particle containing quantitative change it is more, then exist analysis precision reduction trend.Think itself reason for this is that: obtained sample forms micro mist The mixture of the clinker of shape and granular clinker and become uneven, that is, part and micro mist shape more than the ratio of granular clinker Clinker ratio more than part in the sample exist deviate.
In addition, the clinker particle of the micro mist shape of the left and right partial size 0.1mm or less is easy to fly upward, the processing of sample is cumbersome, instead It is not preferred when for analyzing rapidly when operating cost.Therefore, research experiment as shown below is carried out, to the clinker grain of micro mist shape The influence of son is investigated.
Same clinker is crushed, prepares the sample as clinker partial size for following 6 grades using screening operation,
(1)；D90The sample (sample I) of=2.0mm,
(2)；D90=2.0mm and D5The sample (sample II) of=0.1mm,
(3)；D90=2.0mm and D10The sample (sample III) of=0.1mm,
(4)；D90=2.0mm and D15The sample (sample IV) of=0.1mm,
(5)；D90=2.0mm and D20The sample (sample V) of=0.1mm,
(6)；D100The sample (sample VI) of=0.1mm.
Each clinker particle group is filled into the survey of cylindric (the culture dish shape) of internal diameter 90mm in the same manner as experiment above-mentioned It is fixed that assay sample is made with container, basicity of slag (6 points of measuring point) is found out using hand-held fluorescence x-ray analysis equipment And it is evaluated.
The measurement result of basicity is shown in table 2.
[table 2]
* 2: zero；Can be analyzed rapidly suitable for basicity, ×: basicity can not be suitable for and be analyzed rapidly
As shown in table 2, the basicity measured in whole assay samples and the basicity measured by glass bead method are fine Ground is consistent.It will be appreciated, however, that indicating that the standard deviation of analysis precision is more than 0.05, with other samples in sample IV and sample V Compared to being in a disadvantageous position.On the other hand, in sample VI, although accuracy and analysis precision are all excellent, even if only preparing D100= The sample of 0.1mm is also required to 7 minutes or so.Further, since the processing of sample is cumbersome and micro mist shape clinker is attached to fluorescence X and penetrates The operational drawback such as the measurement site of line analysis device, thus 12 minutes or more are needed until the measurement of basicity terminates.
These the result shows that: if 0.1mm clinker particle below is more than 10%, not there is only analysis precision reduce Possibility, and the key factor that 0.1mm micro mist shape below can be swiftness as damage is all made in clinker particle.It is comprehensive On, it is known that the clinker sample for measuring basicity needs to make D10For 0.1mm or more.
According to above experimental result, it is known that the clinker sample of Basicity Determination is necessary for D10>=0.1mm and D90≤ 2.0mm。
According to the above results, the sieve that the sieve and mesh size for being 0.1mm by using mesh size are 2.0mm Net, using be 2.0mm by mesh size sieve and not be 0.1mm by mesh size sieve clinker particle as analysis It is used with sample, 2.0mm or less can be obtained and eliminates the analysis sample of the desired partial size of the particle of micro mist shape.It answers Give explanation, at this point, by make mesh size 2.0mm sieve and mesh size be 0.1mm sieve overlappingly use, thus Making to sieve the required operating time sufficiently shortens, and is suitable for analysis rapidly.
Hereinafter, to including the implementation of the invention for clipping intermediate deslagging process and carrying out pretreated refining procedure to molten iron Mode is illustrated.
Clip intermediate deslagging process and carry out desiliconization processing and dephosphorization treatment molten iron pretreatment in, in order to determine just The additive amount of CaO system appropriate fluxing agent, held at the time of needs before dephosphorization treatment the composition for remaining on clinker in furnace and Quality.It should be noted that quick lime (CaO), lime can be enumerated as the CaO system fluxing agent for controlling the CaO content in clinker Stone (CaCO3), calcium hydroxide (Ca (OH)2), dolomite (MgO-CaO), generated in the carbonization treatment of molten iron decarburization clinker ( Referred to as " vessel slag ") etc..
Therefore, in an embodiment of the invention, in order to promptly analyze clinker composition, when from desiliconization, processing terminate Start to acquire clinker into intermediate deslagging process, by clinker collected converter type refining furnace machine side implement coarse crushing and The simple sample preparation processing of screening, acquisition meet D10>=0.1mm and D90The clinker particle of≤2.0mm.Thereafter, it will be adopted The clinker of collection it is particle-filled to measurement use container and as analysis sample, using fluorescent x-ary analysis to the composition of clinker into Row quantitative analysis measures the basicity of clinker according to the assay value.
Specifically, a kind of method of refining of molten iron successively carries out following process pair using 1 converter type refining furnace Molten iron implements pretreatment: to the desiliconization treatment process for carrying out desiliconization processing from the molten iron of blast furnace casting；So that through desiliconization processing Molten iron remains on the state in above-mentioned converter type refining furnace for the desiliconization clinker generated by above-mentioned desiliconization treatment process from above-mentioned turn The intermediate deslagging process of type of furnace refining furnace discharge；The dephosphorization of dephosphorization treatment is carried out to the molten iron for remaining on above-mentioned converter type refining furnace Treatment process；And the molten iron discharging process that the molten iron through dephosphorization treatment is discharged from above-mentioned converter type refining furnace, wherein in centre In deslagging process, quantitative analysis is carried out using composition of the above-mentioned slag assay method of the invention to desiliconization clinker, according to it Analysis result and find out the basicity of desiliconization clinker.
That is, supply using CaO system fluxing agent and gas oxygen or iron oxide as oxygen source to the molten iron in converter type refining furnace It gives the desiliconization for carrying out of implementing processing in the past after, so that converter type refining furnace is tilted to side opposite when being discharged with molten iron, i.e., With the opposite side for the side for being provided with tapping hole, clinker (intermediate deslagging) is discharged via fire door.Deslagging process among this In, implement the analysis of clinker composition.
As long as assay sample clinker coupons can when from desiliconization, processing terminate after to intermediate deslagging work It acquires in sequence, is just not particularly limited.As the acquisition method of clinker coupons, it can use after processing terminate in desiliconization and stand The method that is acquired out of converter type refining furnace using sublance, in intermediate deslagging from the method for inclined fire door acquisition clinker, The method etc. acquired from the clinker in the clinker accepting container after discharge.
Measurement for the basicity of desiliconization clinker collected, by fluorescent x-ray analyzer, pulverizer, sieve and survey The fixed machine side for bringing converter type refining furnace into container, scene carry out coarse crushing and sample preparation, and acquisition meets D10>=0.1mm and D90The clinker particle of≤2.0mm.Assay sample is made to measurement container by clinker collected is particle-filled, to coming from The fluorescent X-ray intensity of the element of more than two kinds comprising calcium and silicon of the assay sample is measured.Then, standard is utilized Curve method or fundamental parameters method carry out quantifying for clinker composition, calculate the basicity of clinker.
Including coarse crushing sample preparation including from clinker coupons collect Basicity Determination until, can be at 1 point The quantitative analysis of clinker was carried out at every the 1 of analysis sample with about 1 minute or so.The advantages of analysis method of clinker of the invention, exists It is few in deviation therefore enough as long as implementing analysis at 1 to every 1 assay sample.Certainly, every 1 analysis can also be used Sample analysis many places, and using their average value, but since analysis time is elongated, necessity is low.
Fig. 2 be indicated in a manner of comparing the desiliconization clinker found out by slag assay method of the invention basicity and by The figure of the basicity for the desiliconization clinker that the assay value for the assay sample prepared using briquetting method that analysis room implements is found out.Such as figure Shown in 2, it can confirm there is good linear relationship therebetween.Detailed content about Fig. 2 carries out aftermentioned.
In the then dephosphorization treatment process of intermediate deslagging process, the desiliconization furnace found out by analysis method of the invention is utilized Residual slag amount in the basicity and converter type refining furnace of slag, clinker alkali needed for the dephosphorization treatment to reach the molten iron in the furnace The mode of degree calculates the amount of the CaO system fluxing agent of addition, adds CaO system fluxing agent into furnace according to its calculated result and is taken off Phosphorus processing.Quality presumed value and root of the residual slag amount as the clinker in the furnace before intermediate deslagging in converter type refining furnace The mass determinations for the clinker accepting container of clinker being discharged according to storage by intermediate deslagging and the difference of clinker discharge rate that estimates and It calculates.
For dephosphorization treatment process, implement using gas oxygen or iron oxide as oxygen source is supplied in furnace and implement it is previous into Capable dephosphorization treatment method.Phosphorus according to the molten iron after the phosphorus concentration, molten iron temperature, dephosphorization treatment of the molten iron before dephosphorization treatment is dense The target value etc. of degree, sets the target value of basicity of slag, the desiliconization furnace measured according to application slag assay method of the invention Residual slag amount in the composition analysis result and furnace of slag, the additive amount of CaO system fluxing agent is determined based on material balance.It should Illustrate, as long as the clinker before acquiring dephosphorization treatment in each charging in advance, is prepared using glass bead method or briquetting method later Assay sample confirms composition using analysis methods such as fluorescent x-ary analysis to the assay sample, it will be able to which confirmation is real Which kind of degree is the basicity of clinker on border before dephosphorization treatment be.
It tilts converter type refining furnace and arranges the molten iron after dephosphorization treatment from the tapping hole for being set to converter type refining furnace Molten iron accepting container is arrived out, and on the other hand, the clinker generated in dephosphorization treatment process (is known as by the clinker after making dephosphorization treatment " dephosphorization clinker ") part or all remain on converter type refining furnace.Thereafter, by new molten iron (used in charging next time Molten iron) it is encased in converter type refining furnace, start the desiliconization processing of the molten iron of charging next time.After charging next time, due to turning The clinker of residual last time charging is also able to carry out desiliconization processing so even not adding CaO system fluxing agent in type of furnace refining furnace. But when basicity of slag is lower, CaO system fluxing agent is added.
As shown in the above description: according to the sheet for carrying out pretreated refining procedure to molten iron comprising clipping intermediate deslagging process One embodiment of invention, can precisely hold the basicity of slag in intermediate deslagging process, thereby, it is possible to determine to fit In the additive amount of the CaO system fluxing agent of dephosphorization treatment.It is real as a result, it is possible to make the additive amount bottom line of CaO system fluxing agent It does not reduce productivity now and molten iron pretreatment is carried out with low cost.
In above description, to the pretreated situation of molten iron for clipping the intermediate progress of deslagging process desiliconization processing and dephosphorization treatment It is illustrated, but by cast iron melting molten steel, it can also be similar following according to being pre-processed with above-mentioned molten iron Sequentially apply the present invention.
That is, supplying CaO system fluxing agent and oxygen source into converter type refining furnace and being carried out to the molten iron in converter type refining furnace Dephosphorization treatment (since desilication reaction also occurs in the dephosphorization treatment, also referred to as " desiliconizing and dephosphorizing processing "), makes to turn later Type of furnace refining furnace tilts and carries out deslagging.Among this in deslagging process, carry out analytical furnace using slag assay method of the invention Slag composition.For the carbonization treatment process of subsequent processing, implement to supply CaO system fluxing agent and oxygen source into furnace and implement previous The carbonization treatment method of progress.Clinker is set according to target value of phosphorus concentration of liquid steel temperature and molten steel after carbonization treatment etc. The target value of basicity, according to the composition analysis result of the dephosphorization clinker measured using slag assay method of the invention and by receiving The residual slag amount for holding the mass determinations of the clinker accepting container for the dephosphorization clinker being discharged in intermediate deslagging process and estimating, base The additive amount of CaO system fluxing agent is determined in material balance.
After carbonization treatment, tilt converter type refining furnace and by the molten steel of generation from the tapping for being set to converter type refining furnace Mouth is discharged to molten steel accepting container, and part or all of the clinker (decarburization clinker) after making carbonization treatment remains on converter type essence Furnace.Thereafter, new molten iron (molten iron used in charging next time) is encased in converter type refining furnace, starts the de- of charging next time Phosphorus processing.
It should be noted that specifying that the deliming (Ca) in clinker and the ingredient other than silicon (Si) can also be in that same order It is analyzed, for example, passing through measurement and controlling the MgO containing ratio in clinker, can effectively extend converter life and can make The standby clinker that suitably forms few at expansion is as roadbed material.The reasons why converter life is influenced by the MgO containing ratio in clinker Be: the furnace lining refractory material of converter type refining furnace is formed by MgO system refractory material, if the content of MgO in clinker reduces, from category The dissolution of MgO, the service life reduction of MgO system refractory material occurs in the MgO system refractory material of furnace lining refractory material.Therefore, converter is being used In the dephosphorization treatment and carbonization treatment of the molten iron of type refining furnace, use MgO system fluxing agent as a part of slag former.As with The MgO system fluxing agent of MgO containing ratio in control clinker, can enumerate dolomite, the broken product of MgO system brick and magnesia etc..
In addition, in the dephosphorization treatment of molten iron, by measuring and controlling the FeO in clinkerXContent, can efficiently into Row dephosphorization treatment.FeO in the dephosphorization treatment of molten iron, in clinkerXFacilitate the oxidation of the phosphorus in molten iron and the scorification of clinker, In order to efficiently carry out dephosphorization treatment, there are the FeO of 5~15 mass % preferably in clinkerX.Therefore, converter type is being used In the dephosphorization treatment of the molten iron of refining furnace, use iron oxide fluxing agent as a part of slag former.As for controlling furnace FeO in slagXThe iron oxide fluxing agent of content can enumerate iron ore powder, as the burning of iron ore and the mixture of quick lime Dust dust etc. in knot miberal powder, Iron-smelting.It should be noted that FeOXRefer to FeO, Fe2O3The whole of equal ferriferous oxides.
Slag assay method of the invention also can be applied to intentionally to make clinker remain in converter type refining furnace and incite somebody to action In refining procedure of the remaining clinker for the processing of the molten iron of charging next time.
For example, in the dephosphorization treatment that molten iron is repeated using 1 converter type refining furnace (including at desiliconizing and dephosphorizing Reason) the case where or be repeated molten steel decarburization using 1 converter type refining furnace and be made the feelings of the carbonization treatment of molten steel Under condition, sometimes after molten iron discharging (tapping), so that at least part of clinker remains on the state in furnace, to converter type refining furnace In reload molten iron and carry out the refining of the molten iron of next charging.This is in order to will the remaining dephosphorization of treated clinker institute Ability for next time charging molten iron dephosphorization treatment and carbonization treatment and carry out.In this case, by applying this hair Bright slag assay method is come slag composition of analyzing that treated and is evaluated, can the dephosphorizing capacity etc. to clinker comment Valence, the residual quantity of working the slag or the slag former additive amount for adjusting the refining that next time charges.
Embodiment 1
The converter type refining furnace using 1 250 tons of capacity successively carry out desiliconization processing, intermediate deslagging, dephosphorization treatment and When implementing to pre-process to molten iron, in the pretreatment that 45 times charge, desiliconization after treatment acquires desiliconization from converter type refining furnace Clinker.Each clinker collected is divided into 2 parts, it, will be another by portion for slag assay method (the method for the present invention) of the invention Previous slag assay method (previous methods) of the portion for the implementation in the form of procedure analysis.In the method for the present invention and in the past In method, compare basicity ((quality %CaO)/(quality %SiO of desiliconization clinker2)).In the methods of the invention, from analysis examination Sample be prepared into analysis until all converter type refining furnace machine side carry out.
The preparation method and analysis condition of assay sample in the method for the present invention are as follows.
[assay sample preparation method]: clinker is carried out using the jaw crusher for being set as grinding particle size 2.0mm thick Crush, in turn, the sieve that the sieve and mesh size for being 0.1mm with mesh size are 2.0mm is sieved, acquire 0.1mm with Clinker particle that is upper and being less than 2.0mm, is filled into measurement container for clinker particle group collected, assay sample is made.
[analysis condition]: using energy dispersion type hand-held fluorescence x-ray analysis equipment (Olympus DELTA), with The output irradiation X-ray of 50kV, 0.2mA.Measurement points are set as at 1 point in each assay sample, using calcium and silicon as analysis Object elements.The quantitative approach of calcium and silicon uses fundamental parameters method.
On the other hand, the preparation method of the assay sample in previous methods and analysis condition are as follows.
[assay sample preparation method]: assay sample is prepared using briquetting method.Specifically, clinker is crushed to 75 μm of partial size is hereinafter, be attached to dedicated metal container (diameter for the clinker crushed；40mm, thickness；5mm) pressurize into Type, will thus obtained by sample as assay sample.
[analysis condition]: use wavelength-dispersion type fluorescent x-ray analyzer (Rigaku Simultix), with 50kV, The output irradiation X-ray of 50mA.Measurement points are set as at 1 point in each assay sample, using calcium and silicon as analysis object meta Element.The quantitative approach of calcium and silicon uses calibration curve method.
Fig. 2 is the figure that the basicity of the desiliconization clinker found out by the method for the present invention and previous methods is indicated in a manner of comparing. If with the error with previous methods, (the standard deviation d) of deviation evaluates the accuracy of the method for the present invention, for σ d= 0.04, it is thus identified that there is good linear relationship as shown in Figure 2 therebetween.It should be noted that dividing every 1 sample When the analysis time is compared, the method for the present invention is 1 minute, and previous methods are 25 minutes.
According to this as a result, can be confirmed that it is accurate and rapid to be able to carry out by applying slag assay method of the invention The composition analysis of clinker.
Embodiment 2
(example 1 of the present invention) is refined as follows: successively being carried out at desiliconization using 1 250 tons of capacity of converter type refining furnace Reason, intermediate deslagging, dephosphorization treatment and when implementing to pre-process to molten iron, analyze clinker group using slag assay method of the invention At the additive amount for determining CaO system fluxing agent according to the clinker composition analysis result.Specifically, in intermediate deslagging to de- Silicon treated clinker composition is analyzed, according to the clinker composition analysis as a result, finding out desiliconization treated the basicity of clinker ((quality %CaO)/(quality %SiO2)).It calculates the CaO system in the dephosphorization treatment of subsequent processing according to the basicity found out and helps The additive amount of flux, and add the CaO system fluxing agent of calculated amount.When intermediate deslagging clinker composition analysis method from point Analysis sample be prepared into analysis until carried out with condition identical with the above-mentioned the method for the present invention of [embodiment 1].
In addition to this, it also carries out previous molten iron pretreatment (comparative example 1): not analyzing clinker composition after desiliconization processing, And the basicity of desiliconization treated clinker is estimated by calculating, subsequent processing is calculated based on the basicity estimated The additive amount of CaO system fluxing agent in dephosphorization treatment adds the CaO system fluxing agent of calculated amount.
Example 1 of the present invention and comparative example 1 all continuously carry out the pretreatment of a series of molten iron and implement 100 charging (n= 1~100): the target value (upper limit value) of the phosphorus concentration of the molten iron at the end of dephosphorization treatment being set as 0.030 mass %, not make Clinker after dephosphorization treatment is discharged and remains on the molten iron that the state in furnace is packed into charging next time, continues desiliconization and handles it Afterwards, it clips intermediate deslagging and carries out dephosphorization treatment.
In above-mentioned desiliconization treatment process, use decarburization clinker as CaO system fluxing agent, with desiliconization treated clinker The calculated value (calculating basicity) of basicity is that 1.20 mode adjusts the additive amount of decarburization clinker.Even if not adding decarburization clinker, In the case that calculating basicity can also ensure that above-mentioned target value (1.20), decarburization clinker is not added and carries out desiliconization processing.Oxygen source It is supplied according to the silicon concentration in molten iron.
It for the basicity of desiliconization clinker, is calculated in comparative example 1 by (1) formula, is passed through in example 1 of the present invention (2) formula is calculated.
Bc,Si1(n)=[WS,P1(n-1)×α1×Bc,P1(n-1)/{Bc,P1(n-1)+1}+WSL,Si1(n)×β1]/[WS,P1(n- 1)×α1/{Bc,P1(n-1)+1}+WSL,Si1(n)×γ1+(XSi1(n)/100)×WHM1(n)×60/28] …(1)
Bm,Si1(n)=(%CaO)m,Si1(n)/(%SiO2)m,Si1(n) …(2)
Wherein, in (1) formula, (2) formula, each symbol is as follows.
Bc,Si1(n): the calculating basicity of clinker of the pretreated desiliconization of n-th charging when processing terminate
Bc,P1(n-1): the calculating basicity of the clinker at the end of the pretreated dephosphorization treatment of (n-1)th charging
WS,P1(n-1): the calculating clinker quality (t) at the end of the pretreated dephosphorization treatment of (n-1)th charging
WSL,Si1(n): the additive amount (t) of the decarburization clinker in the pretreated desiliconization treatment process of n-th charging
XSi1(n): the silicon concentration (quality %) in molten iron before the pretreated desiliconization processing of n-th charging
WHM1(n): the molten steel quality (t) before the pretreated desiliconization processing of n-th charging
Bm,Si1(n): the clinker of the pretreated desiliconization after treatment of n-th charging utilizes slag assay of the invention Method and the basicity found out
(%CaO)m,Si1(n): the clinker of the pretreated desiliconization after treatment of n-th charging utilizes furnace of the invention Slag analysis method and quantitative CaO concentration (quality %)
(%SiO2)m,Si1(n): the clinker of the pretreated desiliconization after treatment of n-th charging using of the invention Slag assay method and quantitative SiO2Concentration (quality %)
α1: the CaO and SiO in clinker after dephosphorization treatment2Quality ratio average value sum
β1: the average value of the quality ratio of the CaO in decarburization clinker added in desiliconization processing
γ1: the SiO in decarburization clinker added in desiliconization processing2Quality ratio average value
It should be noted that being α in the present embodiment 21=0.6, β1=0.4, γ1=0.1.In addition, about Bc,P1(n-1) and WS,P1(n-1) calculation method, as described later, but in the pretreatment to charge at the 1st time, Bc,P1It (0) is not for the normal of 0 (zero) Amount, and WS,P1(0)=0.
Clinker quality when processing terminate for desiliconization is calculated in comparative example 1 using (3) formula, in example 1 of the present invention It is middle to be calculated using (4) formula.
WS,Si1(n)={ WS,P1(n-1)×α1+WSL,Si1(n)×(β1+γ1)+XSi1(n)/100×WHM1(n)×60/28}/ δ1 …(3)
WS,Si1(n)={ WS,P1(n-1)×α1+WSL,Si1(n)×(β1+γ1)+XSi1(n)/100×WHM1(n)×60/28}/ { ((%CaO)m,Si1(n)+(%SiO2)m,Si1(n))/100} …(4)
Wherein, in (3) formula, (4) formula, each symbol is as described below.
WS,Si1(n): calculating clinker quality (t) of the pretreated desiliconization of n-th charging when processing terminate
δ 1: CaO and SiO in desiliconization treated clinker2Quality ratio average value sum
The symbol illustrated in (1) formula other than the above and (2) formula is as described in the foregoing description.It should be noted that the present embodiment 2 In, δ1=0.5.
In intermediate deslagging process, with bed drain purge relative to desiliconization processing terminate when calculating clinker quality (WS,Si1(n)) at For 50 mass % or more mode confirm institute's deslagging clinker weighing value and carry out intermediate row slag.The weighing of the clinker of institute's deslagging Using be set to load accommodate the clinker container roll-out tray weigher.
Here, in intermediate deslagging, if in order to obtain big deslagging speed or in order in the molding of desiliconization clinker The clinker residual quantity in furnace is reduced when in low level and increases the tilt angle of converter type refining furnace, then molten iron is mixed into clinker From fire door to be discharged to a certain degree together with desiliconization clinker.In this case, the discharge rate of molten iron might not.But, it is thus identified that The quality ratio for the molten iron being mixed into desiliconization clinker in many cases is to compare low level and stable level.It therefore, even if will Quality ratio of the pig iron found out by the analysis sample for the desiliconization clinker being discharged etc. is used as typical value, and is based on effluent Weighing value and calculate the quality of desiliconization clinker be discharged, also there is no problem in many cases.Therefore, in the present embodiment 2, By 0.9 times of the weighing value of the effluent in intermediate deslagging as clinker the quality (=W being discharged after desiliconization processingO,Si1(n)) and It calculates.
In dephosphorization treatment process, used as the quick lime of CaO system fluxing agent, with the calculating alkali of the clinker after dephosphorization treatment The mode that degree becomes 2.00 or more adjusts the usage amount of quick lime.It is all fixation in the primary charging in office of the usage amount of gas oxygen Amount.
For the calculating basicity of the clinker (dephosphorization clinker) after dephosphorization treatment, counted in comparative example 1 using (5) formula It calculates, is calculated in example 1 of the present invention using (6) formula.
Bc,P1(n)=[{ WS,Si1(n)-WO,Si1(n)}×δ1×Bc,Si1(n)/{Bc,Si1(n)+1}+WCaO,P1(n)]/ [{WS,Si1(n)-WO,Si1(n)}×δ1/{Bc,Si1(n)+1}] …(5)
Bc,P1(n)=[{ WS,Si1(n)-WO,Si1(n) } × (%CaO)m,Si1(n)/100+WCaO,P1(n)]/[{WS,Si1(n)- WO,Si1(n) } × (%SiO2)m,Si1(n)/100] …(6)
Wherein, in (5) formula, (6) formula, each symbol is as described below.
Bc,P1(n): the calculating basicity of the clinker after the pretreated dephosphorization treatment of n-th charging
WO,Si1(n): the clinker quality (t) being discharged after the pretreated desiliconization processing of n-th charging
WCaO,P1(n): the additive amount (t) of the quick lime in the pretreated dephosphorization treatment process of n-th charging
The symbol illustrated in (1) formula than that described above~(4) formula is as described in the foregoing description.
For the calculating clinker quality at the end of dephosphorization treatment, calculated in comparative example 1 using (7) formula, in this hair It is calculated in bright example 1 using (8) formula.
WS,P1(n)=[{ WS,Si1(n)-WO,Si1(n)}×δ1+WCaO,P1(n)]/α1 …(7)
WS,P1(n)=[{ WS,Si1(n)-WO,Si1(n) } × { (%CaO)m,Si1(n)+(%SiO2)m,Si1(n)}/100+ WCaO,P1(n)]/α1 …(8)
Wherein, in (7) formula, (8) formula, WS,P1(n) calculating at the end of the pretreated dephosphorization treatment to charge for n-th Clinker quality (t).The symbol illustrated in (1) formula in addition to this~(6) formula is as described in the foregoing description.
After the molten iron discharge after dephosphorization treatment, it is discharged dephosphorization clinker, so that the state that total amount remains in furnace is stayed It charges to next time.
Thus molten iron is implemented to pre-process, by the phosphorus concentration of the molten iron after dephosphorization treatment in example 1 of the present invention and comparative example 1 It is compared.
It is discharged in the molten iron of molten iron accepting container after example 1 of the present invention and the dephosphorization treatment of comparative example 1 is shown in FIG. 3 Phosphorus concentration.The numerical value of such as " 0~5 " of the horizontal axis of Fig. 3 indicates " 0 more than and less than 5 ", other also identical.
As shown in figure 3, with based on the additive amount for determining quick lime by the composition for calculating the desiliconization clinker estimated Comparative example 1 is compared, and in example 1 of the present invention, the phosphorus concentration of the molten iron after dephosphorization treatment is more than that the charging number of 0.050 mass % subtracts It is few.As a result, being 0.028 mass % by the average value of the phosphorus concentration of the molten iron of 1 melting of example of the present invention, relative to comparative example 1 0.035 mass % of average value is greatly reduced.
When the basicity of clinker does not fall within range appropriate in dephosphorization treatment process, dephosphorization treatment is not carried out suitably, is taken off The phosphorus concentration of phosphorus treated molten iron becomes to be above target value.That is, existing in comparative example 1 inclined by calculating the basicity of slag found out A possibility that from actual basicity of slag.
On the other hand, in example 1 of the present invention, due to controlling the clinker of dephosphorization treatment process based on the measured value of basicity of slag Basicity, therefore appropriately can accurately find out the additive amount for making the CaO system fluxing agent of basicity of slag optimum range.Think Thus the phosphorus concentration of the molten iron after dephosphorization treatment is reduced.
It should be noted that above-mentioned (1) formula~(8) formula is corresponding with the operating condition of auxiliary material used in [embodiment 2] etc. Calculating formula by considering that material balance changes these calculating formulas, can also be carried out similarly but under other operating conditions It calculates.
Embodiment 3
The converter type refining furnace using 1 250 tons of capacity successively carry out desiliconization processing, intermediate deslagging, dephosphorization treatment and Part or all for implementing the clinker after handling desiliconization in pretreated method of refining and after dephosphorization treatment to molten iron is residual It stays in furnace, remaining desiliconization clinker is used for the dephosphorization treatment of subsequent processing, be further used for down remaining dephosphorization clinker The desiliconization of the molten iron of secondary charging handles and desiliconization processing and dephosphorization treatment is repeated, and implements at this time using clinker of the invention point The method of refining of analysis method.
Specifically, being refined as follows: dividing the composition of the desiliconization clinker remained in furnace in intermediate deslagging Analysis, the additive amount of the CaO system fluxing agent (quick lime) in dephosphorization treatment is determined according to its composition analysis value and is carried out at dephosphorization Reason.Then, the basicity for dephosphorization clinker being estimated according to the additive amount of the CaO system fluxing agent (quick lime), it is de- according to what is estimated The basicity of phosphorus clinker determines the additive amount of CaO system fluxing agent (decarburization clinker) before the desiliconization processing of charging next time, adds decarburization Clinker.
That is, in the composition of analysis of intermediate deslagging time-division desiliconization clinker, desiliconization is found out treated basicity of slag ((quality % CaO)/(quality %SiO2)), according to the basicity of slag, the basicity of the dephosphorization clinker after predicting dephosphorization treatment, on this basis, The whole amount of clinker after making dephosphorization treatment remains in furnace, becomes 1.2 with desiliconization treated the basicity of slag of charging next time Mode adjust the additive amount of decarburization clinker.Oxygen source is supplied according to the silicon concentration of molten iron.
As described above, implement the basicity based on desiliconization clinker measured value come. while adjusting the additive amount of decarburization clinker Implement the pretreated situation (example 2 of the present invention) of molten iron repeatedly and unlike this in intermediate deslagging without desiliconization clinker Analysis and basicity based on the desiliconization clinker found out by calculating and implement the pretreated situation of the molten iron of charging next time repeatedly (comparative example 2) is respectively compared desiliconization treated basicity of slag.Example 2 of the present invention and 8 chargings of continuous implementation respectively of comparative example 2.
In example 2 of the present invention, the analysis method of clinker composition when intermediate deslagging is from the analysis that is prepared into of assay sample Only with condition identical with the above-mentioned the method for the present invention of [embodiment 1] progress.In addition, in example 2 of the present invention and comparative example 2, The various parameters indicated as needed using (1) formula used in above-mentioned [embodiment 2]~(8) formula.
The desiliconization for being shown in table 3 when implementing desiliconization processing, intermediate deslagging, dephosphorization treatment repeatedly treated clinker alkali Degree.
[table 3]
In example 2 of the present invention, the average value that the basicity of desiliconization clinker is charged with 8 times is calculated as 1.21, and the charging of all batches is fallen Enter the range for being ± 0.05 relative to the 1.20 of target, it can be with good precision controlling furnace of the relative standard deviation less than 3% Basicity of slag.On the other hand, in comparative example 2, it is slightly higher level, phase that the average value of the desiliconization basicity of slag of 8 chargings, which is 1.27, It is 6% or more to standard deviation, and example of the present invention 2 is larger compared to the deviation of desiliconization treated basicity of slag.
Think itself reason for this is that: in example 2 of the present invention, the measured value of desiliconization basicity of slag when due to according to intermediate deslagging come It determines the additive amount of CaO system fluxing agent (quick lime) and carries out dephosphorization treatment, therefore can precisely hold dephosphorization clinker Basicity.In contrast, in comparative example 2, such as the calculating basicity of dephosphorization clinker deviates actual basicity, can as a result, having The decarburization clinker that can be added in the form of CaO system fluxing agent before the desiliconization processing of charging next time becomes excessive.
It may validate that according to the present invention by result above, to next time, the desiliconization treatment process of charging also can be more efficiently Implement refining in ground.

Claims (9)

1. a kind of analysis method of clinker is the analysis method of the clinker generated in the refining of molten iron, there is following process:
The process that the clinker sample acquired from clinker is crushed；
It is acquired from the clinker particle of crushing and the size distribution of the clinker particle by sieve is made with the side of thin particle Be zero and the curve that rises to the right and the cumulative grain-size distribution curve indicated with quality percentage in 10% partial size i.e. D10For 0.1mm or more and 90% partial size, that is, D90For the process of 2.0mm clinker particle below；
By the particle-filled process to measurement container of clinker collected；
The process that fluorescent X-ray intensity from the clinker particle group filled is measured；And
The process for carrying out quantitative analysis is formed to clinker by the fluorescent X-ray intensity being measured to.
2. the analysis method of clinker according to claim 1, wherein in the process for measuring the fluorescent X-ray intensity, Fluorescent X-ray intensity comprising calcium, that is, Ca and silicon, that is, Si element of more than two kinds is measured.
3. a kind of method of refining of molten iron, so that one of clinker caused by the refining of the molten iron in converter type refining furnace The state for remaining on the converter type refining furnace is divided to carry out the subsequent processing for remaining on the molten iron of the converter type refining furnace Refining or the refining of the next molten iron to charge using the molten iron for being newly encased in the converter type refining furnace,
Using the analysis method of clinker described in as claimed in claim 1 or 22 to the group of the clinker generated in the refining of molten iron At carry out quantitative analysis,
Analyze result according to it determine it is being carried out in the converter type refining furnace for remaining clinker, remain in it is molten in furnace Melt the subsequent processing of iron refining or using the molten iron being newly encased in furnace next time charging molten iron refining refining The amount of the slag former added in preceding and/or refining.
4. the method for refining of molten iron according to claim 3, wherein the refining of the molten iron is using 1 converter Type refining furnace carries out multiple refining procedures to molten iron, between multiple refining procedure so that a part residual of molten iron and clinker In the state discharge clinker of the converter type refining furnace remainder and the pretreatment of molten iron that carries out,
The composition of the clinker is analyzed in the discharge of the remainder of the clinker,
According to its analysis as a result, determining the amount of the slag former added in the refining procedure of subsequent processing.
5. the method for refining of molten iron according to claim 3, wherein the refining of the molten iron is using 1 converter Type refining furnace carries out pretreated refining to molten iron,
Molten iron pre-processes so that part or all of the clinker generated remains on the state discharge of the converter type refining furnace Pretreated molten iron is simultaneously newly packed into molten iron into furnace and implements the pretreatment of next charging,
When part or all for making the clinker remains on the converter type refining furnace, the composition of remaining clinker is carried out Analysis,
According to its analysis as a result, determining the amount of the slag former added in the next pretreatment to charge.
6. a kind of method of refining of molten iron, using 1 converter type refining furnace, according to the following processes of following sequences progress to iron Water implements pretreatment, has following process:
Desiliconization treatment process carries out desiliconization processing to from the molten iron of blast furnace casting,
Intermediate deslagging process, remaining on the state in the converter type refining furnace with the molten iron handled through desiliconization will be by the desiliconization The desiliconization clinker that treatment process generates is discharged from the converter type refining furnace,
Dephosphorization treatment process carries out dephosphorization treatment to the molten iron for remaining on the converter type refining furnace, and
Molten iron through dephosphorization treatment is discharged molten iron discharging process from the converter type refining furnace；
Wherein, in the intermediate deslagging process, using the analysis method of clinker as claimed in claim 2 to the group of desiliconization clinker At carry out quantitative analysis,
The basicity of desiliconization clinker is found out according to its analysis result, that is, (quality %CaO)/(quality %SiO2),
According to the basicity found out i.e. (quality %CaO)/(quality %SiO2) determine that adds in the dephosphorization treatment process makes The amount of slag agent.
7. the method for refining of the molten iron according to any one of claim 3~6, wherein the slag former is that CaO system helps Flux.
8. the method for refining of the molten iron according to any one of claim 3~7, wherein use MgO system fluxing agent as A part of the slag former,
The analysis result of the clinker includes the content of MgO in clinker,
The additive amount of MgO system fluxing agent is determined according to the analysis result of the clinker.
9. the method for refining of the molten iron according to any one of claim 3~8, wherein use iron oxide fluxing agent As a part of the slag former,
The analysis result of the clinker includes the iron oxide content in clinker,
The additive amount of the iron oxide fluxing agent is determined according to the analysis result of the clinker.
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