CN102277595A - Deoxidation refining method for titanium and iron alloy - Google Patents
Deoxidation refining method for titanium and iron alloy Download PDFInfo
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- CN102277595A CN102277595A CN2011102629917A CN201110262991A CN102277595A CN 102277595 A CN102277595 A CN 102277595A CN 2011102629917 A CN2011102629917 A CN 2011102629917A CN 201110262991 A CN201110262991 A CN 201110262991A CN 102277595 A CN102277595 A CN 102277595A
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Abstract
The invention belongs to the field of iron alloy and relates to a deoxidation refining method for a titanium and iron alloy. In the invention, a self-made reactor and a fused salt electrolysis process are adopted, a coarse titanium and iron alloy is used as a soluble anode, an alkali metal chloride and a titanium-containing fluorine salt or chlorine salt are used to form an electrolyte, electrolysis is performed at 600 to 850 DEG C, titanium enters into the fused salt in form of low-valence titanium ions and precipitates from a cathode, and thus, oxygen in the coarse titanium and iron alloy is removed and a refining effect is achieved. After electrolysis is accomplished, the cathode product is collected at normal temperature and washed for several times with deionized water and diluted hydrochloric acid at a concentration of 1 percent to wash away electrolyte adhered on the product. The method has the advantages that: more than 5 percent of oxygen in the titanium and iron alloy is removed at a low temperature (600-850 DEG C); the oxygen content is reduced to less than 100 ppm by using the fused salt electrolysis process; and the process energy consumption is low.
Description
Technical field:
The invention belongs to the iron alloy field, relate to a kind of method of ferro-titanium deoxygenation refining, utilize homemade reactor, adopt the fused salt electrolysis technology, reach the purpose that removes residual oxygen in the ferro-titanium, improve the application of ferro-titanium in steelmaking process.
Background technology:
Ferro-titanium is widely used as reductor, air release agent and alloying element additive in Iron And Steel Industry.Titanium is called as " the 3rd metal ".Titanium can improve the weave construction of steel, improves the performance of steel, increases the wear resistance and the tensile strength of steel.Ferro-titanium is the important source material of producing circular chain steel, anchor chain guiding principle, making ship steel, stainless steel, welding electrode and electronics, war products etc.In producing stainless steel and high temperature steel process, the titanium carburet generates titanium carbide, thereby improves heat sealability and corrosion resistance nature.Up to now, generally adopt thermite process and remelting process to produce this kind iron alloy both at home and abroad.
The ferro-titanium quality that remelting process is produced is better, but too high production cost makes it fail to be widely used.The ferro-titanium of thermite process manufacturing is divided into 3 kinds of low titaniums, middle titanium, high titanium.Test analysis factually, titanium content is high more in the ferro-titanium that thermite process is produced, the recovery rate of titanium is low more, because have only by adding the content in ilmenite concentrate or the rutile increase ore, could increase the titaniferous amount in the ferrotianium, but keep under the constant situation of 6-7% at the ferrotianium aluminum content, the titaniferous amount rises, and the recovery rate of titanium then descends.Remaining titanium just is present in the ferro-titanium with the form of titanium oxide, has caused in the high ferrotitanium alloy that thermite process produces titanium content elevated oxygen level also high more quality problems more.Higher oxygen level not only makes the deoxidizing capacity of ferro-titanium in process for making descend in the high ferrotitanium alloy, and the affiliation that adds of oxide compound causes secondary pollution to molten steel in the ferro-titanium, influences steel quality.Therefore, to the high ferrotitanium alloy of thermite process production low oxygen content, The ferroalloy industry does not have specifically terms of settlement efficiently as yet at present.
In order to reduce the oxygen level in the ferro-titanium, the various countries worker seeks redress multi-faceted, mainly be by controlling at present in the ferro-titanium production process, thereby cause the product titanium grade lower (usually less than 40%) of producing, and high ferrotitanium alloy is not had effective method of controlling as yet.In this respect, at present part Study person adopt electrolysis process carried out certain research (Chu Shaojun, Tang Yuezhe, Wang Ti etc. the experimental study of high ferrotitanium alloy electrolytic reduction deoxidation. iron alloy, 2010(3): 14-18).The fundamental technology of research is to adopt the beginning of this century, the FFC technology that Cambridge University proposes, and this technology mainly is to be used for production electrolytic titanium and some high-melting-point high stability metal or alloy, it is used for the electrolysis deoxidation process and mainly has following problem:
(1) adopts the higher CaCl of oxygen dissolving power
2Melt salt system and make the ferro-titanium oxygen level that generates not reach the requirement of steel-making refining procedure, reduce oxygen level and must carry out excessive electrolysis, this has caused current efficiency extremely low again;
(2) the raw material negative electrode is prepared inconvenient, must have higher porosity, adopt solid titanium iron alloy deoxidation effect not obvious, so need be raw material with the ferro-titanium powder, and with its be pressed into have certain geometrical shape block as negative electrode, just can have deoxidation effect;
(3) oxonium ion solid phase diffusion speed causes polarization to make the current density of negative electrode very low too slowly, and along with the electrolytic electrode area that carries out gradually changes, be difficult to realize stable electrolysis on industrial production, and have serious short circuit problem in electrolytic process, current efficiency is low.
Therefore, obtain hypoxemia ferro-titanium employing FFC technology is to be difficult to realize.
Summary of the invention:
The present invention studies the deoxidation problem of production of high titanium iron by use of aluminothermy alloy product mainly according to the metallurgy principle of electrorefining.
A kind of method of ferro-titanium deoxygenation refining, promptly adopt the mode of fused salt electrolysis, with thick ferro-titanium is soluble anode, with alkali-metal muriate and titaniferous villiaumite or villaumite is ionogen, electrolysis under 600-850 ℃ of temperature, titanium are separated out at negative electrode after entering fused salt with the form of low price titanium ion, thereby remove the oxygen in the thick ferro-titanium, reach refining effect.After electrolysis was finished, cathode product normal temperature took out, and with deionized water and concentration 1% dilute hydrochloric acid washing several, fully cleaned the ionogen that clean product attaches.Specific embodiment is as follows:
1. selecting with alkali-metal muriate and titaniferous villiaumite or villaumite is ionogen, and alternative alkali metal chloride mainly contains NaCl, KCl etc., and titaniferous villiaumite or villaumite mainly contain TiF
4, K
2TiF
4, TiCl
2Deng;
2. be anode with thick ferro-titanium, select a kind of cathode material, preferential titanium, carbon steel, nickel are negative electrode;
3. the anode and cathode of selecting with the ionogen and the step 2 of step 1 selection is formed electrolysis system, electrolysis under 600-850 ℃ of temperature;
4. during electrolysis, cathode current density is controlled at 0.5-1.5A/cm
2
5. after electrolysis finished, cathode product normal temperature removed down, washed for several times with deionized water and concentration 1% dilute hydrochloric acid, fully cleaned the ionogen that clean product attaches.
Major advantage of the present invention is, under lower temperature (600-850 ℃), with the oxygen that surpasses 5% in the ferro-titanium, adopts fused salt electrolysis technology to reduce to below the 100ppm, and the process energy consumption is lower, has practical significance.
Description of drawings:
Fig. 1 is an electrolysis reactor of the present invention top sketch;
The 1-water-in; The 2-water outlet; 3-anode and cathode hole; The 4-air inlet port; The 5-production well; The 6-thermometer hole; The standby hole of 7-
Fig. 2 is an electrolysis reactor of the present invention bottom sketch.
The 8-sealing groove; The 9-bolt hole; The 10-reactor wall.
Embodiment
Embodiment 1: the high ferrotianium chemical ingredients of anode is as follows:
| Composition | Ti | Fe | Al | Si | O | S |
| Content/% | 75.08 | 5.54 | 3.51 | 2.16 | 12.20 | 1.51 |
Cathode material is a carbon-point, with NaCl+K
2TiF
4Be ionogen, the according to the form below condition is carried out electrolysis:
| Electrolysis temperature (℃) | The electrolytic solution type | Electrolysis time (h) | Cathode current density (A/cm 2） |
| 750 | NaCl+K 2TiF 4 | 4 | 0.5 |
Electrolytic process current efficiency is 88%, after the electrolysis in the ferro-titanium oxygen level reduce to 100ppm.
Embodiment 2: the high ferrotianium chemical ingredients of anode is as follows:
| Composition | Ti | Fe | Al | Si | O | S |
| Content/% | 75.08 | 5.54 | 3.51 | 2.16 | 12.20 | 1.51 |
Cathode material is a carbon-point, with NaCl+K
2TiF
4Be ionogen, the according to the form below condition is carried out electrolysis:
| Electrolysis temperature (℃) | The electrolytic solution type | Electrolysis time (h) | Cathode current density (A/cm 2） |
| 750 | NaCl+K 2TiF 4 | 8 | 1.0 |
Electrolytic process current efficiency is 92%, after the electrolysis in the ferro-titanium oxygen level reduce to 100ppm.
Embodiment 3: the high ferrotianium chemical ingredients of anode is as follows:
| Composition | Ti | Fe | Al | Si | O | S |
| Content/% | 75.08 | 5.54 | 3.51 | 2.16 | 12.20 | 1.51 |
Cathode material is a carbon-point, with NaCl+K
2TiF
4Be ionogen, the according to the form below condition is carried out electrolysis:
| Electrolysis temperature (℃) | The electrolytic solution type | Electrolysis time (h) | Cathode current density (A/cm 2） |
| 850 | NaCl+K 2TiF 4 | 4 | 1.5 |
Electrolytic process current efficiency is 93%, after the electrolysis in the ferro-titanium oxygen level reduce to 100ppm.
Claims (1)
1. the method for a ferro-titanium deoxygenation refining is characterized in that concrete processing step is as follows:
1). selecting with alkali-metal muriate and titaniferous villiaumite or villaumite is ionogen, and alternative alkali metal chloride mainly contains NaCl or KCl, and titaniferous villiaumite or villaumite mainly contain TiF
4, K
2TiF
4, TiCl
2
2). with thick ferro-titanium is anode, and selecting titanium, carbon steel or nickel is negative electrode;
3). ionogen and the step 2 selected with step 1)) anode and cathode selected forms electrolysis system, electrolysis under 600-850 ℃ of temperature;
4). during electrolysis, cathode current density is controlled at 0.5-1.5A/cm
2
5). after electrolysis finished, cathode product normal temperature took out, and with deionized water and concentration 1% dilute hydrochloric acid washing several, fully cleaned the ionogen that clean product attaches.
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|---|---|---|---|
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|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103111354A (en) * | 2013-01-31 | 2013-05-22 | 攀钢集团攀枝花钢铁研究院有限公司 | Pretreatment method for cathode deposition of molten salt electrorefining |
| CN104694973A (en) * | 2015-02-06 | 2015-06-10 | 铜陵百荣新型材料铸件有限公司 | Process for preparing ferrotitanium alloy |
| CN106011943A (en) * | 2016-05-30 | 2016-10-12 | 安徽工业大学 | Method for simultaneously preparing pure iron alloy and carbide derived carbon by using carbon iron alloy as raw material |
| CN107206501A (en) * | 2014-12-02 | 2017-09-26 | 犹他大学研究基金会 | The fuse salt deoxidation of metal dust |
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| US2920020A (en) * | 1956-04-10 | 1960-01-05 | Chicago Dev Corp | Producing compositions of molten salts composed essentially of alkalinous metal chlorides and soluble titanium chlorides |
| WO2005103338A1 (en) * | 2004-04-27 | 2005-11-03 | Technological Resources Pty. Limited | Production of iron/titanium alloys |
| CN101914788A (en) * | 2010-07-26 | 2010-12-15 | 攀钢集团有限公司 | Method for preparing metallic titanium |
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2011
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Patent Citations (3)
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|---|---|---|---|---|
| US2920020A (en) * | 1956-04-10 | 1960-01-05 | Chicago Dev Corp | Producing compositions of molten salts composed essentially of alkalinous metal chlorides and soluble titanium chlorides |
| WO2005103338A1 (en) * | 2004-04-27 | 2005-11-03 | Technological Resources Pty. Limited | Production of iron/titanium alloys |
| CN101914788A (en) * | 2010-07-26 | 2010-12-15 | 攀钢集团有限公司 | Method for preparing metallic titanium |
Non-Patent Citations (6)
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|---|
| 卢维昌等: "电解精炼回收废海绵钛及对电极过程机理的初步分析", 《稀有金属》 * |
| 卢维昌等: "钛合金阳极溶解过程的研究", 《稀有金属》 * |
| 杜继红等: "熔盐电解还原制备TiFe 合金", 《稀有金属材料与工程》 * |
| 翁启钢等: "熔盐电解法制备高纯钛粉", 《粉末冶金材料科学与工程》 * |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103111354A (en) * | 2013-01-31 | 2013-05-22 | 攀钢集团攀枝花钢铁研究院有限公司 | Pretreatment method for cathode deposition of molten salt electrorefining |
| CN103111354B (en) * | 2013-01-31 | 2014-12-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Pretreatment method for cathode deposition of molten salt electrorefining |
| CN107206501A (en) * | 2014-12-02 | 2017-09-26 | 犹他大学研究基金会 | The fuse salt deoxidation of metal dust |
| US10610929B2 (en) | 2014-12-02 | 2020-04-07 | University Of Utah Research Foundation | Molten salt de-oxygenation of metal powders |
| CN104694973A (en) * | 2015-02-06 | 2015-06-10 | 铜陵百荣新型材料铸件有限公司 | Process for preparing ferrotitanium alloy |
| CN106011943A (en) * | 2016-05-30 | 2016-10-12 | 安徽工业大学 | Method for simultaneously preparing pure iron alloy and carbide derived carbon by using carbon iron alloy as raw material |
| CN106011943B (en) * | 2016-05-30 | 2017-12-15 | 安徽工业大学 | A kind of method that pure ferroalloy and carbide-derived carbon are prepared using carbon ferroalloy simultaneously as raw material |
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Application publication date: 20111214 |