CN102127614A - Control method for vanadium extraction by converter for removing vanadium and holding carbon - Google Patents
Control method for vanadium extraction by converter for removing vanadium and holding carbon Download PDFInfo
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Abstract
The invention provides a control method for vanadium extraction by a converter for removing vanadium and holding carbon, belonging to the technical field of metallurgical vanadium extraction. The control method adopts a fume analysis method and comprises the following steps of: connecting the signals of CO and O2 concentration curves to a computer to form continuous curves; determining the adding time of a coolant in the vanadium extraction converting process according to the change of the CO content in the fume; prolonging the optimum temperature interval of vanadium oxidation in the converting process; and judging the vanadium extraction terminal by combining with the oxygen consumption in a vanadium extraction model. Under the condition of same molten iron, the carbon content of semi-steel can be stably controlled at 3.70-3.90% with the average value of 3.86%, which is improved by 0.14%, thus providing a stable semi-steel condition for the next steelmaking process, effectively avoiding the terminal after-blow phenomenon caused by shortage of steelmaking heat of the semi-steel, and solving the quality problem of the molten steel caused by serious after-blow. The content of residual vanadium is controlled at 0.030-0.050% and reduced by 0.004%, the average content of residual vanadium reaches 0.039%, the vanadium oxidation rate reaches 81-92% with the average value of 85% which is improved by 2% compared with the background art, and the recovery rate of vanadium is correspondingly improved, thus further improving the key technical indexes in vanadium extraction.
Description
Technical field
The present invention relates to a kind of vanadium removal of realizing and protect the vanadium extraction by converter blowing control method of carbon, particularly a kind of vanadium extraction by converter blowing control method of utilizing CO content realization vanadium removal guarantor carbon in the furnace gas belongs to metallurgical vanadium extraction technical field.
Background technology
Vanadium extraction by converter blowing is a kind of smelting technology that grows up on the basis of oxygen top blown converter steel making equipment and technology, be that with the key distinction of converter steelmaking process the main task of vanadium extraction by converter blowing is " a vanadium removal guarantor carbon ", in whole vanadium extraction process, temperature must be controlled at certain scope, by adding refrigerant control bath temperature, suppress reaction between carbon and oxygen, the oxidizing reaction that strengthens vanadium forms vanadium slag.The vanadium oxidation is thermopositive reaction, and " low temperature " helps the oxidation of vanadium, and temperature control is the key link that realizes vanadium removal guarantor carbon.From the thermodynamics angle, the oxidized priority that exists of carbon and vanadium, priority mainly changes according to the variation of bath temperature.The oxidation priority transition temperature of carbon and vanadium is generally between 1340 ℃～1400 ℃.In the vanadium extraction by converter blowing process, when bath temperature hanged down, the vanadium in the molten iron was preferentially oxidized.Along with continuing of oxygen-supply operation, bath temperature constantly raises.When the bath temperature reached transition temperature, carbon began preferential oxidation in the iron liquid, and then reduced ferric oxide in the slag, suppress the further oxidation of vanadium, even when the carbon vigorous oxidation, the barium oxide in the slag is entered in the half steel once more by carbon reduction, thereby has reduced the rate of recovery of vanadium.Vanadium extraction by converter blowing has that speed of response is fast, smelting cycle is short, v slag grade is high, the production efficiency advantages of higher.But simultaneously because the very complicated pyrometallurgical process that this process is made up of the heating and the subprocess such as dissolving, chemical kinetics, mass balance and thermal equilibrium of mass transfer, heat transfer, solid addition material, the factor that influences terminal point composition and temperature is a lot, is not easy to control manually.Present vanadium extraction by converter blowing is artificial experiential operating pattern, mainly be rate of rise in temperature to be judged in the observation of flame by naked eyes, cold burden often occurs and add that very few to cause the molten bath to heat up too fast, shorten the optimum temps interval of vanadium oxidation, or cold burden add the low slag iron of the half steel temperature too much cause separate bad, problem such as Mfe height in the slag.Vanadium extraction by converter blowing in recent years also proves, by rule of thumb, be to cause vanadium slag quality, one of the main reasons that the half steel quality fluctuation is big with the mode of production of sensation vanadium extraction, thereby becomes one of technical problem that this area needs to be resolved hurrily.
Summary of the invention
The object of the invention provides a kind of vanadium removal of realizing and protects the vanadium extraction by converter blowing control method of carbon, improve the key technical indexes of vanadium extraction, prolong the optimum temps interval of vanadium oxidation, control half steel carbon content, improving the oxidation ratio of vanadium falls and the rate of recovery, improve the half steel quality, solve the problems referred to above that exist in the background technology.
Technical scheme of the present invention is:
A kind of vanadium removal of realizing is protected the vanadium extraction by converter blowing control method of carbon, adopts the analysis of fumes method, and CO and O2 concentration curve signal are connected on the computer, forms the continuity curve; Determine adding opportunity of vanadium extraction converting process refrigerant according to the variation of CO content in the furnace gas, converting process prolongs the optimum temps interval of vanadium oxidation, combines with oxygen consumption in the vanadium extraction model to judge the vanadium extraction terminal point.
The present invention more specifically step is as follows:
(1) CO that combustion gas analyzer is collected and O2 concentration data are connected on the industrial computer, form the continuity concentration curve;
(2) oxygen-supplying amount vanadium extraction Model Calculation amount 90% in the time, the CO content is followed the tracks of in the utilization analysis of fumes, and CO content＞5% o'clock in furnace gas thinks that the oxidation priority of carbon and vanadium changes in the iron liquid, carbon begins preferential oxidation in the iron liquid, suppresses the further oxidation of vanadium; At this moment,, add refrigerant and adjust bath temperature, guarantee that the vanadium removal of vanadium extraction process is protected carbon for vanadium in the assurance iron liquid has precedence over the oxidation of carbon;
(3) oxygen supply reach vanadium extraction Model Calculation amount 90% after the time, when CO content in the furnace gas＞5%, no longer add the refrigerant temperature adjustment, guarantee that bath temperature is only low, reduce the metallic iron in the slag; Because it is violent that CO content reaches 10% back reaction between carbon and oxygen in the furnace gas, the barium oxide in the slag is entered in the half steel once more by carbon reduction, can reduce the rate of recovery of vanadium, therefore, for preventing to cause excessive carbon vigorous oxidation, when CO content reaches 10%, as the vanadium extraction terminal point, stop blowing.
Said refrigerant is the ferric oxide ball, adjusts bath temperature.
The principle of the invention: the rationale of " vanadium removal guarantor carbon ", from the thermodynamics angle, the oxidizing reaction of vanadium mainly is indirect reaction, that is:
2[V]+3FeO=（V2O3）+3[Fe]
But from the free energy change of various element oxidizing reactions, exist the problem of selective oxidation between vanadium and the carbon, i.e. the invert point of control " vanadium removal guarantor carbon ".
2/3[V]+COg=1/3(V2O3)+[C]-------△ Ge=-250170+153.09Te changes
△ G=△ Ge+RTlnK=△ Ge+RT changes ln[(aC*a1/3V2O3)/(a2/3V*Pco)]
When △ Ge=0, promptly-250170+153.09Te changeed=0 o'clock, and the oxidation of carbon and vanadium begins to change in proper order.Therefore Te commentaries on classics=250170/153.09=1634K=1361 ℃.It is a variable that influenced by vanadium concentration and oxygen partial pressure that actual invert point T changes, generally between 1340 ℃～1400 ℃.The vanadium oxidation is thermopositive reaction, and " low temperature " helps the oxidation of vanadium, and temperature control is the key link that realizes vanadium removal guarantor carbon.In the vanadium extraction by converter blowing process, when bath temperature was too high, carbon began preferential oxidation, and then reduced ferric oxide in the slag, suppressed the further oxidation of vanadium.In a word, vanadium extraction is a target with " vanadium removal guarantor carbon ", requires to suppress reaction between carbon and oxygen.
Vanadium extraction by converter blowing is that the key distinction with converter steelmaking process is that the main task of vanadium extraction by converter blowing is " a vanadium removal guarantor carbon ", in whole vanadium extraction process, temperature must be controlled at certain scope, by adding refrigerant control bath temperature, suppress reaction between carbon and oxygen, the oxidizing reaction that strengthens vanadium forms vanadium slag.
Beneficial effect of the present invention: according to the characteristics of vanadium extraction by converter blowing, the CO content is followed the tracks of in the utilization analysis of fumes, judges the molten bath reaction between carbon and oxygen severe degree and the bath temperature of in time taking measures to control, and guarantees fully to realize " vanadium removal guarantor carbon ".Compare with background technology, the present invention is under equal molten iron condition, half steel carbon can be stablized and is controlled at 3.70-3.90%, mean value is 3.86%, improve 0.14 percentage point,, effectively stop the terminal point after-blow phenomenon that causes because of the semi-steel making shortage of heat for following road steel making working procedure provides stable half steel condition, and a series of steel quality problem that causes because of serious after-blow, problem such as strong as molten steel oxidation, that inclusion content is high, yield of alloy is low.Surplus vanadium can be controlled between the 0.030-0.050%, average surplus vanadium reaches 0.039%, reduce by 0.004 percentage point than the surplus vanadium of background technology, the vanadium oxidation ratio reaches 81-92%, mean value is 85%, improve 2 percentage points than background technology, the also corresponding increase of the rate of recovery of vanadium further improves the key technical indexes of vanadium extraction.
Description of drawings
Fig. 1 is the embodiment of the invention one converting process furnace gas CO content figure;
Fig. 2 is the embodiment of the invention two converting process furnace gas CO content figure;
Fig. 3 is the embodiment of the invention three converting process furnace gas CO content figure;
Fig. 4 is the embodiment of the invention four converting process furnace gas CO content figure.
Embodiment
Below in conjunction with accompanying drawing, the invention will be further described by embodiment.
A kind of vanadium removal of realizing is protected the vanadium extraction by converter blowing control method of carbon, is applicable to vanadium extraction by converter blowing technology, selects that to return molten iron be main raw material to contain, and adopts the analysis of fumes method, and CO and O2 concentration curve signal are connected on the computer, forms the continuity curve; In converting process, determine the adding opportunity of vanadium extraction converting process refrigerant according to the variation of CO content in the furnace gas, converting process prolongs the optimum temps interval of vanadium oxidation, combines with oxygen consumption in the vanadium extraction model to judge the vanadium extraction terminal point, further improves the key technical indexes of vanadium extraction.
The present invention includes following steps:
1. in converting process, the CO content is followed the tracks of in the utilization analysis of fumes, make the continuous curve that the CO percentage composition changes, when CO content is higher in furnace gas, think that the iron liquid temp is higher, the temperature of transformation takes place in the oxidation priority that reaches carbon and vanadium, and carbon begins to have precedence over the vanadium oxidation in the iron liquid, suppresses the further oxidation of vanadium; At this moment,, add refrigerant ferric oxide ball and adjust bath temperature, prolong the temperature range that vanadium has precedence over oxidation of coal, guarantee converting process vanadium removal guarantor carbon for vanadium in the assurance iron liquid has precedence over the oxidation of carbon;
2. oxygen-supplying amount vanadium extraction Model Calculation amount 90% in the time, CO content＞5% o'clock in the furnace gas adds refrigerant ferric oxide ball 3-5kg/t half steel ([Si+Ti] content height is got the middle upper limit, otherwise gets lower limit) at every turn, realize vanadium removal guarantor carbon, guarantee CO content＜5% in the furnace gas;
3. when oxygen supply reach the vanadium extraction model the static calculation amount 90% after, only low for guaranteeing bath temperature, reduce the metallic iron in the slag, when CO content in the furnace gas＞5%; When reaching 10%, CO content, stops blowing as the vanadium extraction terminal point.
The vanadium extraction index of the present invention and background technology relatively sees the following form under the equal molten iron condition:
Specific embodiments of the invention are as follows:
Embodiment one:
This stove is non-deslagging heat, pack into 115 tons of molten iron of converter extracting vanadium, molten iron [C] 4.37%, [Si+Ti] 0.47% [V] 0.238%, temperature is 1268 ℃, adds 7 tons of iron blocks, goes out 116 tons of half steel amounts, target half steel [C] 3.85%, [V]≤0.04%, temperature 1380-1390 ℃.Open blow the beginning open after, bath temperature slowly rises, reaction between carbon and oxygen is fierce gradually.By 35% o'clock of the plan oxygen step (plan is the percentage ratio of oxygen-supplying amount), CO% was 5%, behind 3kg/t half steel adding ferric oxide ball, suppressed reaction between carbon and oxygen because bath temperature descends, and CO% descends.Along with progressively carrying out of converting process, temperature is progressively gone up.When blowing proceeds to plan oxygen step when being 67%, CO% is 5%, add the ferric oxide ball according to the 3kg/t half steel after, bath temperature descends and suppresses reaction between carbon and oxygen, CO% descends once more.When the plan oxygen step was 92%, at this moment CO content＞5% in the furnace gas no longer added the refrigerant temperature adjustment, as the vanadium extraction terminal point, stopped blowing when CO content reaches 10%.The oxidation ratio of this heat vanadium is 85.2%, and FeO content is 19% in the vanadium slag; Half steel [C] 3.89%, [V] 0.035%, temperature is 1387 ℃;
Converting process furnace gas CO content is with reference to accompanying drawing 1.
Embodiment two:
This stove is non-deslagging heat, pack into 114 tons of molten iron of converter extracting vanadium, molten iron [C] 4.41%, [Si+Ti] 0.65%, [V] 0.306%, temperature is 1301 ℃, adds 8 tons of iron blocks, goes out 116 tons of half steel amounts, target half steel [C] 3.80-3.90%, [V]≤0.04%, temperature 1380-1390 ℃.Open blow the beginning open after, bath temperature slowly rises, reaction between carbon and oxygen is fierce gradually.By 39% o'clock of the plan oxygen step (plan is the percentage ratio of oxygen-supplying amount), CO% was 5%, behind 5kg/t half steel adding ferric oxide ball, suppressed reaction between carbon and oxygen because bath temperature descends, and CO% descends.Along with progressively carrying out of converting process, temperature is progressively gone up.When blowing proceeds to plan oxygen step when being 75%, CO% is 5%, adds the ferric oxide ball according to the 5kg/t half steel, and CO% descends once more.When the plan oxygen step was 95%, at this moment CO content＞5% in the furnace gas no longer added the refrigerant temperature adjustment, as the vanadium extraction terminal point, stopped blowing when CO content reaches 10%.The oxidation ratio of this heat vanadium is 88.9%, and FeO content is 18% in the vanadium slag; Half steel [C] 3.85%, [V] 0.034%, 1388 ℃ of temperature
Converting process furnace gas CO content is with reference to accompanying drawing 2.
Embodiment three:
This stove is the deslagging heat, pack into 115 tons of molten iron of converter extracting vanadium, molten iron [C] 4.37%, [Si+Ti] 0.42%, [V] 0.296%, temperature is 1296 ℃, adds 5 tons of iron blocks, goes out 114 tons of half steel amounts, target half steel [C] 3.75-3.85%, [V]≤0.05%, temperature 1395-1405 ℃.Open blow the beginning open after, bath temperature slowly rises, reaction between carbon and oxygen is fierce gradually.By 24% o'clock of the plan oxygen step (plan is the percentage ratio of oxygen-supplying amount), CO% was 5%, behind 3.5kg/t half steel adding ferric oxide ball, suppressed reaction between carbon and oxygen because bath temperature descends, and CO% descends.Along with progressively carrying out of converting process, temperature is progressively gone up.When blowing proceeds to plan oxygen step when being 43%, CO% is 5%, adds the ferric oxide ball according to the 3kg/t half steel, and CO% descends once more.When the plan oxygen step was 65%, CO content was 5% in the furnace gas, added the ferric oxide ball according to the 3.5kg/t half steel, and CO% descends once more.When the plan oxygen step was 92%, CO content was 5% in the furnace gas, at this moment no longer adds the refrigerant temperature adjustment, as the vanadium extraction terminal point, stopped blowing when CO content reaches 10%.The oxidation ratio of this heat vanadium is 85.5%, and FeO content is 19% in the vanadium slag; Half steel [C] 3.77%, [V] 0.043%, 1401 ℃ of temperature;
Converting process furnace gas CO content is with reference to accompanying drawing 3.
Embodiment four:
This stove is the deslagging heat, pack into 116 tons of molten iron of converter extracting vanadium, molten iron [C] 4.33%, [Si+Ti] 0.66%, [V] 0.308%, temperature is 1310 ℃, adds 6 tons of iron blocks, goes out 115 tons of half steel amounts, target half steel [C] 3.75-3.85%, [V]≤0.05%, temperature 1395-1405 ℃.Open blow the beginning open after, bath temperature slowly rises, reaction between carbon and oxygen is fierce gradually.By 29% o'clock of the plan oxygen step (plan is the percentage ratio of oxygen-supplying amount), CO% was 5%, behind 4.5kg/t half steel adding ferric oxide ball, suppressed reaction between carbon and oxygen because bath temperature descends, and CO% descends.Along with progressively carrying out of converting process, temperature is progressively gone up.When blowing proceeds to plan oxygen step when being 54%, CO% is 5%, adds the ferric oxide ball according to the 5kg/t half steel, and CO% descends once more.When the plan oxygen step was 80%, CO content was 5% in the furnace gas, added the ferric oxide ball according to the 4.5kg/t half steel, and CO% descends once more.When the plan oxygen step was 98%, CO content was 5% in the furnace gas, at this moment no longer adds the refrigerant temperature adjustment, as the vanadium extraction terminal point, stopped blowing when CO content reaches 10%.The oxidation ratio of this heat vanadium is 84.7%, and FeO content is 20% in the vanadium slag; Half steel [C] 3.78%, [V] 0.047%, 1403 ℃ of temperature;
Converting process furnace gas CO content is with reference to accompanying drawing 4.
Claims (4)
1. a vanadium extraction by converter blowing control method that realizes vanadium removal guarantor carbon is characterized in that adopting the analysis of fumes method, and CO and O2 concentration curve signal is connected on the computer, forms the continuity curve; Determine adding opportunity of vanadium extraction converting process refrigerant according to the variation of CO content in the furnace gas, converting process prolongs the optimum temps interval of vanadium oxidation, combines with oxygen consumption in the vanadium extraction model to judge the vanadium extraction terminal point.
2. according to the vanadium extraction by converter blowing control method of the described realization vanadium removal guarantor carbon of claim 1, it is characterized in that more specifically step is as follows:
(1) CO that combustion gas analyzer is collected and O2 concentration data are connected on the industrial computer, form the continuity concentration curve;
(2) oxygen-supplying amount vanadium extraction Model Calculation amount 90% in the time, the CO content is followed the tracks of in the utilization analysis of fumes, and CO content＞5% o'clock in furnace gas thinks that the oxidation priority of carbon and vanadium changes in the iron liquid, carbon begins preferential oxidation in the iron liquid, suppresses the further oxidation of vanadium; At this moment,, add refrigerant and adjust bath temperature, guarantee that the vanadium removal of vanadium extraction process is protected carbon for vanadium in the assurance iron liquid has precedence over the oxidation of carbon;
(3) oxygen supply reach vanadium extraction Model Calculation amount 90% after the time, when CO content in the furnace gas＞5%, no longer add the refrigerant temperature adjustment, guarantee that bath temperature is only low, reduce the metallic iron in the slag; Because it is violent that CO content reaches 10% back reaction between carbon and oxygen in the furnace gas, the barium oxide in the slag is entered in the half steel once more by carbon reduction, can reduce the rate of recovery of vanadium, therefore, for preventing to cause excessive carbon vigorous oxidation, when CO content reaches 10%, as the vanadium extraction terminal point, stop blowing.
3. realize that according to claim 1 or 2 described profits vanadium removals protect the vanadium extraction by converter blowing control method of carbon, it is characterized in that said refrigerant is the ferric oxide ball, adjusts bath temperature.
4. realize the vanadium extraction by converter blowing control method of vanadium removal guarantor carbon according to the described profit of claim 3, it is characterized in that oxygen-supplying amount vanadium extraction Model Calculation amount 90% in the time, CO content＞5% o'clock in the furnace gas, each refrigerant ferric oxide ball 3-5kg/t half steel that adds, realize vanadium removal guarantor carbon, guarantee CO content＜5% in the furnace gas.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104060024A (en) * | 2013-12-02 | 2014-09-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Forecast method of real-time temperature of converter in the process of vanadium extraction by converter |
| CN104131131A (en) * | 2014-07-18 | 2014-11-05 | 重庆大学 | Method for adding coolant in vanadium extraction process by oxidizing vanadium-containing molten iron |
| CN109609718A (en) * | 2019-01-08 | 2019-04-12 | 山东钢铁股份有限公司 | A kind of steelmaking process distributing method based on gas parsing |
| CN111334639A (en) * | 2020-04-14 | 2020-06-26 | 西安建筑科技大学 | Method for promoting vanadium extraction and carbon conservation by using CO |
| CN111378854A (en) * | 2020-04-24 | 2020-07-07 | 四川省达州钢铁集团有限责任公司 | Duplex vanadium extraction method |
| CN111621613A (en) * | 2020-05-27 | 2020-09-04 | 河钢股份有限公司承德分公司 | Computer-assisted vanadium extraction method of converter |
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| CN101798618A (en) * | 2010-03-26 | 2010-08-11 | 河北钢铁股份有限公司承德分公司 | Method for performing vanadium increase and refining in vanadium alloying by utilizing vanadium slag |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104060024A (en) * | 2013-12-02 | 2014-09-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Forecast method of real-time temperature of converter in the process of vanadium extraction by converter |
| CN104060024B (en) * | 2013-12-02 | 2015-12-02 | 攀钢集团攀枝花钢铁研究院有限公司 | The forecasting procedure of converter real time temperature in a kind of vanadium extraction by converter blowing process |
| CN104131131A (en) * | 2014-07-18 | 2014-11-05 | 重庆大学 | Method for adding coolant in vanadium extraction process by oxidizing vanadium-containing molten iron |
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| CN111334639A (en) * | 2020-04-14 | 2020-06-26 | 西安建筑科技大学 | Method for promoting vanadium extraction and carbon conservation by using CO |
| CN111334639B (en) * | 2020-04-14 | 2021-11-23 | 西安建筑科技大学 | Method for promoting vanadium extraction and carbon conservation by using CO |
| CN111378854A (en) * | 2020-04-24 | 2020-07-07 | 四川省达州钢铁集团有限责任公司 | Duplex vanadium extraction method |
| CN111621613A (en) * | 2020-05-27 | 2020-09-04 | 河钢股份有限公司承德分公司 | Computer-assisted vanadium extraction method of converter |
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