CN100475980C - High Ca, silicon-free aluminum calcium iron alloy for deoxidising of molten steel and preparation method thereof - Google Patents
High Ca, silicon-free aluminum calcium iron alloy for deoxidising of molten steel and preparation method thereof Download PDFInfo
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Abstract
The invention discloses calcium-aluminium- ferrum alloy for steel- melting and deoxidizing, the weight proportion of them is as follows: 15%<Ca <=30%, Al: Ca=1-2: 1, the left is ferrum. The optimal range is Ca18-25%, Al: Ca=1-1.3: 1,left is ferrum. It takes calcium, aluminium, and low- carbon steel as raw material, and prepares aluminium- ferrum solution by using frenquency furnance, then presses calcium into aluminium- ferrum solution for deep fusion by using net- container, casts under nitrogen gas protection; or prepares calcium-aluminium intermediate alloy by using low- frequency furnance, then prepares aluminium- ferrum solution by using frenquency furnance, presses calcium-aluminium intermediate alloy into aluminium- ferrum solution for deep fusion by using same container, casts under nitrogen gas protection. The alloy is used for low- silicon and low- carbon aluminium steel deoxidation.
Description
One, technical field
The present invention relates to iron alloy, particularly a kind of high-calcium non-silicon aluminium calcium iron alloy of smelting low silicon, carbon aluminium-killed steel final deoxygenation and preparation method thereof that is used to.
Two, background technology
Entered since nineteen nineties, the essence variation has taken place in China's process for making, and following process also constantly extends, formed hot metal pretreatment → top and bottom combined blown converter steelmaking → LF, RH concise → continuous casting → hot rolling → cold rolling → zinc-plated → complete operational path of coating.Meanwhile, deep drawing steel, extra-deep drawing steel (as car surface slab, container steel etc.) kind proportion are also increasing.
Be used to produce low silicon, the carbon aluminium-killed steel that approaches specification cold-rolling deep-punching product at smelting, mostly prolong at present with metallic aluminium (or ferroaluminium) and make reductor.As everyone knows, the deoxidation products Al of aluminium deoxidizer
2O
3There are two harms: the one, because Al
2O
3Fusing point height (2050 ℃) is solid phase in steel-making under the temperature, wettability extreme difference mutually, and difficult cohesion is grown up, and is difficult for come-up and removes in molten steel, easily sticks to during continuous casting on the mouth of a river, forms dross, causes nozzle clogging, and is totally unfavorable to continuous casting; The 2nd, in steel, form Al
2O
3Inclusion, this inclusion is chain or String structure, has not plasticity-, can reduce the toughness of steel, influences processing characteristics.For this reason, people are seeking to lower Al always
2O
3The technical measures of deoxidation products harmful effect.
Because the avidity of calcium and oxygen is very strong; The CaO that calcium and oxygen reaction back forms can with aluminium deoxidation product A l
2O
3Further form the calcium-aluminate of low melting point (1400 ℃).The latter is liquid phase under the steel-making temperature, wettability is good mutually, can comparatively fast condense and grow up, floats and remove, thereby can reduce Al in the steel
2O
3Be mingled with and nozzle clogging phenomenon when alleviating continuous casting.According to these characteristics of calcium, people have taked the first aluminium deoxidation of using when producing low silicon, carbon aluminium-killed steel just, feed the so-called calcium treatment technology of calcium then again in the concise later stage, to Al
2O
3Be mingled with and carry out denaturing treatment.Yet the way that this is actually a kind of " pollute afterwards earlier and administer " both bothered, and was uneconomical again; Simultaneously, owing to concisely finish to the time of casting very shortly, can not guarantee that inclusion has competent floating interval of floating dock, so this technology promptly enables to reduce nozzle clogging, but Al in the steel
2O
3Be mingled with quantity and but be difficult to drop to perfect condition.
In order to overcome the shortcoming of above-mentioned calcium treatment technology, people begin to seek calcium are directly added technology in the reductor.The applicant had once disclosed Al-Ca-Fe alloy of a kind of low silicon content that is used for deoxidation in steel making and preparation method thereof in Chinese patent ZL03111225.0.This alloy compositions (weight ratio) is Al30-60%, Ca2-15%, and Si2-3%, surplus is Fe.Its preparation method is that to adopt calcium iron (available ore deposit heat furnace method is smelted in advance), aluminium and the iron contain Si 14-18% be that raw material is made with the power frequency induction furnace melting.Limit by the raw material of this smelting technology, contain the composition of silicon in this alloy,, concerning producing low silicon, carbon aluminium-killed steel, be still harmful element although amount is few.Simultaneously, though the upper limit of Ca is fixed to 15% in this alloy, in fact surpasses 8% and be difficult to realize.This be because, according to described preparation method, make the content of Ca in the alloy surpass 8%, just must strengthen the consumption that contains silico-calcium iron in the raw material, this just will certainly cause, and the content of silicon exceeds 3% the upper limit in the alloy.Therefore, this Al-Ca-Fe alloy is a kind of low calcium deoxygenated alloy in fact still, and main deoxidation composition still is aluminium (content of aluminium is 5-10 times of calcium).Use its deoxidation, though can improve deoxidation effect to a certain extent, can not be with whole or most of deoxidation products Al
2O
3Be converted into low-melting calcium-aluminate.That is to say that this alloy can not reduce deoxidation products Al to greatest extent
2O
3Harmful effect, do not reach the ideal deoxidation effect.Therefore, at smelting low silicon, carbon aluminium-killed steel, design and a kind ofly can reduce deoxidation products Al to greatest extent
2O
3The high-calcium non-silicon aluminium calcium iron alloy of harmful effect is an industry problem anxious to be solved.
Yet even design above-mentioned high-calcium non-silicon aluminium calcium iron alloy, how it being produced is another problem.With the reduction simultaneously in iron of ore deposit heat furnace method with aluminium and calcium, fusing point low (838 ℃) because of calcium, boiling point also low (1450 ℃), density little (1.55g/cm), do not wait alloy to come out of the stove, will float from molten metal in smelting process volatilization and oxidization burning loss of most of calcium falls, and can not make calcium contents above 15% high calcium alloy.Simultaneously, also be difficult to control to make do not have sila matter in the alloy with this method.With metallic aluminium, calcium and iron is raw material, with the induction furnace hot-metal process melting of routine, though can obtain not having silicon alloy, same because the These characteristics of calcium, calcium also can volatilize and oxidization burning loss in long fusion process in large quantities, equally also can not make calcium contents and surpass 15% high calcium alloy.
Three, summary of the invention
The purpose of this invention is to provide a kind of high-calcium non-silicon aluminium calcium iron alloy, with its reductor as the low silicon of smelting, carbon aluminium-killed steel, can be with deoxidation products Al
2O
3Whole or major part is converted into low-melting calcium-aluminate, thereby reduces Al to greatest extent
2O
3Harmful effect.
Another object of the present invention provides the preparation method of above-mentioned alloy.
High-calcium non-silicon aluminium calcium iron alloy of the present invention, contain 15%＜Ca≤30%, Al: Ca=1-2 by weight: 1, the Fe surplus.
The preferable range of high-calcium non-silicon aluminium calcium iron alloy component content of the present invention is: contain Ca18-25%, Al: Ca=1-1.3 by weight: 1, and the Fe surplus.
The preferred value of high-calcium non-silicon aluminium calcium iron alloy component content of the present invention is to contain Ca22% by weight, Al25%, Fe surplus.
A kind of preparation method of above-mentioned alloy provided by the invention may further comprise the steps:
(1) component content by described high-calcium non-silicon aluminium calcium iron alloy calculates the quantity that every stove is smelted raw materials used aluminium, calcium and low-carbon waste steel, and takes by weighing respectively, and calcium wherein reduces and the contacting of air as far as possible;
(2) calcium is packed into have in the high-temperature resistant container of mesh, and reduce and the contacting of air as far as possible, standby;
(3) with line frequency induction furnace aluminium and low-carbon waste steel are melt into the ferro-aluminum molten metal;
(4) the above-mentioned high-temperature resistant container that calcium is housed is pressed into above-mentioned ferro-aluminum molten metal deep fast, and makes container in the ferro-aluminum molten metal, stir 5-10 second, make calcium be melt into Al-Ca-Fe alloy liquid, container is taken out, and change step (5) fast over to by the ferro-aluminum molten metal;
(5) with mould above-mentioned Al-Ca-Fe alloy liquid is cast, the alloy liquation that goes out converter nose with the argon gas convection current in the casting cycle is protected;
(6) cooling and demolding obtains high-calcium non-silicon aluminium calcium iron alloy goods of the present invention through fragmentation.
The present invention also provides the another kind of preparation method of above-mentioned alloy, the steps include:
(1) be raw material with metallic aluminium and calcium, press Al40%, the weight ratio batching of Ca60% is smelted into aluminium calcium master alloy with Ajax-Wyatt furnace, and is broken standby;
(2) component content by described high-calcium non-silicon aluminium calcium iron alloy calculates the quantity that every stove is smelted raw materials used aluminium, above-mentioned aluminium calcium master alloy and low-carbon waste steel, and take by weighing respectively, the aluminium calcium master alloy that takes by weighing packed into to be had in the high-temperature resistant container of mesh, standby;
(3) with line frequency induction furnace aluminium and low-carbon waste steel in (2) are melt into the ferro-aluminum molten metal;
(4) the above-mentioned high-temperature resistant container that aluminium calcium master alloy is housed is pressed into above-mentioned ferro-aluminum molten metal deep fast, and make container in the ferro-aluminum molten metal, stir 7-15 second, rapidly container is taken out after making aluminium calcium master alloy be melt into Al-Ca-Fe alloy liquid, and change step (5) immediately over to by the ferro-aluminum molten metal;
(5) with mould above-mentioned Al-Ca-Fe alloy liquid is cast, the alloy liquation that goes out converter nose with the argon gas convection current in the casting cycle is protected;
(6) cooling and demolding obtains high-calcium non-silicon aluminium calcium iron alloy goods of the present invention through fragmentation.
The composition design of high-calcium non-silicon aluminium calcium iron alloy of the present invention is suitably improving on the basis of alloy calcium contents, mainly considers the relative proportion (weight) of Aluminum in Alloy and calcium.The inventor will be with aluminium deoxidation product A l through long-term exploration discovery
2O
3Harmful effect drop to minimumly, taking into account again simultaneously to have a certain amount of residual aluminium in the steel, and factors such as aerial stability of alloy and alloy density, the weight ratio of Aluminum in Alloy and calcium is fixed on 1-2: in 1 the scope; Preferable range is 1-1.3: 1.
First kind of preparation method of above-mentioned alloy adopts fusing ferro-aluminum earlier, when ferro-aluminum is melt into molten metal about 1500 ℃, utilizes the high-temperature resistant container of band mesh in moment calcium to be pressed into ferro-aluminum liquid deep, makes it and can not float.Because the fusing point of calcium is more much lower than ferro-aluminum liquid temp, and boiling point is a little less than the ferro-aluminum liquid temp, and calcium can be melted in the extremely short time, incorporates in the ferro-aluminum liquid.When not having enough time to gasify as yet, just enter the casting operation immediately, when casting, adopt argon shield again, the calcium in the liquid alloy is not contacted with air.Owing in whole process of preparation, avoid calcium directly to contact always, thereby guarantee the high utilization rate of calcium, make and produce high calcium alloy and can realize with air.
Very approaching based on the fusing point (730 ℃) of aluminium with the fusing point (838 ℃) of calcium, and far below the boiling point (1450 ℃) of calcium, second kind of preparation method of above-mentioned alloy adopts the way of preparation aluminium calcium master alloy earlier, makes calcium avoid loss.Because of aluminium calcium master alloy density less than ferro-aluminum molten metal density; for avoiding its come-up; adopted way and the argon shield of (5) step that is pressed into ferro-aluminum liquid deep with the high-temperature resistant container of band mesh equally in (4) step; guarantee that calcium does not directly contact and loses with air in whole process of preparation; improve the utilization ratio of calcium, can make high calcium alloy at last.
Above-mentioned two kinds of preparation methods respectively have its relative merits.The advantage of first method is melting for once, and energy consumption is low relatively; Shortcoming be calcium metal in process of production inconvenience deposit (ingress of air is oxidation very easily).The advantage of second method is that calcium is become more stable kalzium metal earlier, conveniently deposits in the production process; Shortcoming is to have increased secondary smelting, and energy consumption is higher relatively.Consider the stability of production, still adopt second method to be advisable when producing this alloy in enormous quantities.
Al-Ca-Fe alloy of the present invention owing to be raw material with metallic aluminium, calcium and low-carbon waste steel, is guaranteed in the composition not siliceously, and carbon content is low, thereby is specially adapted to smelt low silicon, carbon aluminium-killed steel.Owing to adopt above-mentioned preparation method, the content of calcium in the alloy can be brought up to more than 15%, reach as high as 30%; The weight of Aluminum in Alloy and calcium remains on 1-2 in addition: in the scope of 1 (weight), in the deoxidation process, have the reaction of enough calcium and oxygen to generate CaO, with most of deoxidation products Al
2O
3Be converted into low-melting calcium-aluminate, not only can reduce continous casting sprue dross phenomenon, also can significantly reduce Al in the steel
2O
3Be mingled with, improve the cleanliness factor of steel to greatest extent, thereby reach the ideal deoxidation effect.
Four, embodiment
The invention is further illustrated by the following examples.
Embodiment 1
Prepare high-calcium non-silicon aluminium calcium iron alloy of the present invention according to the following steps:
(1) press Ca15%, Al15%, the weight ratio of the steel scrap 70% of C＜0.05% takes by weighing the raw material of a stove, and calcium is wherein encapsulated with plastics bag, and is standby;
(2) calcium in the above-mentioned plastics bag is taken out, in the high-temperature resistant container (this container usable surface is made with the steel cylinder of graphite, offers mesh on the perisporium of steel cylinder, and top has handle) that has mesh of packing into, with container encloses, standby with plastics bag;
(3) with line frequency induction furnace aluminium is melted, add steel scrap then, be melt into the ferro-aluminum molten metal;
(4) the above-mentioned high-temperature resistant container that calcium is housed is taken out from plastics bag, utilize the handle of container, container is pressed into above-mentioned ferro-aluminum molten metal deep fast, and container was stirred for 7 seconds in the ferro-aluminum molten metal, make calcium be melt into Al-Ca-Fe alloy liquid by the ferro-aluminum molten metal, container is proposed, and change down step fast over to;
(5) with mould above-mentioned Al-Ca-Fe alloy liquid is cast, by pipeline and gas hood argon gas is blowed to the alloy liquid that flows out converter nose in the casting cycle, protected;
(6) be broken into bulk after the cooling and demolding, obtain component content and be respectively Ca15%, Al15%, the high-calcium non-silicon aluminium calcium iron alloy goods of Fe70%.
This alloy is numbered the 1# alloy.
Embodiment 2
The preparation method is identical with embodiment 1, just in step (1) by weight Ca15%, Al30%, Fe55% takes by weighing furnace charge.Make component content at last and be respectively Ca15%, Al30%, the Al-Ca-Fe alloy of Fe55%.Be numbered the 2# alloy.
Embodiment 3
The preparation method is identical with embodiment 1, just in step (1) by weight Ca30%, Al30%, Fe40% takes by weighing furnace charge.Make component content at last and be respectively Ca30%, Al30%, the high-calcium non-silicon aluminium calcium iron alloy of Fe40%.Be numbered the 3# alloy.
Embodiment 4
The preparation method is identical with embodiment 1, just in step (1) by weight Ca30%, Al60%, Fe10% takes by weighing furnace charge.Make component content at last and be respectively Ca30%, Al60%, the high-calcium non-silicon aluminium calcium iron alloy of Fe10%.Be numbered the 4# alloy.
Embodiment 5
The preparation method is identical with embodiment 1, just in step (1) by weight Ca18%, (Al: Ca=1: 1), Fe64% takes by weighing furnace charge to Al18%.Make component content at last and be respectively Ca18%, Al18%, the high-calcium non-silicon aluminium calcium iron alloy of Fe64%.Be numbered the 5# alloy.
Embodiment 6
The preparation method is identical with embodiment 1, just in step (1) by weight Ca18%, (Al: Ca=1.3: 1), Fe58.6% takes by weighing furnace charge to Al23.4%.Make component content at last and be respectively Ca18%, Al23.4%, the high-calcium non-silicon aluminium calcium iron alloy of Fe58.6%.Be numbered the 6# alloy.
Embodiment 7
The preparation method is identical with embodiment 1, just in step (1) by weight Ca25%, (Al: Ca=1: 1), Fe50% takes by weighing furnace charge to Al25%.Make component content at last and be respectively Ca25%, Al25%, the high-calcium non-silicon aluminium calcium iron alloy of Fe50%.Be numbered the 7# alloy.
Embodiment 8
The preparation method is identical with embodiment 1, just in step (1) by weight Ca25%, (Al: Ca=1.3: 1), Fe42.5% takes by weighing furnace charge to Al32.5%.Make component content at last and be respectively Ca25%, Al32.5%, the high-calcium non-silicon aluminium calcium iron alloy of Fe42.5%.Be numbered the 8# alloy.
Embodiment 9
The preparation method is identical with embodiment 1, just in step (1) by weight Ca22%, Al25%, Fe55% takes by weighing furnace charge.Make component content at last and be respectively Ca22%, Al25%, the high-calcium non-silicon aluminium calcium iron alloy of Fe55%.Be numbered the 9# alloy.
The 1#-9# high-calcium non-silicon aluminium calcium iron alloy that embodiment 1-9 is made is respectively applied for that low silicon is produced in 150 tons of converters of certain factory, carbon aluminium-killed steels are made reductor, with usefulness AlFe (Al50%, Fe50%) low calcium (the aluminium calcium iron) alloy (Al50% of patent described in reductor and the background technology, Ca4%, Si2%, surplus is Fe) contrast, result such as following table:
| Reductor | Terminal point [C] (%) | Terminal point [O] (ppm) | [O] (ppm) after the deoxidation | The amount of inclusions (mg/10kg) | Reductor consumption (kg/t steel) | The residual aluminium amount of molten steel (%) | The nozzle clogging degree |
| AlFe | 0.035 | 830 | 76 | 29.28 | 4.40 | 0.012 | Seriously |
| Low calcium alloy | 0.040 | 830 | 40 | 19.30 | 3.35 | 0.020 | Slightly |
| The 1# alloy | 0.042 | 825 | 36 | 18.40 | 3.36 | 0.020 | Slightly |
| The 2# alloy | 0.036 | 827 | 34 | 18.50 | 3.40 | 0.021 | Slightly |
| The 3# alloy | 0.035 | 820 | 28 | 14.20 | 3.32 | 0.022 | In time, have |
| The 4# alloy | 0.041 | 840 | 28 | 14.10 | 3.20 | 0.021 | In time, have |
| The 5# alloy | 0.036 | 840 | 24 | 13.70 | 3.20 | 0.024 | Accidental |
| The 6# alloy | 0.035 | 845 | 22 | 12.50 | 3.15 | 0.020 | Accidental |
| The 7# alloy | 0.035 | 850 | 22 | 11.50 | 3.15 | 0.026 | Do not have |
| The 8# alloy | 0.041 | 830 | 18 | 10.01 | 3.15 | 0.027 | Do not have |
| The 9# alloy | 0.035 | 835 | 18 | 10.01 | 3.10 | 0.030 | Do not have |
As seen from the above table, use high-calcium non-silicon aluminium calcium iron alloy of the present invention deoxidation with the deoxidation of AlFe reductor, deoxidation effect is good, steel inclusion (Al
2O
3) obviously reduce, the mouth of a river is difficult for dross, residual aluminium height in the steel, and economic benefit is obvious.
Compare Al in the deoxidation effect of high-calcium non-silicon aluminium calcium iron alloy of the present invention and the steel with low calcium Al-Ca-Fe alloy
2O
3Inclusion content all is better than low calcium Al-Ca-Fe alloy.
Compare the 1#--9# Al-Ca-Fe alloy, also can draw:
(1) as Al in the alloy: Ca=1-1.3: in the time of 1, Al in its deoxidation effect and the steel
2O
3Inclusion content all is better than the alloy beyond this scope.This is because in this scope, whole or most Al
2O
3Be converted to low-melting calcium-aluminate.
(2) work as Ca18-25%, Al: Ca=1-1.3: 1 o'clock better effects if, wherein again with 9# alloy effect optimum.
(3) when calcium is got 25-30%, Al: Ca should not surpass 1.5, otherwise can cause the Fe content of alloy low excessively (below 40%), it is too much to make alloy density be lower than molten steel density, drop into the scaling loss that easily floats in the steel, cause the reductor effective rate of utilization to reduce relatively, the reductor consumption increases relatively.Simultaneously, it is too much that Al and Ca total content surpass Fe, the aerial stability meeting of alloy variation, and easily efflorescence is difficult for storing.
(4) be lower than 18%, Al as Ca: Ca=1-1.3: 1 o'clock, Fe content will surpass the total content of effective deoxidation composition Al and Ca greater than 60% in the alloy, reach same deoxidation effect, and the reductor consumption increases relatively.
At last, need to prove that high-calcium non-silicon aluminium calcium iron alloy of the present invention is not limited to only be used as the reductor of smelting low silicon, carbon aluminium-killed steel, also can be used as the reductor of smelting other steel grade that identical requirement is arranged.
Claims (2)
1, a kind of preparation method who is used for the high-calcium non-silicon aluminium calcium iron alloy of deoxidation in steel making is characterized in that may further comprise the steps:
(1) Ca18-25% by weight, Al: Ca=1-1.3: 1, the alloying constituent cubage of Fe surplus goes out the quantity that every stove is smelted raw materials used aluminium, calcium and low-carbon waste steel, and takes by weighing respectively, and calcium wherein reduces and the contacting of air as far as possible;
(2) calcium is packed into have in the high-temperature resistant container of mesh, and reduce and the contacting of air as far as possible, standby;
(3) with line frequency induction furnace aluminium and low-carbon waste steel are melt into the ferro-aluminum molten metal;
(4) the above-mentioned high-temperature resistant container that calcium is housed is pressed into above-mentioned ferro-aluminum molten metal deep fast, and makes container in the ferro-aluminum molten metal, stir 5-10 second, make calcium be melt into Al-Ca-Fe alloy liquid, container is taken out, and change step (5) fast over to by the ferro-aluminum molten metal;
(5) with mould above-mentioned Al-Ca-Fe alloy liquid is cast, the alloy liquation that goes out converter nose with the argon gas convection current in the casting cycle is protected;
(6) cooling and demolding obtains described high-calcium non-silicon aluminium calcium iron alloy goods through fragmentation.
2, a kind of preparation method who is used for the high-calcium non-silicon aluminium calcium iron alloy of deoxidation in steel making is characterized in that may further comprise the steps:
(1) be raw material with metallic aluminium and calcium, press Al40%, the weight ratio batching of Ca60% is smelted into aluminium calcium master alloy with Ajax-Wyatt furnace, and is broken standby;
(2) Ca18-25% by weight, Al: Ca=1-1.3: 1, the alloying constituent cubage of Fe surplus goes out the quantity that every stove is smelted raw materials used aluminium, above-mentioned aluminium calcium master alloy and low-carbon waste steel, and takes by weighing respectively, the aluminium calcium master alloy that takes by weighing packed into to be had in the high-temperature resistant container of mesh, standby;
(3) with line frequency induction furnace aluminium and low-carbon waste steel in (2) are melt into the ferro-aluminum molten metal;
(4) the above-mentioned high-temperature resistant container that aluminium calcium master alloy is housed is pressed into above-mentioned ferro-aluminum molten metal deep fast, and make container in the ferro-aluminum molten metal, stir 7-15 second, rapidly container is taken out after making aluminium calcium master alloy be melt into Al-Ca-Fe alloy liquid, and change step (5) immediately over to by the ferro-aluminum molten metal;
(5) with mould above-mentioned Al-Ca-Fe alloy liquid is cast, the alloy liquation that goes out converter nose with the argon gas convection current in the casting cycle is protected;
(6) cooling and demolding obtains described high-calcium non-silicon aluminium calcium iron alloy goods through fragmentation.
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| CN112501477A (en) * | 2020-11-06 | 2021-03-16 | 郭鸿鼎 | Micro-carbon low-sulfur high-aluminum iron-free aluminum-magnesium-calcium alloy deoxidizer and preparation method and application thereof |
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Owner name: BENXI SMELTING GROUP CO., LTD. Free format text: FORMER OWNER: GUO QINGCHENG Effective date: 20110610 |
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Free format text: CORRECT: ADDRESS; FROM: 117100 CARE OF BENXI TRANSPORTATION BUREAU, XIAOSHI TOWN, BENXI COUNTY, LIAONING PROVINCE TO: 117100 NO. 549, CHANGJIANG ROAD, XIAOSHI TOWN, BENXI COUNTY, LIAONING PROVINCE |
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Effective date of registration: 20110610 Address after: 117100 Changjiang Road in Liaoning province Benxi County small town No. 549 Patentee after: Benxi Smelting Group Co., Ltd. Address before: 117100 Liaoning County of Benxi Province town Benxi County Department of transportation. Patentee before: Guo Qingcheng |
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Effective date of registration: 20190307 Address after: 117100 Ma Pinggou Village, a small town in Benxi Manchu Autonomous County, Liaoning Province Patentee after: Benxi new smelting Co., Ltd. Address before: 117100 Changjiang Road 549, Xiaoshizhen, Benxi County, Liaoning Province Patentee before: Benxi Smelting Group Co., Ltd. |
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